RESEARCH AND DEVELOPMENT OF ABRASION WEAR RESISTANT CAST ALLOYS FOR

ROLLS OF ROLLING AND PULVERIZING MILLS

YASUHIRO MATSUBARA Dr. Eng.

Professor Emeritus
Kurume National College of Technology

INTRODUCTION
For last half a century past, materials of hot work rolls in the steel industry, which are shown as an example in
Fig.1, changed from low -alloyed white iron through adamite or hyper-eutectoid Ni-Cr steel and Ni-hard cast iron
to high chromium cast iron. [1] On the other side, the abrasion wear resistant cast alloys for the components of
cement and mineral pulverizing mills have been changed by following the transition of the roll materials. The
high chromium cast iron, which was developed in the nineteen-seventies, is even now used not only for hot
working mill rolls but also for pulverizing mill rolls because of its high wear resistance. A typical example of the
pulverizing mill roll is shown in Fig.2. According to the demands in upgrading the productivity and the quality of
products, the roll materials are being compelled to shift to a new type of material with much higher performance.
The multi-alloyed white cast iron or multi-component white cast iron is a new type of alloy which contains plural
kinds of strong carbide forming elements such as Cr, V, Mo, W, and resultantly, plural kind of their special
carbides with high hardness and strong matrix with secondarily precipitated carbides. This iron was developed
around 15 years ago in Japan and has been tried to apply to the work roll of hot finishing stands for the past 10
years.[2] Nowadays, a large portion of work rolls in hot rolling mills is replaced from high chromium and Ni-hard
white cast iron rolls, and such types of rolls are now pleading over the world. It is worthy of note that this kind of
trial roll was served recently to the pulverizing mills.

Fig.1 Rolling mill rolls made of multi-component

white cast iron.

Fig.2 Pulverizing mill Roll made of high chromium

white cast iron.

This paper describes the basic researches for developing the multi-component white cast irons for the hot
work rolls of rolling mill roll and the abrasion wear resistant materials of pulverizing mill by taking following
approach:
1) Alloy designing
2) Solidification structure
3) Solidification sequence and phase diagram
4) Phase transformation behavior
5) Heat treatment characteristics
The field test results for wear resistance of this type of cast iron are also introduced in comparison with
conventional roll materials.
1

