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CRYSTAL

GROWTH

ELSEVIER Journal of Crystal Growth 144 (1994) 353—366 ______________________

Peritectic formation in the Ni—Al system


J.H. Lee, J.D. Verhoeven *

Iowa State University and Ames Laboratory, USDOE, Ames, Iowa 50011, USA

Received 27 April 1994; manuscript received in final form 1 August 1994

Abstract

Directional solidification studies have been carried out on Ni—Al alloys at compositions in the two-phase region
of the two phases, y and y’, that form the peritectic in this system. It was found that under certain conditions of
G/V, the two phases form with the banded structure found in previous directional solidification studies of peritectic
systems. However, under other G/V conditions the two peritectic phases were found to grow into the liquid along
an isothermal front lying just below the peritectic temperature. The growth front resembles those of lamellar and rod
eutectic alloys because it lies as close to an isotherm as the growth fronts observed in eutectic alloys. However, the
two solid phases display a morphology resembling that of classical two phase cellular growth where a second phase
forms in-between the primary cells. The structure has been termed cellular coupled growth, and its morphology and
the conditions for its formation are characterized and compared to eutectic and cellular growth morphologies.

1. Introduction Fig. 1 presents a schematic peritectic phase


diagram where the two solid phases are given the
In a series of papers [1—3] the authors have symbols which correspond to those used in the
shown that studies of quenched directionally so- Ni—Al system. The stability of a planar solid—
lidified samples of Ni—Al alloys reveal several
interesting phenomena at compositions near the
eutectic and peritectic reactions. Under certain
growth conditions one finds: (a) a metastable \ L
eutectic structure [11,(b) an unusual cellular type
eutectic structure of both metastable and stable
phases [31,and (c) etching characteristics that
allow the position of the freezing front to be
revealed in quenched alloys [2]. The system also
shows some unusual results in the growth charac-
teristics of two-phase peritectic alloys and these
are reported in this paper.
I— (1) ~.~~_____~ _________ (3)
~--—-~ (2) n—
Cv Cp
I Composition
* Corresponding author. Fig. 1. Hypothetical peritectic phase diagram.

0022-0248/94/$07.OO © 1994 Elsevier Science B.V. All rights reserved


SSDI 0022-0248(94)00609-1
354 iii. 1,cc. .1.1). Vcrhoeien /Jour;ial of(sta/ Growth 144 (1994) 353—366

liquid interface has been found to be predicted other directional solidification studies of peritec-
fairly accurately by the constitutional supercool- tic alloys [7—9].
ing criteria of Tiller Ct al. [41.For the alloy of Fig. In this paper we present directional solidifica-
1, plane front growth from the liquid at steady tion experiments on Ni—Al alloys having composi-
state conditions should produce 3 types of solids tions in the 2-phase regions of this alloy system.
depending upon the composition: (1) From 0 to In contrast to the previous studies, it is observed
C~,one expects single phase y solid. (2) From in this system that under certain G/V conditions
to C~,one expects a two-phase y + y’ solid. (3) a type of coupled growth does seem to occur
Above C7 one expects single phase y’ solid. The between the y and y’ phases.
critical value of G/V (liquid temperature gradi-
ent/solidification velocity) required for planar
growth is found from the constitutional super- 2. Experimental procedure
cooling theory to he,
/ , Alloys were prepared by directional solidifica-
G/V~mt,C —C )/D. ~ . .

/ s tion in hard fired alumina tubes in an apparatus


In composition regions (1) and (3), G/V in- that has been described in detail elsewhere [1].
creases because C1 C5 increases due to the
— Briefly, a platinum resistance furnace fitted with
divergence of the liquidus and solidus lines in a water cooled Cu toroid at its bottom end was
these regions. The behavior in region 2 is not so passed upward at controlled rates around a 5 mm
clear. Chalmers [51was apparently the first to ID alumina tube filled with the alloy under study.
point out that one might expect the two solid In some experiments a miniature thermocouple
phases of region (2) to form from the liquid at the was inserted down into the molten metal and the
peritectic temperature, T~,in a coupled growth temperature gradients in the solid and liquid
mode if plane front conditions were maintained, regions were determined by advancing the solid—
similar to that which is commonly found in eutec- liquid interface past the thermocouple at a fixed
tic alloys. In this case the liquid would remain at growth rate. These studies found that the gradi-
composition C1, and the solid composition would ents varied with growth rate and plots were pre-
now he an average over the two phases, -y + y’. pared of gradients versus growth rate for various
Hence in region (2) the numerator of Eq. (1) furnace temperatures and cold finger positions.
decreases as the average solid composition rises The technique allowed the liquid temperature
from C7 to C~and one has a decreasing G/V in gradient to vary from 25 to 42°C/cm at the
the 2-phase region. slowest growth rate studied, 0.8 gm/s. and from
There have been many studies of directionally 21 to 29°C/cmat the highest growth rate studied,
solidified peritectic alloys in the 2-phase region 61 j.~m/s.In experiments with no thermocouple.
[6—91and none of them have found coupled pen- after the desired volume fraction of the original
tectic growth similar to coupled eutectic growth. liquid had been solidified, f5(Q), the alumina
The work of Boettinger appears to be the most containment tube was dropped into a quench
thorough. He did careful directional solidification bath of either stagnant water or molten Gain
studies in the 2-phase region of the Sn—Cd sys- alloy causing the remaining liquid to freeze
tern at G/V values above and below the critical rapidly, thereby preserving the solid microstruc-
values. At the high G/V values, the planar inter- ture formed at the solid—liquid interlace. Sam-
faces did not produce a coupled 2-phase struc- pIes were then sectioned and polished to reveal
ture. but rather produced alternating bands of the microstructures with optical microscopy. The
the two solid phases, the y and y’ phases for the target compositions varied from 23% to 24% Al
nomenclature of Fig. 1. At low G/V values, an
apparent cellular interface was observed with cells
of the -y phase surrounded by intercellular y’ _______

phase. Similar results have been found by the ‘ All compositions will he given in atomic ~1.
J.H. Lee, J.D. Verhoeten /Journal of Crystal Growth 144 (1994) 353 —366 355

and the solid—liquid growth fronts were dendritic . ‘.1-- -. . -~ a,:’ - ..~ ~. -

at the high rates and planar at the low rates. . -

The phase diagram for the Ni—Al system in . . -

the region of interest is shown at the top of Fig.


