Metal Science and Heat Treatment Vol. 48, Nos.

3 4, 2006

STRUCTURE FORMATION IN FERROUS ALLOYS.

NONEQUILIBRIUM STRUCTURES
We present the fifth (last) paper1 of a series devoted to processes of structure formation in ferrous alloys. The results
of the analysis of the Fe C Mn phase diagram performed in the first four papers and of a eutectic polyhedration
of this diagram are used to consider the process of formation of nonequilibrium structure in high-manganese white
iron. The effect of silicon on the formation of structure and on the properties of alloys of the Fe C Mn system is
considered. Mechanical properties of the irons are described.

UDC 669.15784.74

ALLOYS OF THE Fe C Mn SYSTEM.

PART 5. SPECIAL FEATURES OF STRUCTURE FORMATION
IN WHITE HIGH-MANGANESE IRONS

G. I. Silman2

Translated from Metallovedenie i Termicheskaya Obrabotka Metallov, No. 3, pp. 3 8, March, 2006.

Eutectic polyhedration of the diagram is presented and special features of structure formation in high-manga-
nese irons are analyzed. It is shown that eutectics of two kinds (alloyed ledeburite and a eutectic based on
M7C3 carbides), which are in peritectic equilibrium with the melt, can be formed and be accompanied by a
special austenite-carbide component having a pearlite-like structure. The quasi-eutectic and the M7C3-bearing
eutectic in heat-treated high-manganese irons have a special morphology with composite arrangement of car-
bides in austenite. It is shown that additional alloying of manganese irons with silicon might be a promising
direction. Silicon stabilizes the M7C3 carbide in its competition with cementite and ensures the possibility of
fabricating austenitic mottles with such carbide. Mottles alloyed with manganese and silicon and having glo-
bular graphite, M7C3 carbides and metastable austenitic matrix are characterized by high wear resistance,
good antifriction properties, and a combination of high mechanical properties.

EFFECT OF MANGANESE ON STRUCTURE
FORMATION IN WHITE IRONS
We considered structure formation in alloys of the
Fe C Mn system on the basis of sections and projections
of the phase diagram plotted in [1 3].
1 crease the degree of transformation-induced austenite due to
The first paper was published in Metalloved. Term. Obrab. Met.,
No. 2, pp. 11 15 (2005).
The second paper was published in Metalloved. Term. Obrab.
Met., No. 4, pp. 3 9 (2005).
The third paper was published in Metalloved. Term. Obrab. Met.,
No. 9(603), pp. 3 7 (2005).
The fourth paper was published in Metalloved. Term. Obrab.
Met., No. 1(607) (2006).
2
Bryansk State Engineering-Technological Academy, Bryansk,
Russia.
In white irons manganese austenizes the matrix (metallic
base) less intensely than in steels, which is explainable by its
prevailing segregation into carbide phases. The austenitic
structure of manganese irons bearing less than 25% Mn is
unstable thermodynamically and can undergo phase transfor-
mations under the conditions of deformation. In order to in-
its straining the manganese content in the iron should be re-
duced to 5 8%. If it is required that the matrix be very hard,
the manganese content should be lowered to 2 5% (de-
pending on the conditions of cooling of the articles, their ge-
ometry, and the content of other elements in the chemical
composition). In this case the degree of the transformation of
austenite is considerable, and it yields martensite-bainite
structures.

95
0026-0673/06/0304-0095 2006 Springer Science + Business Media, Inc.
96 G. I. Silman