ALLOY DESIGNING
The designing of chemical compositions of the multi-component white cast iron was carried out on
consideration of not only the solidification structure, i.e. the type and morphology of carbide precipitating during
solidification, but also the transformation behavior of the matrix by heat treatment. The main purpose was focused
on improving the abrasion wear resistance from room to elevated temperatures by availing hard eutectic carbides
and matrix hardened by secondary precipitation of carbides due to heat treatment.
Chromium: Cr distributed into matrix improves the hardenability of the cast iron by postponing the pearlite
and bainite transformations. At the same time, eutectic carbide as M7 C3 contributes to good abrasive wear
resistance. Therefore, Cr was selected as one of the basic alloying elements of multi-component white cast iron.
However, Cr content has to be limited in order to give priority to the precipitation of other types of carbides with
much higher hardness.
Molybdenum and Tungsten: Mo and W are strong carbide-forming elements and they act similarly. In case
that both of Mo and W are added to ferro-alloy containing carbon, complex carbides of (Mo,W,Fe)2C or M2 C,
(Mo,W,Fe)6C or M6 C are able to form. [3] These carbides have higher hardness than chromium carbide of M7 C3 .
Even in a small amount, on the other hand, Mo and W dissolve into matrix and improve the hardenability of the
iron. W and Mo also promote the secondary precipitation hardening of matrix by tempering, and they should be
adopted in the multi-component white cast iron. Then, a value of tungsten equivalent (Weq ) is introduced to set up
the total content of these two elements, and it is expressed by the following equation,
Weq = %W + 2%Mo
(1)
Vanadium: V forms (V,Fe)C (simplified as MC) or (V,Fe)4 C3 carbide in ferro-alloy with C [4] and it greatly
works upon the secondary precipitation hardening by the carbide reaction in the later stage of tempering. V
carbide, VC or V4C3 , has higher hardness than M2C and M6C. From the viewpoints of hardness and morphology,
V is expected to be the most beneficial alloying element in the multi-component white cast iron.
Cobalt: It is well known that Co has not been widely used in steels because of decreasing the hardenability.
However, Co improves high temperature strength due to an increase in the eutectic temperature and the
suppression of grain coarsening due to the rising of temperature. An available result is expected by adopting Co to
the multi-component white cast iron.
Carbon: C contained in cast iron is spent at first by combining with strong carbide formers during
solidification, and the remaining C dissolves into the iron matrix. In the multi-component white cast iron that
contains plural carbide formers, several types of carbide s are expected to precipitate. A term called carbon balance
(Cbal ), which is defined by the next equation, is employed as a parameter to express the behavior of C dissolved in
iron matrix,[5]
Cbal = % C Cstoich
(2)
where, % C is the C content of the cast iron and Cstoich means the stoichiometric amount of carbon, i.e., carbon
content that combines equally with all the carbide -forming elements in the cast iron. In multi-component white
cast iron, Cstoich can be expressed by the following equation,
Cstoich = 0.060 % Cr + 0.063 % Mo + 0.033 % W + 0.235 % V
(3)
here, carbon is supposed to exist in the forms of Cr23C6 , Fe 4 W2 C (W2 C) or Fe 4 Mo2 C (Mo2 C), and VC,
respectively. However, if sufficient amount of Cr7 C3 carbide forms in eutectics, the equation should be modified
as,
Cstoich = 0.099 % Cr + 0.063 % Mo + 0.033 % W + 0.235 % V
(4)
In the last stage of heat treatment, Cbal is a very important factor for the transformation of matrix in the cast
iron. It determines whether more or less carbon than the equilibrium state will dissolve to matrix, and therefore
predominantly affects the property of the matrix. A positive Cbal value means extra carbon remains in the iron
matrix in an equilibrium condition, and a negative value means that carbon lacks in the matrix. As a basic alloy
composition, approximately 5 % for each element of Cr, Mo, W and V, and 2 % C is settled in this study so that
the Cbal value can be around 0 %.
SOLIDIFICATION STRUCTURE
As-cast microstructure of multi-component white cast iron consists of carbides crystallized from liquid and
2

matrix. [6]
Carbide
Several types of eutectic carbides precipitate in the solidification structure of the cast iron and they show
diversities of morphology according to the chemical composition.
MC carbide: The MC carbide contains more than 50% V and it precipitates as a eutectic during solidification.
This carbide can be classified into petal-like, nodular and coral-like morphologies as shown in Fig.3 to 5,
respectively. Petal-like MC in Fig.3 precipitates in a low carbon cast iron where the crystallization of austenite
dendrite proceeds before eutectic of ( + MC) forms. Nodular MC carbide shown in Fig.4 precipitates in the cast
iron with high carbon content. Coral-like MC carbide in Fig. 5 consists of primary MC crystals in the center and
eutectic MC carbides growing in radial directions from the primary MC. The coral-like MC carbides precipitate in
the iron containing high vanadium content, and can co-exist with M7 C3 carbide or small amount of M2 C carbide
depending on the carbon content of the iron. Hardness of MC carbide is about 2800HV and MC carbide may be
very effective to the wear resistance of the cast iron, and the nodular morphology of MC carbide may also
improve the toughness of the cast iron because of less notch effect. When chemical composition of the iron
changes, however, nodularity of MC carbide may deteriorate to chunky or flaky morphology.
M2 C carbide: Molybdenum- and tungsten-rich carbide precipitates as M2 C type in as cast state and takes fine
lamellar and/or coarse plate-like morphology as shown in Fig.6 and 7, depending on the chemical composition of
the iron. However, it is reported that the M2 C carbide transforms into M6 C carbide by heating. [7] Lamellar eutectic
M2 C carbide exists in isolation and this indicates that the M2C carbide precipitates in last stage of solidification.
The plate-like M2 C carbide consists of large and thick plates. This type of carbide can be usually seen in the cast
iron with high Weq value. In the iron with higher carbon content, the plate-like M2 C carbide exists together with
M7 C3 carbide as shown in Fig.8.
M7 C3 carbide: Chromium carbide M7 C3 similar to that in high chromium white cast iron shown rod-like or
ledeburitic morphology in the iron with higher Weq value and higher carbon content, and it sometimes co-exists
with MC and M2C carbides (Fig.4 and 8).