2. As expected from this diagram, alloys in the I

23% to 24% Al range were found to initiate -

solidification from the liquid as pure -y phase for


gradient-to-velocity (G/V) ratios adequate to -

avoid instability of the planar interface. As the -

planar solid—liquid interface moves upward in


these experiments, it produces an Al rich solute
boundary layer which would lead to solutal con- .

vection. Because of this effect and the inherent


segregation produced by the phase equilibria, one
would expect a macrosegregation along the length

(a) 1385

1383 ~

1381 / . .,.,S-S-,,

1379
- / ‘~
— — — — — — - •“-~‘-~

vL
- Fig. 3. Trancition from single phase y grosc ih through handed
growth to cellular coupled peritectic growth. Run 94, 20 x.

1377 1’
of the rod with the solid composition rising in %
1375 - I I I Al from the start of solidification to the quench
21 22 at Al 24 25 point. Under G/I/ conditions adequate to avoid
_____________________________________ dendritic or cellular interfaces the phase diagram
(b) - • yP predicts a transition from -y to y’ to eutectic
II I1 structures and The
thistransition
expected from
phase
y’ sequencing
~ (Ps’) B
I • (y+y’) C was observed. to eutectic
- I A Eutectic I
I I occurred abruptly and is not of interest in this
-~ ~ . . - o A paper. The transition from plane front y growth
- I I to plane front y’ growth occurred in a zone along
~ 3 I - I I the rods. The transition zones contained either a
series of alternating y and y’ bands, a type of
2 ) • ~ ) I cellular coupled growth of the y and y’ phases,
I or a mixture of these two types of structures. Fig.
1 ~fy)1) - 3 presents a sample displaying a transition from
— 1 ° ,~ I the banded structure to the cellular coupled
I I I growth structure. The alloy began solidification as
21 22 - - 23 24 25 pure y phase which appears as the black etching
Solid composition, Cs (at % Al)
- . . - - phase at the bottom of the micrograph. Then
Fig. 2. (a) The phase diagram near the eutectic and peritectic
points [3]. (b) Comparison of the critical values of G / V from bands of the y phase began to form, first at the
Eq. (1) (the three lines labeled yP, (y + y’)P and y’P) to outer surface of the sample and later at the
experimental data, center to give the curved bands of y’ seen at the
356 iii. Lee, J.D. Verhoef-en /Journal of Crystal (irowth /44 (1994) 353 —366

bottom of Fig. 3. It is seen that about 4 to 5 and its mode of formation was studied in previ-
distinct bands of y’ are formed in a matrix of the ous work [2], where it was shown that the lower
y phase after which there is a transition to a new boundary of the band had been the location of
structure which consists of vertically oriented ir- the solid liquid interface at the moment of
regular cells of the y’ phase with the -y phase at quenching. Hence, it is seen that the upward
the cell walls. The two phases, y + y’, in this zone growing -y + y’ phases each have their growth
are seen to grow upward and terminate their fronts with the liquid positioned close to the
growth at the lower boundary of the sharp y’ same isotherm. (Quenching experiments on eu-
hand lying horizontally across the top of the tectic alloys under the growth conditions of these
micrograph. This white horizontal band of y’ experiments have shown that the heat transfer
phase has formed during the quenching operation conditions of the experimental arrangement pro-

Table I
The results of low rate experiments in Al 23, Al 23.5, and Al 24 alloys
Alloy Rate Exp. G/V f5(Q)
2) Initial
structure Transition
Coupled structure
Band Q interface
(/im/s) No. (l0~~C s/em
Al 23 0.8 106 5.18 0.87 yP No Yes Eutectic
1.1 86 3.76 0.72 yP No Yes y
1.1 85 3.76 ((.99 yP No Yes Eutectic
0.8 91 3.55 0.55 yP Yes Yes y’
0.8 48 3.14 0.58 yP Yes Yes y’
((.8 97 3.14 0.75 yP Yes Yes Euteetic
2.0 94 2.06 0.52 yP Yes Yes (y + y’)C
1.3 51 1.93 ((.48 yP Yes Yes yP, (y +
.3 64 1.93 0.45 yP Yes Yes yP. (y +
1.3 65 1.93 (1.54 yP Yes Yes y’
1.5 47 1.67 0.58 yC/D Yes No yC, (y + y’)C
2.0 55 1.25 0.39 yC/D Yes No yC, (y + y’)C’
3.2 21) 0.78 1)62 yC’/D Yes No yD. (y + y’)C
3.2 104 1.28 0.46 yC/D Yes No yD, (y + y’)C’
6 135 0.62 ((.43 yC/D Yes No yD. (y + y’)C
12 136 ((.33 (1.40 yC/D Yes No yD. (y + y’)C
20 137 ((.21) 0.44 yC/D Yes No yD. (y + y’)C
25 139 1 0.17 0.71 yC/D Yes No yD. (y + y’)C, y’. L(met), (‘(met)
30 138 (1.13 0.56 yC/D Yes No yD. (y + y’)C, y’. L(mct). C(met)