Dl
are inconsiderable and cannot affect the morphology of the
eutectic. Kinetic factors have a more considerable influence.
It has been shown experimentally that a high content of man-
ganese in the composition of iron increases supercooling of
the melt during crystallization and promotes formation of a
b quasi-eutectic with a reduced content of carbides and strong
supersaturation of austenite with carbon and manganese.
These factors affect the morphology of the quasi-eutectic,
which becomes looser as compared to the ledeburite eutectic
c
and bears outlines of breaks in the carbide chains. The
amount of cementite in such a eutectic is insufficient for the
formation of a continuous matrix, and the eutectic can grow
in the form of a conglomerate of phases with prevalence of
tough and ductile austenite. Such changes are typical already
100 300 500 700 900
t, C for irons with a g + Cem eutectic (which will be designated
E1 below). Still more considerable morphological changes
Fig. 1. Dilatograms of manganese irons: a) 4.8% Mn; b ) 12% Mn; occur upon the transition to the g + e eutectic (E2 ). We will
c) 21.5% Mn.
illustrate this below by photographs of microstructures of
high-manganese white irons.
t, C The competition of the eutectics and the transition from
one eutectic to another are illustrated well by the eutectic
1168 polyhedration of the Fe C Mn diagram presented in
L Fig. 2. It can be seen that both eutectics are in peritectic equi-
librium with the melt at about 1160C. In order to replace
L L + E2 eutectic E1 by eutectic E2 , the melt should be alloyed with
1164
about 30% Mn. Eutectic E1 should also contain about 30%
Mn and eutectic E2 should contain about 33% Mn.
However, the mentioned content of manganese can be in-
1160
E2 sufficient for practical implementation of such a transition
L + E1 due to the effect of the kinetic conditions of the crystalliza-
tion. In accordance with the known rule of Umanskii [4], the
1156 probability of formation of a phase with chemical composi-
E1 E1 + E2 tion closer to the composition of the alloy increases upon de-
viation of the kinetic conditions of structure formation from
1152 the equilibrium ones. In our case this phase is alloyed
cementite and the corresponding eutectic. For this reason a
27 28 29 30 31 32 33 34
eutectic with M7C3 carbides (e-phase) can be detected in the
Mn, at.%
structure of iron only if the latter is very highly alloyed with
Fig. 2. Eutectic polyhedration of the Fe C Mn diagram: manganese (substantially higher than 30%). Indeed, an x-ray
E1 ) g + Cem eutectic; E2 ) g + e eutectic; L ) liquid phase in peri- diffraction analysis of irons bearing up to 37% Mn and hard-
tectic equilibrium L + e Cem. ened from the temperature at which the crystallization pro-
cess finishes (about 1120C) has shown the presence of only
one carbide, i.e., alloyed cementite. However, after heat
The constructed low-temperature parts of polythermal treatment (high-temperature annealing) the structure of iron
sections have been confirmed by the results of a dilatometric with 37% Mn contains two carbide phases, i.e., cementite
analysis of manganese irons (Fig. 1). Even at 12% Mn the and e-phase.
range of the eutectoid transformation is reduced to Another special feature of structure formation in high-
520 650C in heating and to 430 290C in cooling. The manganese irons is strong supersaturation of eutectic auste-
design values of the range of eutectoid equilibrium lie within nite with carbon and manganese. Elevation of the content of
the hysteresis loop, which reflects good coincidence of com- these elements has been determined computationally even
putational and experimental data. for equilibrium (not supersaturated) austenite, which can be
It can be seen from sections of the Fe C Mn diagram seen in the sections and projections of the diagram. With de-
[2, 3] that manganese raises somewhat the temperature of the crease in the temperature the solubility of carbon and manga-
eutectic transformation and shifts the eutectic point toward nese in austenite decreases markedly, for example, in iron
the side with lower carbon content. However, these changes with 28 wt.% Mn and 1.5 wt.% C. In cooling from 1160 to
Alloys of the Fe C Mn System 97

a b

c d

Fig. 3. Microstructure of white cast irons with different content of manganese ( 300): a) 4.8% Mn; b ) 12% Mn; c)
21.5% Mn; d ) 35.7% Mn.

700C the chemical composition of equilibrium austenite
changes from 2 wt.% C and 19.6 wt.% Mn to 0.35 wt.% C
and 15 wt.% Mn, which is connected with segregation of a
large amount of secondary carbides (about 20%). The
amount of carbides segregated from austenite is still higher
in iron with 30 wt.% Mn, especially with allowance for the
supersaturation of the austenite during the crystallization of
iron. It is also important that intense segregation of second-
ary carbides occurs at a high temperature (1100 900C),
when the process of the decomposition of supersaturated so-
lution occurs rapidly.
We studied the structure of high-manganese white irons
experimentally with the help of metallographic analysis. Fi-
gure 3 presents the structure of cast iron bearing 2.8% C and
various amounts of manganese. With growth in the content
of manganese the amount of brittle eutectic colonies and
their sizes decreases. At 12% Mn the carbide inclusions be-
gin to be separated by layers of austenite. This is well ob-
servable at 21.5% Mn.
Inclusions of secondary carbides can be seen in the struc-
ture of cast iron at any content of manganese. At 12% Mn
these carbides have the form of individual inclusions of a