Fig.3 Petal-like MC carbide.

Fig.4 Nodular MC carbide.

Fig.5 Coral-like MC carbide.

Fig.6 Fine lamellar M 2C carbide.

Fig.7 Coarse plate-like M 2C carbide.

Fig.8 M 7C3 and M 2C carbides.

Matrix
Matrix in as-cast state consists of bainite, martinsite and some retained austenite (R). The volume fraction of
retained austenite (V) ranges widely from 5 to 50 % depending on the carbon content of the iron. However, the R
is supposed to transform into the useful phases after heat treatment.
SOLIDIFICATION SEQUENCE AND PHASE DIAGRAM
Solidification Sequence
The content of carbon and alloying elements were varied so that several combinations of eutectic carbides
could be obtained in multi-component white cast iron and the solidification sequences were investigated by means
of quenching test during thermal analysis.[8]
As an example, the solidification sequence of the cast iron with basic chemical composition
(Fe-5%Cr-5%Mo-5%W-5%V-5%Co-2.0%C alloy), in which the petal-like MC and plate -like M2 C carbides
co-exist, is shown in Fig.9 a, b: a thermal analysis curve in a and the quenched microstructures in b. First of all,
the primary austenite dendrite forms at 1590K, and follows by precipitation of (+MC) eutectic at 1558K, and
finally (+M2 C) eutectic solidifies at 1422K.

Fig.9 Solidification sequence of multi-component white cast iron with basic chemical composition
(Fe-5%Cr-5%Mo-5%W-5%V-5%Co-2%C). a: Thermal analysis curve, b: quenched microstructures

In the case of cast iron increasing carbon content to 3%, the solidification sequence is expressed as follows,
L0 ( + MC)E +L 1

at 1523 K

L1 ( + M7 C3 )E + L2

at 1441 K

L2 ( + M2 C)E

at 1365 K

The solidification sequences of the other kinds of multi-component white cast irons with more variation of
chemical composition than the basic alloy composition are summarized in Table 1.
Table 1 Solidification sequences of multi -component white cast iron varying chemical composition
from the basic alloy

No.

Chemical composition
2%C
5%Cr
2%Mo
2%W
9%V
5%Co
3%C
5%Cr
2%Mo
2%W
5%V
5%Co
3%C
5%Cr
2%Mo
2%W
9%V
5%Co