Al 23.5 ((.8 120 5.18 ((.74 yP No Yes Eutectic


((.8 114 5.18 ((.66 yP No Yes y’
3.2 III 1.28 ((.81 yC/D yes No Eutectic

i\I 24 0.8 125 5.18 ((.93 (y + y’)B No Yes Eutectic


((.8 49 3.14 ((.49 (y + y’)B Yes Yes y’
1.5 57 1.67 0.44 (y + y’)B Yes Yes y’
3.2 27 ((.78 0.44 (y + y’)C Yes No (y + y’)C. (y’). Eutectic
3.2 56 ((.78 (1.33 ()‘ + y’)C Yes No (y + y’)C. (y’)
6 142 1 )).67 ((.31 (y + y’)C Yes No (~‘+ y’)C, (y’)
6 143.1 ((.67 )).52 (y + y’)C Yes No (y + y’)C. (y’)
6 144 1 1)67 (1.62 (y + y’)C’ Yes No (y’)
6 140 ‘ (1.67 0.68 (y + y’)C Yes No Eutectic
The quench bath was GaIn. For the rest of the samples, quench was water.
P is planar, C is cellular, D is dendritie. C/D is cellular or dendritic, (y + y’)C is coupled peritectic. (y + y’)B is hands ot
periteetic phase.
The coupled structure is located at intercellular or intcrdcndritic regions.
J.H. Lee, J.D. Verhoeven /Journal of Crystal Growth 144 (1994) 353—366 357

duces planar horizontal solid—liquid interfaces.)


The growth front here appears virtually identical ID
to those observed in coupled growth of eutectic
alloys where the leading edges of the two phases
of the eutectic lie along an isotherm. The growth
mode seen in Fig. 3 is termed cellular coupled
peritectic growth for reasons discussed below. ______________________________________________
Table 1 presents a summary of the experi-
ments. The first 5 columns from the left list: the
target composition of the alloy, the velocity of
solidification, an experiment number, the ratio of
the temperature gradient to growth velocity, G/V,
and the fraction solidified at the point of quench-
ing. The 6th column gives the structure of the
alloy at the initial point of solidification, where
‘yP means a planar interface of y phase and _______ ________________ __________________

yC/D means that primary y phase cells or den-


drites were present. The banded structure is des-
ignated (y + ‘y’)B and the coupled growth struc-
ture is (y + y’)C. The 7th and 8th columns spec -______________

ify whether the y + y’ regions display the coupled _____

or banded or both structures. The last column ________________

specifies the structures observed in the solid at __________________

the quench interface. Here the interface shape _________

was preserved by the quench and it was possible __________________________


to distinguish between primary y cells versus
dendrites as is shown below. The symbols yC,
(‘y + ‘y’)C and D, (y + y’)C mean primary y _____

cells surrounded by the (y + y’)C structure or _____ __________________________

primary y dendrites surrounded by the (‘y + y’)C . - .


Fig. 4. (a) Longitudinal section of growth front of cellular
structure, respectively. The structures labeled coupled structure, (y + y’)C. Exp. 94, 80x. (b) Transverse
C(met) and L(met) will be discussed later. section of the cellular coupled structure, (y + y’)C. Exp. 56,
The banded structure. It can be seen from the 80 x.
data of Table 1 that the banded structure only
occurred for the higher values of the ratio of
G/V. At the highest G/V values the transition Fig. 4a presents a higher magnification view of
from plane front y to plane front y’ growth the quench interface region of this structure and
occurred fairly abruptly with distinct single phase one sees two horizontal interfaces. Previous work
bands, similar to the type of bands found in [2] has shown that upon quenching a band of the
previous studies of directionally solidified peritec- y’ phase grows laterally over the solid liquid
tic alloys [6—9].At lower G/V values the transi- interface and terminates the growth of the solid
tion usually involved bands that became cellular front. The upper interface marked II in Fig. 4a is
similar to the structure seen at the bottom of the top of this band and it is not of interest here.
Fig. 3. The lower interface reveals the position of the
The cellular coupled structure. The coupled growth front at the moment of quenching and
cellular structure illustrated in Fig. 3 was often illustrates that the two peritectic phases are form-
found to occur in both plane front growth and in ing along an isotherm. The important question of
the interdendritic regions between y dendrites, how much additional growth of the original front
358 iii. Lee, iD. Verhoeien /Journal oJ Crystal G,oii-ih /44 (/994) 353—366

occurred during the quench has been studied in I ‘ ‘ . - -

the previous work [21and it was concluded that


the etch is revealing the original interface posi-
tion. Hence, one sees that the y’ phase is cusped -,

upward ahead of the surrounding darker y phase


and leads it by a small amount. The amount that . -. . . . -

the y’ cusps lead the neighboring y phase is -

quite small and is similar to that observed in


coupled eutectic growth. In coupled eutectic
growth the two phases are known to grow along
an isotherm just slightly undercooled from the
eutectic temperature and it appears likely that
the two peritectic phases are growing along an
isotherm just slightly above or below the peritec-
tic temperature in this case. Therefore, it seems
reasonable to term this growth mode a type of
coupled growth because we have a pair of phases -

growing along a planar front into the liquid.


