UDC 620.192.43 : 620.154.
Solidification Structure and Segregation
Iron-Chromium-Nickel Alloys*
By Taira OKAMOT 0,* * Katsuhiko KISHITAKE***
Synopsis
The equilibrium distribution coefficients
for chromiumand nickel in the
unidirectionally solidified iron-chromium-nickel alloys containing 5 to
20wt%Cr and 5 to 30wt%Ni were evaluated on the basis of the micro-
segregationratio for the alloying elements. The solidificationpaths cal-
culatedfrom the values of the coefficientswere in good agreementwith those
obtained experimentally.
The primary arm spacing in the alloys was proportional to the square
root of the inverse cooling rate. The alloys whose primary crystal is o
had slightly larger primary arm spacing than those forming r as the
primary phase. The secondaryarm spacing measuredfor somealloys was
inverseas the 0.4 to 0.5 power of cooling rate and was independentof the
alloy composition.
I. Introduction
Inhomogeneity of composition in stainless steels is
unfavourable from the standpoint of corrosion resist-
ance, heat resistance, and workability. Some works
have been reported about dendrite arm spacings and
microsegregation, which closely relate to homogenizing
kinetics, in the ternary iron-chromium-nickel system.
The segregation ratios for chromium and nickel
have been measured in many alloys with compositions
of 20wt%Cr and 6 to 80wt%Ni,1,2~ 26wt%Cr and
19wt%Ni,3~ and 14 to 26wt%Cr and 6 to 35wt%Ni.4~
According to Siegel and Gunzel,4,5~ the two alloying
elements caused " like manner " segregation in the r
phase and " unlike manner " segregation in the o
phase. Although this interesting phenomenon has
been found, any method to predict the segregation
ratios in the alloys has not been presented yet.
In order to find a parameter describing the segre-
gation ratios, iron-chromium-nickel alloys are most
suitable as experimental materials, because the dif
fusivities of chromium and nickel in solid iron are
comparable and the liquidus and solidus of this system
are given in detail.6~ Even though diffusion of both
chromium and nickel occurred in solid during and
after solidification, the segregation for these elements
would be decreased to the same extent because of the
comparable diffusivities for the two elements.
The iron-chromium-nickel alloys with composi-
tions at which the peritectic reaction occurs consist of
the both phases of o and r at room temperature. In
the alloys that form the o phase as the primary crystal,
a difficulty has been encountered in observing the
dendritic structure of the primary phase, because the
dendritic isoconcentration lines of solutes become in-
distinct on account of the appearance of the secondary
* Received September 4, 1980.
** The Institute of Scientific and Industrial Research, Osaka University,
*** Formerly The Institute of Scientific and Industrial Research,
Sensui-cho, Tobata-ku, Kitakyushu 804.
in
and Kenji MURAKAMI* *
phase. Accordingly, the primary arm spacing of
columnar dendrites in these alloys could not be mea-
sured. For iron-chromium-nickel alloys the relation
of primary arm spacing to an average cooling rate
during solidification has been examined for only an
alloy with 26wt%Cr and 19wt%Ni,3) that forms r as
the primary phase. On the other hand, the relation-
ship between secondary arm spacing and cooling rate
during solidification has been examined for the two
alloys with compositions of 26wt%Cr and 19wt%Ni,3)
and of 26wt%Cr and 2lwt%Ni.'~ Commercial alloys
generally contain many components. It is desirable
to represent the effect of alloying elements on dendrite
arm spacings in these alloys by a definite parameter.
The present work has been carried out to find out
factors influencing the microsegregation behaviour
and the dendrite arm spacings in the ternary iron-
chromium-nickel alloys within the composition range
of 5 to 20wt%Cr and 5 to 30wt%Ni. This alloy
system may be apt for an understanding of the effects
of chemical compositions and solidification variables
on the dendritic structure and the microsegregation in
ternary alloys.
II. Experimental Procedure
Iron-chromium-nickel ternary alloys with the com-
position ranging from 5 to 20wt%Cr and from 5 to
30wt%Ni were made from electrolytic iron, electro-
lytic nickel, and electrolytic chromium. Each alloy
weighing about 1 kg was molten in an alumina cru-
cible in vacuum by use of a high frequency induction
furnace and was poured into an exothermic mould
placed on a water-cooled copper chill in the atmo-
sphere. The size of the mould cavity was 2.7 x 3.9
cm at the top, 2.5 x 3.6 cm at the bottom, and 10.5
cm in height, as shown in Fig. 1. The melt in the
mould was covered with exothermic powder so as to
achieve upward unidirectional solidification. Table
1 shows the chemical composition of alloy ingots made
in the present work.
Solidification variables were determined by thermal
analysis during solidification at three given locations
of 2.5, 4.5, and 6.5 cm from the bottom of the ingots.
For the thermal analysis, Pt-20 %Rhf Pt-40 %Rh ther-
mocouples (0.5 mm diameter) protected by double
silica sheaths of 2 mm i.d. and 4 mm i.d. were hori-
zontally placed in the mould cavity through the mould
wall at the three locations. The temperatures at the
Yamadaoka, Suita 565.
Osaka University. Now at The Kyushu Institute of Technology,
Research Article (641)
 (642) Transactions ISIJ, Vol. 21, 1981

locations of stationary thermocouples in a solidifying in the reagent presented by Moharil et al.8~ in order
metal were recorded against time after pouring. From to observe the dendritic structure of the primary phase.
the curves obtained, the cooling rates at the beginning The reagent was prepared by adding hydrochloric
of the solidification were given by measuring the acid (specific gravity 1.19) of 7 cc into 50 cc of an
slopes of the cooling curves below the liquidus tem- aqueous solution with 23% sodium thiosulfate before
perature. use.
Each ingot was longitudinally cut in half and half The fineness of dendritic structure was represented
of it was transversely sectioned at several locations for by primary and secondary arm spacings which were
metallographic examination and X-ray microanalysis. measured on transverse and longitudinal sections, re-
The sectioned surface was polished and then etched spectively. Microsegregation of nickel and chromium
on the transverse section was examined by use of an
electron probe microanalyzer at the condition of an
accelerating voltage of 20 kV and a sample current of
0.02 pA. Distribution profiles of nickel and chro-
mium on the transverse section were taken by line-
scanning through the centre of a primary arm and at
an angle of 45° to the secondary arms branched from
the primary arm.

