THEORY

SHAPE OF GROWING CRYSTALS OF PRIMARY PHASES IN EUTECTIC ALLOYS OF

THE SYSTE~IS Fe--Fe=B AND Ni-NiaB

7o No Tavadze~ Vo I. Garibashvili, t~C 669o!~781+669°24~781:669.017.1

and Sh~ G~ Nakaidze

Eutectic-type alloys used in practice only have a purely eutectic structure in individu-
al :ases~ fomning as a result of multiphase crystallization. Normally, eutectic crystalliza-
tion is preceded by segregation of primary crystals whose shape generally predetermines alloy
structure and properties.
It is well known that the crysta!lochemical nature of the crystallizing phase and also
temperature and concentration conditions for carrying out this process have a marked effect
on the mechanism and kinetics of structurally free crystal growth° According to the entropy
criterion for the stability of crystal boundary shape (the Jackson criterion), with crystal-
lization under conditions close to equilibrium, a substance having an entropy change on fu-
sion ASf exceeding 4 cal/(mole-°K) tends to solidify in the shape of sharply bounded crystals.
During crystallization, metals normally have a rounded phase boundary which corresponds to a
comparatively small value of their entropy of fusion, i.e., <2 calf/ (mole" °K) [i].
However~ it should be noted that this idea is not always vsJ_id° We consider, as an ex-
ample, the features of structure formation in two systems of the solid solution--bromide type;
Ye--Fe2B and Ni~Ni3B (Fe and Ni are solid solutions of boron in iron and nickel, respectively).
During solidification of eutectic composition alloy, at first there is segregation of
excess crystals of Fe2B and Ni-Ni3B from the melt. There are no data in the literature for
the entropy of fusion for these compounds°
Under such conditions, in order to calculate values of ASf, according to the data of
[2], it is possible to use the equation

Corrections ~, and ~= in Eqo (I) are calculated by the equations

~ . . . . ~ c,~+ ~ ( ~ ~ ~--~-~ +.~-%--~,~~ ~ + m], (2)

T Anz,~7~ T AT~Bu
. (r)dr , dr
I T+ i c2(r) T. <3)

Taking account of the significan~ change in short-range order structure during melting
of borides Fe2B and Ni3B [3], the value of sufficient k was assumed to be close to unity. The
temperature dependences for specific heat Cp(T) and entropy of fusion AS for iron, nickel,
and boron were borrowed from [4, 5].
Calculations showed that ASFe2B ~ 1.5 cal/(mole,°K) ; ASNi3B ~-3 cal/(mole °°K)°
Judging from the data obtained, nickel boride should be more inclined to grow with an
edge phase boundary thaniron boride. In actual fact, the opposite case applied. Primary
crystals of Ni3B with a rhombic structure in hypereutectic alloys with a low degree of eu-
tectic formation at slow cooling rates take on a spherical form (Fig. la)~ The spherical
shape of growing crystals is maintained with a change in temperature and concentration con-
ditions; with increasing concentration of boron or with increasing supercooling there is a
tendency to change from spherical shape to dendrites with rounded branches (Fig. ib).

Institute of Metallurgy, Academy of Sciences of the Georgian SSR~ Tbilisi. Translated

from Meta!lovedenie i Termicheskaya Obrabotka Metallov, Noo i, pp. 2-3~ january, 1983.

0026-0673/83/0102-0003507o50 © 1983 Plenum Publishing Corporation 3

 Fig. i. Shapes of growing crystals of primary phases
in alloys of the systems Fe-~B (etched in sodium ni-
trate) and Ni--B (etched in a mixture of copper sul-
fate and hydrochloric acid): a) spherical crystal of
Ni~B; b) dendritic crystal of Ni3B; c) primary crys-
tals of Fe2B; d) structure of freely grown Fe=B; e)
dendritic crystal of Fe=B; f) eutectic colony of the
alloy Fe--Fe2B; g) structure of hypoeutectic alloy Fe--
Fe~B ; h) structure of hypoeutectic alloy Ni--Ni3B: a)
x630; b, h) x800; c, d, e) ×500; f) x400; g) x320.