A transverse section taken just below a growth I’m. 5. I ongitudmal seCtion ol gross th trout shos’. np pi iniir\
front such as Fig. 4a is shown in Fig. 4b. One sees y cells in a matrix ot the is + y’ (C structure. I xp. )7 42 - -

that the morphology of the structure is clearly


cellular and not the highly regular lamellar or rod with 23% Al occurred for Exp. 47. and a longitu-
type structures found with eutectics. Boettinger dinal section of the quench interface region is
has presented longitudinal and transverse micro- shown in Fig. 5. The large vertical dark features
graphs of one of his alloys grown at G/V values may be considered to be either unbranched den-
below the critical value (Fig. 5 of Ref. [6]) which drites or cells of the primary y phase. The lack of
he has classified as a cellular structure. It con- side branches coupled with hemispherical tips is
tains cells of the primary phase and the growth often used as the criteria for distinguishing cells
front shows the typical cusped cell tips when from dendrites and this convention will he
viewed on transverse sections. If one compares adapted here. The distinction between yC and
the structures of Figs. 3 and 4 to his cellular yD in the final column of Table 1 is based on the
structure, they are very similar except for two presence of side branches. The two cells on the
important differences. The growth front of Fig. left in Fig. 5 display an unexpected interface at
4a here is flatter and the dominant cells here are the locations marked A. Previous work has shown
formed by the secondary y’ phase and not the that the y phase often recrystallizes during the
primary y phase. However, the larger size of the quench and the interfaces at A have resulted
/ phase must simply result from the alloy corn- from such recrystallization, and are therefore not
position being closer to pure y’ and one could significant here. Notice that the cellular coupled
consider both phases, y and y’ as having very flat peritectic growth positioned between the primary
cellular fronts. cells terminates along an isotherm lying below the
The existence of a unique temperature along tips of the primary cells, which is labeled I in Fig.
which the cellular coupled growth is occurring in 5. (Again, the interface at II forms during the
this system is further illustrated by examining the quench and is not of interest here.) All of the
transverse sections of alloys that were grown with quenched interfaces on experiments showing pri-
G/V values low enough to produce classical con- mary cells or dendrites displayed this same termi-
stitutionally supercooled cells and dendrites of nation of the cellular coupled structure along an
the primary 1, phase. The highest value of G/V isotherm appearing at temperatures below the
which produced a non planar interface in alloys cell or dendrite tips. At the lowest G/V values
J.H. Lee, J.D. Verhoeven /Journal of Crystal Growth 144 (1994) 353—366 359

found for the higher growth velocities, the struc- transverse sections were cut at a small angle to
tures became quite complex and these will be the growth front (the taper section technique
discussed later, discussed in Ref. [3]) to ensure that they were
Mixed structures. In previous work [3] it was located as close as possible to it. Because the
shown that an unusual variety of eutectic mi- solid state reactions which occur upon cooling
crostructures occur in this alloy system which modify and sometimes destroy the microstruc-
were coded R(cell), L(met) and C(met). The tures produced at the growth front, it is necessary
R(cell) structure is a rod eutectic where the /3 to quench samples at various values of fraction
phase rods are not arranged in the usual close solidified, f~(Q),in order to evaluate variation of
packed arrays in the y’ matrix, R(cp), but appear microstructure versus fraction solidified. As may
only along cell boundaries of the matrix. The be seen from Table 2, it was found that the
L(met) structure is a regular lamellar structure cellular coupled structure occurred with
composed of the metastable phases, /3 + y. In the metastable structures at rates of 10 ~.rm/s and
C(met) structure the metastable /3 + y phases solidification fractions of 0.21 and 0.40. Fig. 6
appear as alternating blades arranged along cell presents a transverse taper section at f5 0.21=

boundaries of a y’ matrix. At the higher G/V and the mixed structure consists of the two
values it was found that some of these eutectic metastable eutectic forms, L(met) and C(met),
microstructures began to appear at interdendritic plus the coupled cellular structure, (y + y’)C. The
locations mixed in with the cellular structure. It taper section passes through the solid—liquid
was difficult to understand the arrays of struc- growth front on the left side of the micrograph so
tures occurring between the dendrites because of that the quenched liquid appears in a vertical
the small regions into which they were restricted band at the left. The locations of the ~met)
by the primary dendrites. Therefore, studies were structure are the obvious lamellar regions. The
done on alloys of higher Al compositions where locations of the C(met) structure are the dark -

planar interfaces were stable to higher growth boundary regions in the larger cell structure. The
velocities and it was found that a rich variety of C(met) structure has the blade form shown in the
mixed structures were obtained along planar in- previous study [31 only along the outer regions of
terfaces under certain conditions of fraction so- the sample. In the center region where it appears
lidified and G/V. as a dark continuous phase, higher magnification
A series of experiments was carried out on an pictures show that it has a new structure not
alloy of 24.5% Al in which planar solidification found in the previous study [3] which is shown in
fronts were maintained to higher G/V values the higher magnification view of Fig. 7. This
and these experiments are listed in Table 2. Be- second form of the C(met) structure consists of a
cause the metastable eutectic products are only central /3 lamella with thin lamellae of y on
present very close to the freezing interface, the either side. Hence, it appears as a lamellar eutec-
experiments employed GaIn quenching and the tic with only three lamellae which are all wrapped
around cellular regions of the (y + y’)C structure.
Table 2 The structure of primary interest to this study
Experiments in a 24.5% Al alloy with the GaIn quench
(y +y )C is found throughout the center of the
Rate Exp. G/V f5(Q) Interface structure sample where one sees a cellular structure within
(j.tm/s) No. (10~°C
2) a cellular structure. The white y , matrix is di-
. .

s/cm vided into a large cellular array by the dark


3.2 147 1.07 0.49 y planar
152 1 07 0 77 R(cp) C(met) structure and each of these large cells is
divided into the smaller cells of the (y + y’)C
6.3 148 0.53 0.45 R(cp), y’, C(met) structure. Fig. 6b presents a longitudinal section
10 150 0.33 0.21 (y + y’)C, L(met), C(met) through the growth front which was made on the
149 0.33 0.40 (y + y’)C, C(met), L(met) half of the sample opposite that used for the
151 0.33 0.77 C(met) taper section of Fig. 6a. The micrograph contains
361) i.H. Lee, iD. Verhoei en /Journal of Crystal Growth /44 (/994) )5 ~66

sections through three structures, C(met), L(met) ‘d~~~’ T”’ ~‘ — -.

and (y+y’)C. It is important to note that even ‘.~ . “\ .

though GaIn quenching was used, a quenching “ J ,~ -

artifact appears on the growth front of each of ‘ ., . ~“r -

the larger cell regions. The actual growth front . ~ ‘ .1~ -

terminates along the faint interlace marked I . . . . . -

along which one sees that the dark y component


of the (y + y’)C structure also terminates. As has
been shown previously [1], a small cap of solid y’ ,

with very fine larnellae of y form above the large ‘~‘ ~‘ ..

cells during the GaIn quench. Fig. 6b presents .

important experimental information because it


allows one to estimate the relative temperatures ..., .