Combination of carbide

Coral-like MC
+
lamellarM 2 C

Nodular MC
+
rod-like M 7 C3

Chunky and coral-like MC

+
rod-like M 7 C3

Solidification Sequence
L0? P + L1

at 1651 K

L1? ( + MC)E + L2

at 1631 K

L2? ( + M2 C)E

at 1498 K

L0? P + L1

at 1556 K

L1? ( + MC)E + L2

at 1515 K

L2? ( + M7 C3 )E

at 1452 K

L0? (MC)p + L1

at 1732 K

L1? ( + MC)E + L2

at 1550 K

L2? ( + M7 C3 )E

at 1453 K

Practical Phase Diagram

Since it was found that the solidification processes of multi-component white cast iron with plural eutectic
carbides were accurately revealed using the techniques of thermal analysis and quenching experiment, the
practical phase diagram of the iron was considered to be possibly made by using the same method. [9] The phase
diagram of quasi-binary M(Fe-Cr-Mo-W-V)-C alloy system and the liquidus surface diagrams of quasi-ternary
M(Fe-Cr-Mo-W)-V-C alloy system were constructed. The quasi-binary phase diagram of the basic iron
(M(Fe-5%Cr-5%Mo-5%W-5%V-5%Co)-C alloy) and the liquidus surface diagram of the iron
(M(Fe-5%Cr-5%Mo-5%W-5%Co)-V-C alloy) are shown in Fig.10 a, b respectively.
It is obvious that the high temperature part of the quasi-binary phase diagram (Fig.10 a) exhibits a simple
eutectic system between austenite and MC carbide. As the eutectic point lies near a carbon content about 2.8%,
the cast iron with the basic alloy content bears hypo-eutectic microstructure. However, this phase diagram also
tells that after the eutectic reaction of ( + MC), the melt may thereafter undergo two other eutectic reactions
including M7 C3 and M2C carbides, corresponding to the carbon content. On the other side, quasi-ternary liquidus
surface diagram (Fig.10 b) shows a liquidus surface construction when the vanadium content varies with
accompanying carbon content. Reactions among delta-ferrite, austenite, MC carbide as well as M7C3 and M3 C
carbide are displayed, while the reaction including M2 C carbide cannot be expressed on this liquidus surface
diagram. The re are two peritecto-eutectic points, U1 and U2, and the temperature of U1 located at high vanadium
and low carbon is around 200K higher than that of U2 at low vanadium and high carbon. Therefore, the ( + MC)
eutectic reaction progresses down to the U2 followed by ( + M7C3 ) or ( + M3 C) eutectic. Anyway, these phase
diagrams have been giving useful instructions to the alloy designing for practical applications.

Fig.10 Quasi-binary phase diagram of base alloy M(Fe-5% Cr-5% Mo-5%W-5% V-5%Co)-C alloy (a) and
quasi-ternary liquidus phase diagram of M(Fe-5% Cr-5% Mo-5%W-5%Co)-V-C alloy (b).

PHASE TRANSFORMATION BEHAVIOR

The carbide forming elements are also distributed into matrix and so they have effects on transformation. The
wear resistance and the mechanical properties of multi-component white cast iron are affected by not only the
type and morphology of eutectic carbide but also the matrix structure varied depending on heat treatment. In order
to get instructions of heat treatment endowing the cast iron with desired properties, it is necessary to clarify the
transformation behavior of matrix. Here, the continuous cooling transformation behavior of the cast irons
containing 5% of each element, Cr, Mo, W, 2% of Co, and 2.0 and 2.8% C were investigated.[10]
The continuous cooling transformation (CCT) curves of low and high carbon cast irons obtained by cooling
from austenitizing temperatures (T ) of 1273K and 1373K after annealing (1223K-18ks-FC) are shown in Fig. 11
a, b. In spite of the difference in carbon content and T, pearlite and bainite transformation separate to the top and
the bottom individually. The nose temperatures of both the pearlite and bainite transformations range in 920K to
980K and 570K to 610K for low carbon iron, and 900K to 950K and 590K to 640K for high carbon iron,
respectively. With respect to transformation time or nose time, the low carbon iron shows great difference in nose
time of pearlite and bainite transformations at 1273K austenitization and the pearlite transformation is located at
the long time side more than 3 times as much as the bainite transformation. When the T increases 100K more to
1373K, both transformations are delayed approximately twice. In the case of high carbon iron, on the other hand,
the nose time of pearlite and bainite transformations are almost the same at 1273K austenitization and both are
shifted to the long time side at 1373K austenitization. The critical cooling rate of the pearlite transformation (V C-P )
in 1273K austenitization is 0.12K/s in the low carbon iron and this is remarkably small in comparison with that in
the high carbon iron (0.39K/s). In 1373K austenitization, VC-P of the low carbon iron decreases greatly to 0.08K/s
but that of the high carbon iron is similar (0.38K/s) regardless of an increase in the T. This result tells that the
pearlite transformation is difficult to occur in the low carbon iron and the tendency increases as the T rises.
The critical cooling rate of the bainite transformation (V C-B) is nearly the same in the low and high carbon
irons, i.e., 0.84 and 0.77K/s at 1273K austenitization, and 0.50 and 0.48K/s at 1373 austenitization. It is
understood that the direct transformation from austenite to bainite takes place in the small range of the cooling
rate and usually the both of pearlite and bainite transformations occur. Therefore, the matrix structure in which
pearlite and bainite co-exist will be obtained. This will give an important instruction to the practical heat treatment
of multi-component white cast iron with high carbon content which will be applied to a mineral pulverizing mill
roll.
Next, the effect of T on pearlite and bainite transformations is described. Because the carbon and the other
alloying elements dissolve more into matrix due to an increase of solubility at higher T, both the pearlite and
bainite transformation can be delayed. In SEM observation of the matrix, quench from each T, it was confirmed
that the amount of indissolved carbide is less in the matrix quenched from 1373K than that quenched from 1273K.
From the fact that these dissolved carbides are considered to act possibly as nucleation sites of their
transformations, it can be inferred that the matrix austenitized at high temperature oppositely lies in the situation
that is difficult to transform.
6

a
b
Fig.11 Continuous cooling curves of multi-component white cast irons with basic alloy composition.
a: 2.0%C iron , b: 2.8%C iron

