STRUCTURE OF METASTABLE EUTECTICS

E. Yu. Bereza

USC 66g.017.3

Accelerated cooling in crystallization often leads to phase and structural changes in

alloys, which has a considerable effect on their properties. Of particular interest are the
structures of rapidly cooled eutectic alloys whose solidification proceeds already at a relatively small increase of the cooling rate: up to 102 K/sec. Stereographic microanalysis
reveals a certain tendency in the change of structure of eutectics when an increased cooling
rate entails the appearance of a metastable phase among the eutectic partners. This tendency
can be illustrated by comparing the results of the investigation of eutectics in two systems:
F e ~ and AI-Ge.
In ordinary slow solidification, an equilibrium structure arises and a stable eutectic
forms in both systems: an austenitic-graphite one in Fe-~ a n d a n aluminum-germanium one in
AI-Ge alloys. When we investigate the morphological features of the structure of colonies
of these eutectics, we have to note that both of them, according to the data of [i], belong
to the skeleton type of eutectic structures. In both cases the leading phase in crystallization is the more high melting and crysta!lographically more complex one, i.e., graphite and
germanium. The crystals of these phases (each in its own system) in the process of cooperative eutectic crystallization are the first to grow into the liquid; they form the skeleton
of the eutectic grain, i.e., colonies. The dependent phases in both cases are solid solutions
on the basis of iron (austenite) and aluminum which edge the crystals of the leading phase,
being situated in the gaps between its spurs and forming the matrix of the colony.
In a detailed investigation of the dependence of the shape of the colonies of the stable
eutectic AI + Ge on the cooling rate a regularity was discovered which is analogous to the
one observed in the system Fe-C. Bunin et al. [2] described in detail the change of shape
of the colonies of austenite-graphite eutectic from rosette-crabiike to spherical with increasing degree of undercooling. A similar effect was also found in the system AI-Ge. When
crystallization proceeded at increased cooling rate (to 102 K/sec), the colonies of stable
eutectic assumed a spherical shape. Thus in the process of development of the eutectic
colony there proceeded some strong ramification of the skeletal frame of the leading phase
(graphite or germanium) with the most intense growth of radially directed spurs, in consequence of which the colony had the above-described shape. Consequently, the aspect of the
stable eutectic in all cases is alike to the outline of the base crystal; this testifies to
the leading role of the graphite inclusions and germanium crystals in the process of crystallization.
In addition to the change of shape of the colonies of stable eutectic, accelerated
cooling of alloys of the systems Fe-~ and AI-Ge leads to a change of the phase composition
consisting in the formation a metastable intermediate phases. In iron-carbon alloys this
is cementite. Microscopic analysis of aluminum-germanium alloys with hypereutectoid composition, cooled at a rate of 102-103 K/sec, revealed structurally free crystals of the metastable intermediate phase identified by electron microprobe and x-ray diffraction analyses
as the compound AIGe with tetragonal lattice. It was established that the metastable phase
AIGe takes directly part in the colonial eutectic crystallization, and this was confirmed by
electron probing of the phases. The eutectic point of the metastable eutectic corresponds
to 32% Ge (in atomic fractions) and to 420C, i.e., it is shifted slightly downward and to
the right from the eutectic point in the stable phase diagram.
In iron-carbon alloys the metastable diagram is also shifted relative to the stable one,
and cementite plays a considerable role in the formation of the eutectic structure. Henceforth we will call eutectics with metastable intermediate phases metastable eutectics:
Fe + Fe~C (ledeburite) and AI + AIGe, respectively.
Translated from Metallovedenie i Termicheskaya Obrabotka Metallov, No. g, pp. 4-6, September, 1987.

0026-0673/87/0910-0641512.50

1988 Plenum Publishing Corporation

641

1200

800 ~

fl
J

__-,,_.. . . . . . . .

#or,

%Fe

99%C

t,C
800

/.

~o :'~E
0
%A].