a b c

Fig. 4. Pearlite-like component in the structure of high-manganese white irons: a, b ) 900; c) 1450.
98 G. I. Silman

a b

c d

e f

g h

Fig. 5. Microstructure of high-manganese white irons in cast state: a, b ) 30% Mn; c, d ) 35% Mn;
e, f ) 35% Mn + modifying with ZhKMK; g, h ) 37% Mn; a, c, e, g ) 300; b, d, f, h ) 900.

granular or lamellar form. At a higher content of manganese
their amount increases; they form clusters of fine lamellas or
needles separated by austenite layers. These clusters have a
pearlite-like structure, which is especially well observable
under high magnifications (see Fig. 4). Formation of such a
component is explainable by the high-temperature decompo-
sition of supersaturated austenite.
Figure 5 presents the structure of white high-manganese
irons. In all the cases massive carbides are broken into indi-
vidual inclusions often connected by a fine carbide bridge.
Considerable refinement of the structure is ensured when the
metal is cast into metallic molds (Fig. 6). Rapid cooling of
the iron causes separate crystallization of the phases of the
eutectic.
Alloys of the Fe C Mn System 99

The mechanical properties of high-manganese irons in

cast state differ little from the properties of conventional
white irons; sr = 220 300 MPa at KC = 1 2 J/cm2. The
hardness of the iron depends on the content of carbon in it; at
2% C it is 27 30 HRC, at 2.5% C it is 35 38 HRC, and at
2.8% C it is 40 43 HRC. The relative abrasive wear resis-
tance Irel (the standard for comparison is steel 45) of high-
manganese cast iron as determined by testing in a Kh4-B ma-
chine is 1.5 against an electrocorundum abrasive paper and
3.1 against a silicon abrasive paper. These results are higher
than for alloy steels. They can be improved by heat treatment.
We used heat treatment in the following mode: isother-
mal hold at 1050 1100C plus cooling to room temperature
in water, in air, or in the furnace. Figure 7 presents the struc-
ture of irons differing in the content of manganese. Even in
the metal with 12 15% Mn such treatment (as a result of
the high-temperature isothermal hold) ensures isolation of
individual inclusions of eutectic cementite (Fig. 7a ). How-
ever, the shape and the mutual position of the carbides re-
main unfavorable, which is responsible for the low proper-
ties, i.e., sr = 300 370 MPa, KC = 2 3 J/cm2, and hard-
ness 40 43 HRC. b
At 20% Mn in the metal the conditions are more favor-
able for well-manifested separation of carbide inclusions and Fig. 6. Microstructure of white high-manganese irons cast into me-
improvement of their shape in heat treatment. It can be seen tallic molds: a) 300; b ) 900.
from Fig. 7b e that individual inclusions
of carbides in such heat-treated iron can be
fully separated from each other. The final
structure depends on the cooling condi-
tions. Cooling in water ensures supersatu-
rated austenite and separate carbide inclu-
sions; considerable regions of a pearlite-
like component are encountered. After the
heat treatment mentioned the metal has en-
hanced properties, namely, sr = 400
600 MPa, KC = 20 J/cm2, and hardness b
27 43 HRC depending on the content of
carbon in the metal. For example, at 2.2% C