6opm -
1 ‘ -. /
Fig. 7. Upper lctt center shoss s ness ui iii il the (‘I met I
structure in the center region of Fig. 6a. Lower right shows a
neighboring L(met) structure. Exp. 15)), 215 x -

_____________ of the growth fronts of the C(met), L(met) and


______ _____________________ (y + y’)C structures.
_______ interdendritic structures at high rates. At the
highest rate studied, 61 gm/s, the interdendritic
structure was always found to he the L(met)
________________ structure. However, as shown by the data of Table
____________ I, mixed structures were found in the interden-
_____ dritic regions at rates of 25 to 30 ~cm/s in the
23% Al alloy. Fig. 8a presents a longitudinal
___________ section of the growth front for the 25 ~.rm/s
___________ -- experiment and one sees well developed y den-
drites with a sharp growth front at their base.
The transverse section of Fig. 8b at 0.5 mm below
this growth front shows several regions of both
the L(met) and C(met) eutectics. The (y + y’)C
structure appears around the periphery of all of
~ the primary dendrites and as one moves away
__________________________________________ from the dendrites the (y + y’)C structure be-
comes pure -(/ phase. This transition is probably
- the result of increasing Al composition, as one
‘iiet) ~ expects increasing Al concentration between den-
drites, and the same transition was often found in
_______________ plane front growth experiments with the (y + y’)C
______________ structures. In those experiments, the central re-
_____________ ______ gion of the rods had the (y + y’)C structure and a
_____ thin annular region of pure y’ appeared around
the periphery. Chemical analysis showed the y’
I ic. O. (a) Tapei seetioii through solid—liquid giossth runt.
Lx1, 150. 33x. (6) longitudinal section at the growth front, to he higher in % Al, which was attributable to
I xp. 151), l34~. the radially outward convection shown to he pre-
J.H. Lee, J.D. Verhoecen /Journal of Crystal Growth 144 (1994) 353—366 361

Table 3
Chemical analyses of various structures in the solidified rods
Alloy V Exp. f5 Structure C
(JLm/s) No. (Al at%)
A123 1.1 85 0.22 y 21.2
0.35 y 21.5
0.43 (center) y 21.7
0.43 (edge) (y + y’)B 22.5
0.46 (center) (y + y’)B 22.7
0.46 (edge) y’ 23.5
0.48 y’ 23.6
0.83 y’ 23.8 .1
0.87 Eutectic 24.5
0.97 Eutectic 24.5
2 94 0.47 (center) y 21.5
0.47 (edge) (y + y’)C 22.7
0.49 (y + y’)C 23.2

Al 24 3.2 27 0.13 (y + y’)C 23.2


0.15 (y+y’)C 23.5
0.40 (center) (y + y’)C 23.5
0.40 (edge) y’ + (y’ + /3) eutectie 24.2
3.2 56 0.32 (center) (y + y’)C 23.5
0.32 (edge) y’ 24.0
a These values are an average of 3 slices cut right next to each other.

sent in previous work [3]. The longitudinal sec- arises from a small convection effect as discussed
tion, Fig. 8a, gives the appearance of a well previously [3]), the portions of the center and
rounded classical cellular shape for the growth edge were cut and analyzed. From Table 3, it is
fronts of the interdendritic regions. However, possible to determine the compositions for the
careful examination of various sections at higher regions of y, (y + y’)B, (y + ‘y’)C, and y’ struc-
magnifications shows that the (y + y’)C + y’ re- tures. While the banded structure formed in the
gions are nearly flat and the rounded cell caps of narrow composition range of 22.5—22.7% Al, the
Fig. 8a result primarily from the quenching arti- (y + y’)C structure formed in a broader composi-
fact discussed above. tion range from 22.7% to 23.5% Al.
Chemical analyses. Because of the macroseg-
regation inherent in these experiments it is clearly
important to experimentally establish the solid 3. Discussion
compositions along the rods for the various struc-
tures of interest. Therefore, on several samples The previous studies on directional growth or
the solid compositions were measured for each peritectic alloys [6—9]have all found results simi-
structure along the directionally solidified rod by lar to one another and the present results will be
chemical analysis using the ICP (induction con- compared only to those of Boettinger [6].Whereas
pled plasma) technique. As has been previously directional solidification of two-phase alloys at
discussed [3], the accuracy of this technique is G/V values sufficient for plane front growth
quite good. The samples of 50 mg were cut and have always produced a banded structure of the
analyzed for regions of the samples containing ‘y, two peritectic phases in previous work, Ni—Al
y + y’ and y’ structures, and the results are shown alloys display both a banded and a type of cellu-
in Table 3. When the microstructures of the lar growth at G/V values above the critical value
center and edge regions were different (which for instability. Fig. 2 presents the phase diagram
362 i/I / Cl .1/) I er/us) in iourna/ of Crystal (,rowt/, /44 (/994) 353—366