It is clear from Fig.11 that the temperature for the martinsite transformation to start (Ms) appears but that to
finish (Mf) does not in this kind of cast iron. The Ms temperature increases as the cooling rate decreases down to
the VC-B and then lowers gradually as the bainite transformation increases. In 1273K austenitization, the Ms
temperature is 475K to 495K in the low carbon iron and 375K to 380K in the high carbon iron. The reason for Ms
temperature to rise may be explained by that the alloy concentration in matrix decreases because of an increase in
the precipitation of carbides, as the cooling rate reduces. The reason for Ms temperature to lower may be
explained by that the enrichment of carbon in austenite and resultant stabilization of austenite take place due to
the discharge of carbon with the proceeding of the bainite transformation. In the recent investigation, it is proved
that the Ms temperature of the multi-component white cast iron is uniformly reduced with an increase in carbon
content of the iron.

HEAT TREATMENT CHARACTERISTIC

Multi-component white cast irons with alloy concentration (Fe -5%Cr-5%Mo-5%W-5%V-2%Co-1.4~2.4%C)
were annealed under the condition of 1123K-18ks-FC, and hardened by forced air from 1272, 1323 and 1373K
austenitization. Then they were tempered in the temperature range from 623K to 873K for a constant holding time
of 12ks.[11]
The relationships between macro-hardness, volume fraction of retained austenite (V) and tempering
temperatures of the irons with different carbon content are shown in Fig. 12 a, b, c,. In each iron, the tempered
hardness curve with remarkable secondary hardening is obtained and the V begins to reduce rapidly when the
tempering temperature rises over a certain temperature.
In the cast iron with 1.8%C, the hardness in as-hardened state is almost the same in the irons hardened from
1323K and 1373K but the tempered hardness curve shifted to the high hardness side as the T increases.
Maximum tempered hardness (HTmax) is obtained near 773K regardless of T and it increases as the T rises. The
higher is the T, the more is the degree of secondary hardening. The V in as-hardened state is less than 10% and it
becomes 0% when the tempering temperature exceeds 800K.
In the case of cast iron with 2.0%C, the hardness of the irons hardened from 1273K and 1323K are similar but
that of the iron hardened from 1373K is lower. The tempered hardness curves show the marked secondary
hardening in the irons hardened from 1323K and 1373K, and the H Tmax are over 900HV. The tempering
7

temperature corresponding to H Tmax is a little higher when the T is high. The hardness in as-hardened state differs
depending on the T, and it increases in the order of 8%, 15% and 23% as the T rises from 1273K to 1373K. In
each iron, the V starts to reduce over the tempering temperature of 723K and gets down to 0% over 823K. When
the hardness is corresponded to the V, it is found that the HTmax is obtained near a tempering temperature when
the V approaches 0%.
The hardness of as-hardened iron with higher carbon content of 2.4% greatly decreases as the T increases. In
the following tempering, however, each iron shows an evident secondary hardening. The HTmax of the irons
hardened from 1273K and 1323K are 960HV at the tempering temperatures, 773K and 823K, respectively. In the
iron hardened from 1373K, the HTmax is 915HV at 823K tempering and this value is lower in spite of higher
austenitization. This is because around 20% V is still left after tempering, and also it tells that this tempering
condition is not enough to decompose completely such a large amount of R (65% in as hardened state).

a
b
c
Fig.12 The relationship between hardness, volume fraction of retained austenite (V ) and tempering temperatures.
a: 1.79%C iron , b: 2.05%C iron , c: 2.36%C iron