in the composition sr = 450 500 MPa,
KC = 14 20 J/cm2, and hardness 23
30 HRC. Such iron has structure and prop-
erties intermediate between carbide steels
and white hypoeutectic irons.
The other cooling modes used give
worse results. After cooling in air the car-
bide inclusions are coarser; in some places c d
they are separated incompletely (Fig. 7c
and d ). This explains the lower properties
of the metal, i.e., sr = 250 350 MPa and
KC = 2 3 J/cm2.
Fig. 7. Microstructure ( 300) of white
Slow cooling of iron with the furnace
high-manganese irons bearing 2.5 2.8% C,
worsens the properties even more, i.e., 15% Mn (a), 2.5 2.8% C, 30% Mn
KC = 1 3 J/cm2 and sr = 200 250 MPa. (b, c, d ), and 1.8% C, 30% Mn (e) after an
In this case carbide inclusions do not de- isothermal hold at 1050 1100C and cool-
tach from each other and form a continuous ing in different media: a, b, e) in water;
e
carcass. c, d ) in air.
100
Fig. 8. Microstructure of white high-manganese iron (chill casting) after quenching: a) 30% Mn, 300; b ) 37% Mn, 300;
c) 30% Mn, 900.
The best results are obtained after heat treatment (high-
temperature holding and cooling in water) of chill castings.
In this case the resulting structure is fine-grained and bears
separate and uniformly distributed carbide inclusions (see
Fig. 8). In such cast iron sr = 550 650 MPa at KC of up to
80 J/cm2 and d of up to 8%. Such an alloy can be subjected
to plastic deformation without fracture even under an impact
load.
Iron bearing 30% Mn and 2.5% C and having a hardness
of 35 HRC after heat treatment with water cooling possesses
an elevated wear resistance; in operation in a free abrasive it
has Irel = 1.9 2.2, when rubbed against an electrocorundum
abrasive paper it has Irel = 1.8, and when rubbed against a si-
licon abrasive paper it has Irel = 4.13. The wear resistance of
such iron exceeds that of alloy steels (for example G9F6).
The enhanced properties of heat-treated high-manganese
cast iron (bearing 30% Mn and more) are ensured to a con-
siderable degree by the special features of their phase com-
Fig. 9. Microstructure of heat treated white irons with 30% Mn (a) and 35% Mn (b, c) ( 900): a, b ) thermal etching; c) nital
etching.
G. I. Silman
b c
position; their structure (including the eutectic one) bears not
only cementite but also M7C3 carbide. This has been con-
firmed metallographically. Figure 9 presents the microstruc-
ture of iron with two kinds of eutectic E1 and E2 (or with a
ternary eutectic g + M3C + M7C3 ) (Fig. 9a ) and with
eutectic E2 (Fig. 9b and c).
The microstructure presented in Fig. 9b and c is similar
to the microstructure of chromium white irons with a eutectic
based on M7C3 carbides (see Fig. 10) [5]. In both cases we
can see dissected carbide crystals in the form plates and
hexagons.
EFFECT OF SILICON ON STRUCTURE
FORMATION IN HIGH-MANGANESE IRONS
It is known that silicon dissolves primarily in matrix
phases of cast iron (austenite, ferrite) and is virtually insolu-
ble in cementite, which explains the thermodynamic nature
b c
Alloys of the Fe C Mn System 101

e (202)a
g (111)a
I

Cem (121)a

G (002)a
Fig. 10. Microstructure of white iron with 12% Cr [5], 200.