‘.& ~ ~ I cellular coupled structure occurring at an isother-


• ... mal front, (y + y’)C, as illustrated in Fig. 4a.
Comparing these two figures it is clear that there
is a large difference in the size of the y phase
cells
pear in
in these twowhich
structures.
showsBoth
that structures ap-
________________________________________ Fig. 5, at the same

growth rate the classical y cells are larger than


_____ the y component of the (y + y’)C structure by a
factor of — 50. It therefore seems reasonable to
~ . assume that the instability mechanism induced by
- ) the constitutional supercooling which produces
I the classical cellular structure is different than
- the mechanism inducing the cellular planar (y +
jim y’ )C structure. This conclusion ts supported by
- ‘. ,.~ the data shown on the lower part of Fig. 2. The
classical cells appear at 0/V values lower than
- 1—..~ . the constitutional supercooling line of Eq. (1) on
Fig. 2 for the primaty y phase. However, the
—- ~‘.‘. . isothermal cellular structure appears at values
above the constitutional supercooling cutve for
this case of two phases growth, which indicates
the absence of the constitutional supercooling.
-- ‘ This result is different from that found by Boet-
tinger where the cellular structures of his two
phase Sn—Cd alloys occurred for values of G/V
- less than the critical values. His cells were formed
-~ . ,, by the primary phase forming along non-isother-
mal fronts and appear to be a form of classical
a - .. constitutionally supercooled induced cells.
5 - ./~ The growth front of the cellular coupled strue-
-. . I tures formed here lies along an isotherm just as
closejy as is found in eutectic alloys. This result
was observed for plane front growth as well as for
.~.. ~ . growth with primary phase dendrites or cells
I IL. 5. (.1) I ininiudiri,iI seenon it solid—liquid puiss th Ii~iiL, where the isothermal cellular front appears at
I sp. 13). 33+. (I’) Ii .tnsscise section (.5 mm hrlos~ he lower temperatures, behind the dendrite or cell
pl.in.tr front of (a). 52 . . 1 he hiniht sshite regions esull from tips. as illustrated in Figs. 5 and 8. Hence. al—
recrystallization iiii cool LII ‘Oil
though the morphology of the cellular coupled
structure formed here appears nearly identical to
the cellular structures of the Sn—Cd alloys, the
and a corresponding plot of the critical G/V present cellular structure seems to he forming by
values from Eq. (1) using the value of D evalu- a different mechanism. Because the two peritee-
ated experimentally, 1.5 x l0~ cm/s [3]. tic phases form along an isotherm in the present
One can consider that there are two levels of cellular structures, it seems reasonable that the
cellular structures found in this study. First, there temperature of the isotherm is close to the equi-
is the classical constitutionally supercooled type librium peritectic temperature and that it is ap-
of cells of the primary y phase which is illus- propriate to call the growth a type of cellular
(rated in Fig. 5 and then there is the unusual coupled growth.
J.H. Lee, iD. Verhoecen /Journal of Crystal Growth 144 (1994) 353—366 363

The shape of the y’ cells of the cellular cou- C~,must be made larger than the composition of
pled growth morphology, (y + y’)C, is character- the liquid at the y’/liq. interface, ~ This analy-
ized by a lack of regularity. If the cells were sis will begin by neglecting curvature effects on
uniform elongated cylinders, they could still ap- the phase diagram so that compositions can be
pear with irregular side walls on longitudinal taken directly from it. One can then postulate
sections because of difficulty in sectioning paral- two different models for producing the required
lel to their axes. However, the cells found here composition change. If the growth front tempera-
never come close to exhibiting straight sides on a ture were to lie above the peritectic temperature,
longitudinal section. As seen in Fig. 3, the side see T1 of Fig. 1, then the condition of C~’>C.~,is
walls of the cells move back and forth in the automatically obtained at an isothermal front. II
lateral direction (the direction normal to the the growth front temperature were to lie below
growth direction) in an apparent random mode. the peritectic temperature then it is not possible
This means that the liquid/y/y’ triple junction to achieve the required condition of C,~’>C~,
on the growth front is undergoing dynamic mo- with a truly isothermal front. In this case the
tion in the lateral direction during growth. Hence, mass transport would require the y’ phase front
it might be appropriate to term the (y + y’)C to protrude ahead of the y phase to slightly
structure a type of dynamic coupled growth. Such higher temperatures in order to satisfy the C~>
behavior is in sharp contrast to that of eutectics C~,condition, where the protruding y’ tips would
where the triple junction does not move laterally be at temperature ~‘2 of Fig. 1 and the y front at
during constant velocity growth. temperature T3.
The (y + y’)C structure appears in these ex- It is possible to show for the present experi-
periments as a type of transient structure sand- ments that the growth front temperature of the
wiched between the initial plain front grown y cellular coupled growth structures must lie below
phase and the final plain front grown y’ phase. the peritectic temperature. Fig. 6b reveals the
There is no reason to believe, however, that this growth front of both metastable eutectics, L(met)
structure could not be made to grow with con- and C(met), plus the cellular coupled growth
stant composition under steady state conditions. structure, (y + y’)C. Taking into account the small
The experiments show that the structure can be cap of solid formed during the quench, Fig. 6b
made to grow over cm or more lengths and that shows that the centerline position of the (y + y’)C
its average composition rises as it grows due to structure leads the L(met) and C(met) structures
the inherent solutal convection in this system. It by somewhere between 0 to 5 ~m. The tempera-
seems most likely that if the solutal convection ture gradient in this experiment was 3.3°C/mm,
could be eliminated from the liquid that the which means that the temperature at the center-
composition of the solid would become fixed and line of the (y + y’)C structure is hotter than the
the (y + y)C structure would form with constant L(met) and C(met) growth fronts by a maximum
composition under steady state conditions with possible value of only 0.017°C. Referring to the
respect to macrosegregation. phase diagram at the top of Fig. 2 one sees that
An essential requirement for any model of these results present very strong evidence that
coupled growth of two phases is a mechanism for the (‘y + y’)C structure must be forming at tem-
the mass transport required to partition the liq- peratures below the equilibrium peritectic tern-
uid composition into the two different composi- perature.
tions of the two solid phases. It is well established Examination of the (y + y’)C interface in Fig.
in eutectic alloys that the required mass transport 5a shows that the y’ phase does lead the y phase
occurs by diffusion in the liquid phase at the by a small amount. However, the lead distance
growth front and a similar mechanism is probably only ranges from 3 to 7 jim, which, in the liquid
occurring here in the cellular coupled growth. To gradients of these experiments, corresponds to a
transport Al preferentially into the y’ phase, the temperature increase of only 0.01 to 0.02°C.This
composition of the liquid at the y/liq. interface, small temperature difference demonstrates that
364 J.H. Lee, iD. (+rhoeren /iournal of Crystal Growth /44 (/994) 353—366