In the case that this type of cast iron is practically applied to a rolling mill roll, the R is undesirable because it
may decompose and/or transform into martinsite and consequent cracks may be produced. Therefore, it will be
useful if the optimum tempering condition to reduce the R effectively is shown for the cast iron with each
chemical composition. Then the tempering temperatures for the V to be less than 2% (T2%) are obtained and they
are related to carbon content and hardening condition. At every T, T2% is proportional to the carbon content of
the iron and it is expressed respectively by the following equations,
For T = 1273K, T2% = 588 + 79%C
(5)
For T = 1323K, T2% = 555 + 117%C
(6)
For T = 1373K, T2% = 564 + 126%C
(7)
The more is the carbon content in the iron, the higher is its tempering temperature, and the higher is the T, the
higher should the T2% be chosen in all the irons with different carbon content. In order to express the T2% as a
function of T and carbon content, the multiple regression analysis is carried out and the relation is given by the
next equation,
T2%(K) = -355.7 + 0.7 T +144.4%C
(8)
Fig.13 shows the comparison of T2% calculated from equation (8) with the experimental values. A close
agreement between them was obtained and the tempering temperature to make the R mostly free can be
calculated from the carbon content of cast iron and the austenitinzing temperature.

Fig.13 Corresponding between experimental and calculated values for T2% .

WEAR RESISTANCE
Rolls for the later finishing stands of steel hot rolling mill and a Loesche type slag pulverizing mill were made
of multi-component white cast iron with basic chemical composition and they were supplied to the field test.
Fig.14 shows the roll wear in finishing mills relative to a parameter of rolling load in which the rolling force in
unit width in the direction of roll axis and the number of rolling cycles. The wear of multi-component white cast
iron roll is very small compared with conventional rolls, that is, it is less than 1/5 of indefinite chilled cast iron
roll and less than 1/3 of high chromium cast iron roll. Therefore, the shape of rolled products is improved and it is
possible with multi-component white cast iron roll to display their shape controllabilit y in high function rolling
mill. The test results in the pulverizing mill are shown in Fig.15 compared with that of conventional high
chromium cast iron roll. It is evident that the wear resistance of multi-component white cast iron roll with 2.0%C
(Multi-a lloy (1)) is much better than that of the high chromium cast iron roll with 27%Cr and eutectic carbon
content, and that the wear of multi-alloy roll (2) containing high carbon content of 2.3% decreases more and it is
two-thirds to that of high chromium cast iron roll.
As to the wear performance for hot working roll made of the basic multi-component white cast iron, the test
result is shown in another paper [12] that is presented later. The wear resistance is much higher than those of
conventional Ni-hard and high chromium cast iron rolls, and it showed roughly one fifth and one fourth to those
of rolls made of Ni-hard and high chromium cast irons, respectively.

Fig.14 Comparison of wear resistance among different roll

materials for hot rolling mill .

Fig.15 Comparison of wear resistance among different roll

materials for pulverizing mill.

CONCLUSIONS AND PROSPECTS

The development processes of a new material, multi-component white cast iron, which contains several strong
carbide forming elements and their special carbides with very high hardness, for roll in hot finishing stands, by
researching it totally from the view points of alloy designing, solidification structure and solidification sequence
and phase diagram, and phase transformation behavior and heat treatment characteristics are shown in this paper.
As the results, the solidification structure, particularly type and morphology of eutectic carbides, could be
controlled in a wide range by combination of alloying elements. Phase transformation behavior, obtained from the
continuous cooling curves gave useful instructions to the heat treatment process. The hardness and retained
austenite in matrix could be widely controlled and the remarkable secondary hardening due to precipitation of
special carbides was found to make the matrix hard and strong enough for practical use.
The excellent performance of hot work roll made of the multi-component white cast iron was proved by the
field test and it is very popular in Japan and the good reputation has been spreading over the world. It is also noted
that this type of cast iron is gradually being applied to the pulverizing mill rolls and that a good performance has
been reported in the cement industry.
Finally, it is convinced that the multi-component white cast iron will also find wider applications as the wear
resistant materials, especially cold working mill rolls.
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1
2
3

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Raynor, G.V. , and Rivlin, V.G.: Phase equilibria in iron ternary alloys, The Institute of Metals, pp 177-191 and 201-212(1988)

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10