Iron boride is related to the structural type CuAI2~ and it crystallizes in a tetragon-
al crystal system. Structurally free crystals of Fe2B in hypereutectic alloys of the Fe B
system follow the shape of an elementary cell. During metallographic study of flat sections
of primary boride crystals they were observed in the form of squares, rhombuses, rectangles,
parallelograms, and triangles, i.e., all of the possible sections of a tetragonal prism (Fig.
ic).
Growth of Fe=B crystals starts with the development of outgrowths at the tips of grow-
ing prisms. Tip outgrowths branch parallel to the basal planes of the original prism. These
branches, intergrowing with each other, form ribbed outcrops from which there is layered
growth of prism boundaries and a gradual increase in polyhedral dimensions (Fig. id). Under
actual conditions there is not always complete reproduction of the growing prism shape. Crys-
tals grow along densely packedplanes, and this growth tendency is more marked the lower the
boron concentration in hypereutectic alloy.
As the boride crystal progresses, the critical dimensions of the polyhedron lose their
stability and dendritic branching begins. Dendrite branches consist of successively placed
prisms; the center of each succeeding prism is the tip of the previous one° As a result of
this, a dendrite forms with the typical skeletal structure (Fig. le).
The shape of growing boride phase crystals has a marked effect on eutectic structure of
the test alloys. In hypereutectic alloys primary boride crystals are structural centers for
growing colonies which reproduce the shape of their principal crystallizing phase, i.e.,
borides. In the iron--boron alloy the eutectic colony is a bicrystalline form of the hour-
glass type with clearly defined sectoral boundaries (Fig. if).
In hypereutectic alloys of the Ni--Ni3B system, eutectic, as it were~ borders primary
boride segregates; in the presence of primary crystals it takes the shape of spherical colon-
ies, and with rounded dendrites of primary borides it takes the dendrite shape.
In hypoeutectic alloys of the systems Fe B and Ni--B crystallization starts with segre-
gation of excess solid solution crystals in the form of rounded dendrites. Eutectic Fe--Fe2B,
independent of the locations of primary segregates, grows on boride crystals and forms in the
same colonies as in hypereutectic alloys (Fig. ig)o In alloys of the Ni--B system there is
growth of boride Ni3B (in the form of a border) on excess solid-solution dendrites, which
initiates the start of eutectic colony formation (Fig. lh). Colony morphology and shape in
the test alloys for both hypereutectic and hypoeutectic concentration governs the shape of
primary crystals of the principal phase.

CONCLUS IONS
i. With structurally free growth, Ni~B crystals have a rounded shape, and Fe2B crystals
have flat boundaries, although according to entropy of fusion values (ASNi3B m 3.0 cal/(mole.
°K), ASFe2B m 1.5 cal/(mole'°K) growing crystals of Fe2B should also have a rounded shape
for phase boundaries.
2. Shapes of growing Fe--Fe2B and Ni--Ni3B eutectie colony crystals are governed by the
shapes of the principal eutectic crystallization phases, i.e., borides.

LI TERATURE CITED
I. Yu. N. Taran and V. I. Mazur, Structure of Eutectic Alloys [in Russian], Meta!lurgiya,
Moscow (1978), p. 312.
2. V . N . Vigdorovich, V. A. Evseev, and A. N. Krestovnikov, "Refinement of the method for
estimating heat of fusion of chemical compounds," Izv. Vyssh. Uchebn. Zaved., Tsvetn.
Metall., No. i, 28 (1971).
3. F . N . Tavadze, I. A. Bairamashvili, and D. V. Khantadze, "Surface tension and density
of iron, cobalt, and nickel borides," in: Surface Phenomena in Melts and Solid Phases
Arising from Them [in Russian], Kabardino-Balkarskoe Knizhnoe, Nal'chik (1965), p. 376.
4. O. Kubaschevski, E. Evans, and C. Alcock, Metallurgical Thermochemistry, Pergamon
Press, Oxford, London (1967), p. 495.
5. l~ermal Constants of Substances: Manual [in Russian], Vol. 5, VINITI (1971), p. 530;
Vol. 6 (1972), p. 369.