the growth front is essentially isothermal and , L


similar to the growth fronts of eutectic alloys. In V Centerhin~ r ~‘ ~

the Jackson—Hunt [10] theory of coupled eutectic \,~ ~‘ I


growth, curvature of the two phases at the solid— ‘\ )
liquid interface plays a key role in allowing the - C I
interface to remain isothermal while still provid- _.,,~ -

ing the liquid concentration difference needed to ~T0 I _________

drive the diffusion, as was nicely illustrated by ~ d


Hunt and Chilton [11]. Because of the similarity
in the isothermal nature of the (y + y’)C struc- I

ture to eutectic interfaces it seems highly unlikely I I “

that one can neglect curvature and explain the —~—-———~--—-~—~— ~ y


mass transport with a model of protruding y’ 1 C~
phase, because without a curvature effect the
concentration gradients would he too small to
drive the diffusion. Support for this conclusion
may be obtained by comparing the mean distance
between cell walls versus solidification velocity y V
for the (y + y’)C structures and the equilibrium
eutectic structures in these NiAI alloys [3], as I , L(
shown in Fig. 9. One sees that at a given velocity
the spacing is approximately the same as for the c
equilibrium eutectic. This result shows that the P r
lateral liquid concentration difference along the
interface between the two solid phases., ~C, for
the (y + y’)C structure needs to he of the same Fig. 1(1. Top: variation of curvature undereooling, il,, and
diffusional undcrcoohing. iT), hetwccn centerlines of a y /
order as that for the equilibrium eutectic to drive structure. Bottom- liquid composition profile between center-
the diffusional mass transport necessary for lines.
growth. Because curvature effects play a strong
role in providing the ~iC for diffusion in the
eutectic case, it is reasonable that curvature must
also he involved in providing the JC along the
IOC ‘‘‘‘‘I’’) II~) II. isothermal (y + y’)C structures.
Slope -0.49 Fig. 10 presents an analysis of the tradeoff
~s- ,.V between the curvature undercooling, iT., and
- diffusional undercooling, iTd, at locations along
E .-4Slope=-0.32 the solid—liquid interface between the centerlines
Slope=-0,42 ~“‘‘~ ~- of y and y’ phases for a hypothetical lamellar
10 - ~-._ - peritectic structure. The analysis is simply a mod-
a ‘+ II I ification of the eutectic analysis presented by
_.~.. rod- R(cp) and R(cell)
y’~-~ Hunt and Chilton [11], converting it to this hypo-
- .. -. y÷13Iamellar - L(met) thetical lamellar peritectic structure. The y’ een-
- 0 - y±~C(met) terline composition, C~’.has been arbitrarily taken
III) 11 II’ to lie below the peritectic composition, C0, which
(il I - 10 10(1 requires an overheating, iTo, near the centerline
- , - a e(6rn ~ . where the signs of iT and iT, are opposed.
Fm. 9. of the mean distance between cell walls in
(omparison d
the (y + y’)C structure to the various eutectic forms that The bottom of the figure shows a hypothetical
occur in this system. composition profile illustrating how the model
J.H. Lee, J.D. Verhoei:en /Journal of Crystal Growth 144 (1994) 353—366 365