28 27 17 16 q, deg

of the strong graphitizing action of silicon. For a long time, Fig. 11. Fragments of a diffractogram obtained for the surface of al-
researchers thought that by analogy with cementite silicon loy 2: Cem ) cementite; e) M7C3 carbide; G ) graphite.
does not dissolve in other carbide phases. However, deeper
studies of the Fe C Si and Fe C Cr Si systems dis-
credited this assumption [6]. It has been shown that silicon
the distribution of elements between the e-phase and the
can dissolve in considerable amounts in M7C3 carbide e - Cem e - Cem
cementite. For cast alloys K Mn 1.2 and K Si =
(e-phase) and can stabilize this carbide markedly in its com-
e - Cem
petition with cementite. However, the graphitizing action of 6 10; for heat-treated alloys K Mn = 1.20 1.25 and
silicon manifests itself in this case too, and special measures e - Cem
K Si = 30 35. Note that the values of the coefficient of
(additional alloying with carbide-forming elements, accele-
distribution of silicon between the e-phase and the cementite
rated cooling in crystallization, microalloying with bismuth,
are very high, especially in heat-treated iron. This means that
tellurium, etc.) are required for obtaining iron with a fully or
silicon increases markedly the stability of the e-phase in its
partially chilled structure.
competition with cementite. Therefore, it is quite clear that
Manganese is an element promoting carbide formation in
iron. For this reason it is expedient to study the joint effect of the e-phase and the eutectic with this phase appear in the
manganese and silicon on structure formation in iron and de- structure of the alloys with silicon at a substantially lower
content of manganese than in the alloys without silicon.
termine the distribution of these elements between the
Note that the coefficient of distribution of silicon be-
phases. Taking into account the special features of the action
of both elements we chose partially graphitized (mottle) and tween the e-phase and the austenite is less than unity (Ta-
fully white irons for our study. The chemical composition of ble 2), which means that in alloys with the e-phase silicon
both groups of iron is presented in Table 1. Alloys 1 and 2 produces a graphitizing effect too. Indeed, despite the pre-
belong to mottles with globular graphite (the spheroidization sence of a large amount of carbide-forming element (manga-
of graphite has been ensured by modifying them with a com- nese) in alloys 1 and 2 their structure is of a mottle kind with
a considerable amount of graphite.
plex ZhKMK additive); alloy 3 has a stably white structure.
The microstructure of alloy 2 in cast and heat-treated
An x-ray diffraction analysis showed the presence of carbide
states is presented in Fig. 12. It can be seen that the morpho-
phases of two kinds, i.e., of alloyed cementite and M7C3 car-
logical features of carbide inclusions correspond mainly to
bide (e-phase) in all the three metals. Figure 11 presents the M7C3 carbides. After the heat treatment the structure of the
diffractogram of alloy 2, which confirms the mentioned iron has a composite nature; in combination with globular
phase composition.
We used carbide analysis as described in [1] to determine
the values of the coefficients of phase distribution of manga-
nese and silicon in all the three alloys. TABLE 1. Chemical Composition of Irons Alloyed
The distribution of elements between cementite and aus- with Manganese and Silicon
tenite virtually did not differ from the known one. On the ave- Content of elements, wt.%
-g -g
rage K Cem
Mn
= 1.5 1.8 for alloys 1 and 2; K CemMn
1.1 Iron
-g
C Mn Si Cr V
and K Cem
Si
= 0.05 0.1 for alloy 3. In heat-treated alloys 1
1 3.54 7.1 4.06 0.30 0.20
-g -g
and 2 K Cem
Mn
= 1.8 2.1; in alloy 3 K Cem
Mn
= 1.1 1.2 and 2 3.98 9.8 3.44 0.40 0.10
-g
K Cem
Si
0.02. We also determined the special features of 3 2.67 28.0 2.90 0.15 0.05
102
b structure should be used as a wear-resistant material with ele-
Fig. 12. Microstructure of alloy 2 ( 300): a) cast state; b ) after an-
nealing.
graphite this ensures high mechanical and operating proper-
ties of the iron. Alloy 1 has similar structure and properties.
The microstructure of the matrix in alloys 1 and 2 con-
sists primarily of metastable austenite and a low amount of
products of its decomposition (martensite and troostite). The
austenitic structure of the matrix ensures enhanced values of
ductility and impact toughness of the iron, and the reinforce-
TABLE 2. Coefficients of Distribution of Manganese
and Silicon between e-Phase and Austenite
Coefficient of distribution K e g of elements
Iron
Mn Si
1 2.11/2.42 0.66/0.68
2 2.04/2.21 0.69/0.69
3 1.23/1.32 0.64/0.65
Notes. 1. The coefficients of phase distribution of
manganese and silicon in the metal were evaluated for
the conditions of double-phase equilibrium carbide
M7C3 (e-phase) austenite.
2. The numerators present the distribution coefficients
for cast irons; the numerators give the same figures for
annealed irons.
G. I. Silman
Fig. 13. Microstructure of eutectic in alloy 3, 900.