i
I

32 ~1
20

"~1

60

80

%Oe

Fig. i. Stable (solid line) and

metastable (dashed line) phase
diagrams of the systems Fe-C
(content of elementes in weight
fractions) and AI-Ge (content of
elements in atomic fractions).
A detailed analysis of the structure of these metastable eutectics also reveals much
that they have in common. However, this was discovered primarily in the investigation of
structurally free cementite crystals and of the metastable phase AIGe which have crystal lattices with the same type of packing: orthorhombic, close to tetragonal in Fe3C, and tetragonal in AIGe.
The results of the investigation of the structure of the metastable eutectic A1 + AIGe
made it possible to determine that its morphological type is the honeycomb type. Ledeburite
is also a classical example of a honeycomb eutectic.
In the metastable eutectic of aluminum-germanium alloys, like in ledeburite, the intermediate phase is a matrix of colonies pierced by filamentary ramifications of the solid solution. Regardless of such a change in the roles during the process of paired growth of the
eutectic phases (for the matrix in stable eutectics is the solid solution), the metastable
intermediate phase is in both cases the basic phase leading the process of crystallization,
and the outer aspect of the eutectic colony follows the outline of the base crystal.
On the basis of a morphological analysis of the stable and metastable eutectics in
Fe-C and AI-Ge alloys the following conclusion may be reached. Accelerated crystallization
of eutectic-type alloys causing the appearance of metastable phases may lead to fundamental
changes in the structure of eutectic colonies. Instead of skeletal eutectics, where the
matrix phase is the solid solution, eutectics form whose matrix consists of the metastable
intermediate phase. Apparently the transition to the crystallization of honeycomb eutectics
is a general regularity of structure formation in eutectic-type alloys when cooling is accelerated to such an extent that the formation of metastable phases is guaranteed but the
possibility of cooperative eutectic crystallization, i.e., of paired growth of the phases
within the eutectic colonies, is retained.
When we now turn to simple eutectic systems, this can be explained fairly simply. In
accordance with the general rule, the eutectic point in the phase diagrams of such systems is
shifted toward the low melting component, i.e., iron or aluminum. The solid solution based
on these components also provides the basic bulk of the eutectic colony, forming its matrix.
Within the matrix there are ramified crystals of the second, more high melting phase (graphite or germanium). The volume fraction of this phase is relatively small but it acts as
leading phase and forms the skeleton of the colony.
In accelerated cooling the kinetically more advantageous is the formation of a metastable
intermediate phase (Fe3C or AIGe) which contains a certain amount of the low melting component; this is illustrated by the corresponding regions of the stable and the metastable
phase diagrams of the systems Fe-C and AI-Ge (see Fig. i). The volume fraction of the meta-

642

stable phase in the eutectic therefore greatly increases; however, since the leading role of
this phase is retained, the eutectic colonies assume a honeycomb structure, which exerts some
influence on the properties of the alloy [3].
LITERATURE CITED
.

2.
3.

Yu. N. Taran and V. I. Mazur, The Structure of Eutectic Alloys [in Russian], Metallurgiya, Moscow (1978).
K. P. Bunin, Ya. N. Malinochka, and Yu. N. Taran, Fundamentals of the Metallography of
Cast Iron [in Russian], Metallurgiya, Moscow (1969).
I. S. Miroshnichenko, G. P. Brekharya, and E. Yu. Bereza, "The morphology of eutectics
with metastable phases in the system aluminum-germanium," Dokl. Akad. Nauk SSSR, 256,
No. 3, 595-597 (1981).

EFFECT OF THE COOLING RATE ON THE MECHANISM

AND THE KINETICS OF THE PHASE TRANSFORMATIONS
IN SOLIDIFICATION OF W-Mo HIGH-SPEED STEELS
P. F. Nizhnikovskaya, E. P. Kalinushkin,
E. V. Arshava, and O. S. Yakushev

UDC 669.017.3:669.14.018.252

The presently used high-speed W-Mo steels are characterized by low hot ductility; this
is due to peculiarities of their structure in the cast state which forms as a result of complex multistage crystallization. In accordance with the existing pseudobinary phase diagram
plotted for alloys type steel R6M5 with different carbon content [i], the process of solidification of most industrial W-Mo steels entails the following phase transformations: L + ~,
L + ~ + y, L + y + K. However, whereas the general form of this schema does not evoke any
doubts, the mechanism of separate crystallization processes under actual kinetic conditions
of cooling steel was incompletely investigated, the literature data on this question are
scarce and often contradictory [1-4].
The discrepancies between experimental data obtained by different authors are ascribed
to the complexity of fixing the high-temperature state of specimens by quenching and by the
considerable dependence of structure formation in alloy steels on the conditions of their
melting and crystallization. In the present work we therefore investigated the solidification of steel R6M5, and also of steels R6M5F3, R6M5K5 by the method of "stop-quenching" on
an installation of original design; this is a horizontal-type vacuum furnace with a quenching
tank provided with a thyristor system of the electric power supply to the heater [5].
Quantities of steel weighing 1 g each were heated in an atmosphere of highly pure flowing argon to tmp 1570C, held for i0 min, cooled to te, and then quenched in a 10% aqueous
solution of cooking salt. The cooling rate in the interval tmD-t e was varied within the
limits 0.1-10 = K/sec; these rates are characteristic of the c~o!ing of different parts of
industrial castings weighing 400-1150 kg, and they were strictly checked. The obtained specimens were subjected to complex investigation by the methods of optical (Axiomat, West Germany) and scanning electron (JSM-35, Japan) microscopy, and also of electron microprobe analysis (MS-46, France).
The solidification of steel R6M5 at relatively low cooling rates (0.1-1K/sec), studied
earlier [4, 6, 7], showed that the process of crystallization begins at 1400-1420C and is
accompanied by the nucleation and intense development of dendrites of 6-ferrite. In consequence of the merging of neighboring dendritic branches within the bulk of the solid solution, spherolitic microsections of the liquid phase form, and these are, completely or partly
isolated from the principal melt (Fig. la). This may be due to the transition of the principal alloying elements of the steel into the solid phase (Fig. 2), and also to the mutual com-

Denpropetrovsk Metallurgical Institute. Translated from Metallovedenie i Termicheskaya

Obrabotka Metallov, No. 9, pp. 7-ii, September, 1987.

0026-0673/87/0910-0643512.50

1988 Plenum Publishing Corporation

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