meets the requirement for Cv’> C.~.At the y—y’ corresponds to the y phase, and their /3 phase to
interface the curvature undercooling was as- the y’ phase). For the case where a~> a5~,an
sumed to undergo a jump discontinuity, similar to overheating of the interface is predicted, which is
the same assumption generally made in the eu- not what is found here. For the case where a~<
tectic case. Also, similar to the eutectic case, at a~,an undercooling is predicted, and this case
the peritectic composition the total undercooling, corresponds to the present experiments. In this
iTo, is composed only of curvature undercooling, case the iT versus spacing curve does not con-
iTo. The analysis shows that there is a significant tam a minimum but increases monotonically as
difference in the requirements for the curvature the spacing decreases. Boettinger points out that
undercooling for this peritectic case versus the Cahn has shown that this condition is inherently
eutectic case. In the eutectic case the magnitude unstable to perturbations in lameUar widths and
of i7~ decreases in both phases as one moves is an additional reason why one does not expect
away from the common interface. This condition regular lamellar or rod growth for undercooled
holds for the y phase here, but in the y’ phase peritectic alloys. However, it may be that the
iT~ increases moving away from the common reason steady state growth is not observed here is
interface. This means that for the y’ phase the because of the curvature problem discussed
shape must change to produce more curvature as above.
its centerline is approached. There does not ap- At the lower G/V values the two phases do
pear to be any physical reason why this could not grow at a common front possessing the same
occur, but in view of the larger volume fraction of isothermal character as steady state coupled eu-
the y’ phase, it is difficult to construct an inter- tectic growth fronts. However, the y—y’—liquid
face shape to satisfy this condition. trijunctions do not achieve steady state conditions
Boettinger [6] has applied the Jackson—Hunt with respect to lateral motion but move laterally
analysis to the peritectic case and shown that it in a dynamic manner that produces a cellular
does predict conditions for growth of steady state microstructure with irregularly shaped cylinders
structures. The predicted dependence of iT on of the matrix y’ phase. Transverse sections of the
velocity is opposite of that for eutectic growth. cellular structure often show the individual cells
For the peritectic an increase of velocity in- with one or more protrusions of the y phase
creases the interface temperature as opposed to extending into the cell centers, as illustrated at
decreasing it for the eutectic case. Boettinger has the arrows in Fig. 4b. The cells appear to contin-
argued that this difference might give rise to an ually change their cross sectional shape as they
inherent instability for coupled peritectic growth grow from the liquid and these protrusions ap-
because the tip of a perturbation extending into a parently provide the mechanism for this change.
positive liquid temperature gradient would expe- It would appear that this structure results from
rience a higher temperature and hence require a continuous lateral motion of the trijunctions along
higher velocity. The predicted iT versus spacing the isothermal front. Trivedi [121has pointed out
relations depend on the relative magnitude of the to us that Datye and Langer [13] have found
curvature terms, solutions to the coupled eutectic growth problem
that involve sinusoidal lateral motion of the tn-
— ‘ — junctions. Perhaps the cellular coupled peritectic
a). — L5 ~ ~ a5/ — L5 ~ ~“ structure found here might be related to similar
types of solutions for the peritectic case.
where L5 and L5~are the heats of fusion per unit
volume, a~~’and o~ are the liquid—solid surface
energies per unit area and and are charac- 4. Summary and conclusions
teristic angles at the y—y’—liquid trijunction de-
fined by Jackson and Hunt (where in this applica- (1) It is found that an unusual type of 2-phase
tion the a phase of the Jackson—Hunt analysis coupled growth occurs in the Ni—Al system be-
366 .I.H. Lee, iD. Verhoeuen /iournal of C~rystalGrowth 144 (/994) 353—366

tween the peritectic y and y’ phases at certain (6) The mass transport required to produce
growth conditions and compositions. The growth the (y + y’)C structure has been discussed using
is characterized by a cellular morphology of the Boettinger’s application of the Jackson—Hunt
two phases and a growth front that is isothermal model for eutectics to peritectic systems. The
to the same extent as that found with coupled discussion shows that there are several unan-
growth of eutectic alloys. The growth mode has swered theoretical questions concerning this
been termed cellular coupled growth and coded, structure.
(y + y’)C.
(2) The morphology of this penitectic cellular
coupled growth differs from that of regular cou- Acknowledgements
pled eutectic structures in that it has a distinct
cellular form rather than the lamellar or rod The authors would like to acknowledge helpful
form. It differs from the classical cellular growth discussions with R.K. Trivedi and T.A. Lograsso.
in penitectic alloys in that the growth front is Personnel from the Materials Processing Center
isothermal, the cells are about a factor of 50 of the Ames Laboratory carried out the initial
smaller in thickness, and the cell walls are never sample preparation and the analytical chemistry
observed to be straight sided. In addition, the work. This study was performed at the Ames
structure is formed in the absence of constitu- Laboratory which is run for the US Department
tional supercooling for 2-phase growth condi- of Energy by Iowa State University under con-
tions. tract No. W-7405-ENG-82, supported by the Of-
(3) Under G/V conditions that produce cells fice of Basic Energy Sciences, Division of Materi-
or dendrites of the primary y phase, the (y + y’ )C als Sciences.
structure is found to form along an isotherm
behind the cell or dendrite tips at lower growth
rates. At higher growth rates the structure is References
present in mixtures with various eutectic mor-
phologies in interdendritic regions and it is com- [I] J.H. Lee and J.D. Verhoeven. J. Phase Equil. IS (1994)
pletely replaced by a metastable eutectic form at 136. . -.
[21J.H. Lee and J.D. Verhoeven, J. Crystal Growth 142
the highest rates studied. (1994) 193
(4) Under G/V conditions adequate to give [31J.H. Lee and iD. Verhoeven, J. Crystal Growth 143
plane front growth, the cellular coupled growth (1994) 86.
form. (y + y’)C, occurs only at lower G/V val- [41WA. Tiller, K.A. Jackson, J.W. Rutter and B. C’halmers,
ues. At higher 0/V values the two peritectic Ada Met. 1(1953) 428.
[5] B. Chalmers, Physical Metallurgy (Wiley, New York.
phases, y and y, are found to form in an alter- 1959) ~ 271—272;
nating banded structure similar to structures B. Chalmers, Principles of Solidification (Wiley, New
found in previous directional solidification stud- York, 1964) pp. 224—227.
ies of penitectic alloys. [6] W.J. Boettinger, Met. Trans. 5 (1974) 2023.
(5) Studies of plane front quenched interfaces [7] A. Ostrowski and E.W. Langer, in: Solidification and
Casting of Metals (Metal Society. London. 1979) p. 39.
containing mixtures of the (y + y )C structure [8] A.P. Tichener and J.A. Spittle, Acta Met 23 (1975) 497.
and the two metastable eutectic structures occur- [9] lID. Brody and S.A. David, in: Solidification and Cast-
ring in this system have shown that isothermal ing of Metals (Metal Society, London, 1979) p. 144.
temperature of the growth front of the (y + y’)C [101 K.A. Jackson and J.D. 1-lunt, Trans Met. Soc. AIME 236
structure lies below the peritectic temperature of (1966) 1129.
[11] J.D. Hunt and J.P. Chilton. J. Inst Metals 92 (1963) 21.
this system. (These studies have also found a new [12] R.K. Trivedi, Iowa State Univ., Ames, Iowa. private
form of the cellular metastable eutectic for this communication, 1994.
system.) [13] V. Datye and J.S. Langer Phys. Rev. B 24(1981)4155.