ment of the alloy with carbides (primarily M7C3 ) is responsi-
ble for the high strength properties and for the wear resis-
tance. The presence of a great enough number of inclusions
of globular graphite in the structure of the iron in combina-
tion with its composite nature creates good anti-friction
properties.
Alloy 3 in cast state has a structure with prevalence of a
eutectic bearing M7C3 carbides (Fig. 13). Heat treatment re-
moves cementite-type carbides from the structure of the iron
almost fully and gives it a composite nature. Iron with such a
vated impact toughness.
The described example of complex alloying of manga-
nese iron demonstrates the possibility of effective additional
action on structure formation and development of new alloys
with special properties.
We studied experimentally the mechanical and tribo-
technical properties of mottles alloyed with manganese and
silicon. The wear tests were made using a MI-1M friction
machine in which the tested specimen was rubbed against a
disc 50 mm in diameter fabricated from hardened steel 45.
The hardness of the disc was 45 HRC; the speed of rotation
was 250 rpm. The specific load on the specimen was varied
within 1.5 20 MPa. The tests were performed under condi-
tions of dry friction.
The alloys had the following mechanical properties:
sr = 680 750 MPa, d = 3 5%, KC = 25 40 J/cm2, and
hardness 277 293 HB.
The studied mottles had a higher wear resistance under
friction than any known alloy. The friction factor f depended
on the specific load p, i.e., f = 0.55 0.65 at p = 1.5 MPa and
f = 0.33 0.38 MPa at p = 20 MPa.
CONCLUSIONS
1. In white iron manganese austenizes the matrix (metal-
lic base) less intensely than in steels, which is caused by its
prevalent segregation into carbide phases. The austenite
structure of manganese iron bearing less than 25% Mn is
Alloys of the Fe C Mn System
thermodynamically unstable and undergoes phase transfor-
mations under the conditions of deformation.
2. The performed eutectic polyhedration of the diagram
and its analysis have shown that two kinds of eutectic can
form in high-manganese iron, namely, a ledeburite
(g + Cem ) eutectic and a eutectic based on M7C3 carbides
(g + e). Both eutectics are in peritectic equilibrium with the
melt at about 1160C; in order to replace the g + Cem
eutectic by a g + e eutectic the melt should be alloyed with
about 30% Mn. Due to the effect of kinetic factors the critical
content of manganese increases by 5 7%.
3. Manganese raises somewhat the temperature of the
eutectic (ledeburitic) equilibrium and shifts the eutectic point
toward lower carbon content. However, these changes are in-
considerable and cannot affect the morphology of the
eutectic. The kinetic factors play a greater role. High alloy-
ing of iron with manganese increases the supercooling of the
melt during crystallization and promotes formation of a
quasi-eutectic with reduced content of carbides and strong
supersaturation of austenite with carbon and manganese.
4. The quasi-eutectic in high-manganese iron alloys is
looser than the conventional ledeburite and the carbide
chains in it are prepared for breaking. This is especially typi-
cal for iron with a eutectic based on e-phase. In heat treat-
ment of such iron individual carbide inclusions become fully
separated, and a composite fine-grained structure is formed,
which ensures a high level of mechanical and operating
properties of the iron. In order to obtain a refined structure
with granular austenite-carbide composite, it is necessary to
ensure a high cooling rate during crystallization (for exam-
ple, by chill casting) and subsequent heat treatment of the al-
loy, which should consist of a long enough high-temperature
hold and rapid cooling (in water).
5. Supersaturated eutectic austenite in white high-man-
ganese iron undergoes high-temperature decomposition that
103
yields a double-phase austenite-carbide component having a
pearlite-like structure.
6. Stabilization of the M7C3 carbide in its competition
with cementite can be ensured by additional alloying of
high-manganese iron with silicon. In the structure of iron
with silicon the M7C3 carbide and the eutectic with this phase
appear at a substantially lower manganese content than in
iron bearing no silicon. However, silicon is a graphitizing
element in such alloys too, which ensures the possibility of
fabricating austenitic mottles. Mottles with globular graphi-
te, M7C3 carbides, and a metastable austenitic matrix, which
are alloyed with manganese and silicon, have a very high
wear resistance under the conditions of friction, a set of high
mechanical properties, and good anti-friction properties.
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tem and some structural effects in this system. Part 2. Design and
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Term. Obrab. Met., No. 4, 3 9 (2005).
3. G. I. Silman, Phase diagram of alloys of the Fe C Mn sys-
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Term. Obrab. Met., No. 9(603), 3 7 (2005).
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