III. Results
1. Microsegregation
Photograph 1 shows the dendritic structures on
transverse and longitudinal sections of all the alloy
ingots presented in Table 1.
Distribution profiles of chromium and nickel were
measured on the transverse section where the cooling
rate was about 1.3 K/s, some examples of which being
shown in Figs. 2 and 3. The profiles for the alloy
ingots except Alloy C' (the distribution profile in
Alloy C' was not measured) reveal a concentration
minimum at the centre of each primary dendrite arm
and concentration maxima in the interdendritic re-
Fig. 1. A schematic drawing of a mould for unidirectional gion. On the other hand, Alloy C has serrated solute
solidification of Fe-Cr-Ni alloys. distribution profiles that resulted from a duplex struc-

Table 1. Chemical composition, equilibrium distribution coefficient and microsegregation for chromium and nickel
in the alloy ingots.

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 Transactions ISI1, Vol. 21, 1981 (643)

Photo. 1.
Microstructures of the alloy
ingots on (a) transverse and
(b) longitudinal sections.

ture of r and o phases formed during and after solidi- dendritic region.
fication and the small peaks on the nickel distribution The microsegregation behaviour of the alloying
profile correspond to the valleys on the chromium elements is best represented by following the composi-
one. Smoothing the peaks and valleys gives solute tion change on the distribution curves of nickel and
distribution which had been taken if only the o phase chromium and drawing it on the iron-chromium-
would have been formed. Thus, it is known that the nickel ternary phase diagram. The results are illu-
distribution of chromium in this alloy shows a con- strated by arrows in Fig. 4. These arrows give us
centration maximum at the centre of each primary information on the directions of composition changes
dendrite arm and nickel is concentrated in the inter- of solidifying solid, along which compositions of the

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(644) Transactions ISIJ, Vol. 21, 1981

Fig. 2. Solute distribution in Alloy I along a line schemati-

cally shown as P-R.

Fig. 4. Solidification paths drawn together with the liquidus

and solidus isotherms in the Fe-Cr-Ni ternary phase
diagram presented by Schurmann and Brauckmann.

Fig. 3. Solute distribution in Alloy C.

Fig. 5. Primary arm spacing dl as a function of coo] mg rate

solid at dendritic solid-liquid interfaces should vary
V.
as solidification proceeds. Although arrows are drawn
with straight lines, strictly they are slightly curved.
In Table 1 the values of S; are presented, where S; 2. Dendrite Arm Spacings
denotes the ratio of the limiting concentration (maxi- 1. Primary Arm Spacing
mum or minimum concentration) of element j (j = The primary arm spacing in an ingot becomes
Cr, Ni) in the interdendritic region to the concentra- larger with the distance from the bottom of the ingot,
tion at the centres of primary dendrite arms. When i.e., with a decrease in the cooling rate during solidi-
Si value for an alloy is larger than unity, this value is fication. The relationship between primary arm spac-
equal to the segregation ratio. Furthermore, the ing, d1, and cooling rate, V, is summarized for all the
values of K; are tabulated in Table 1, where K; denotes ingots in Fig. 5. This figure makes it clear that the
the ratio of the concentration of element j at the centre primary arm spacing is roughly proportional to the
of each primary dendrite arm to the mean concentra- square root of the inverse cooling rate and is written
tion of the ingot. Plotting S~ against li ~, we obtain a by the following equation;
line with a negative slope of about -2.0. d1= A/V"2 ........................(1)
When the arrow for an alloy ingot in Fig. 4 is ex-
tended in its opposite direction, it intersects the iron- where A is a constant depending on alloy composition
chromium or iron-nickel axis. Intersection with the and its value is equal to the primary arm spacing at a
iron-chromium axis means that the ingot has SNi unit cooling rate.
value larger than Scr value, whereas intersection with To reveal the effect of alloy composition on the
the iron-nickel axis inverts the above relation. Thus, primary arm spacing, the value of A is plotted against
the direction of each arrow plays an important role composition in Fig. 6. This figure indicates that the
in the segregation behaviour of the alloying elements. primary arm spacing in the ternary iron-chromium-
When an alloy forms r as the primary phase and its nickel alloy increases slightly with decreasing chro-
chromium content is larger than about 10wt%, the mium or nickel content so long as the primary crystal
ratio SNI/Scrdecreases with increasing nickel content is r and that it abruptly increases to a greater value
and chromium content. For the alloys forming r as when the alloy forms o as the primary phase.
the primary phase, SNivalue tends to decrease to unity 2, Secondary Arm Spacing
with an increase in nickel and chromium contents, The secondary arm spacing, d2, in some alloy ingots
and Scr value is from 1.13 to 1.21. The alloys with is plotted against cooling rate, V, on a log scale in
the o primary phase have larger SNivalues and smaller Fig. 7. There exists a linear relationship, whose slope
Scr values, as compared with the alloys having the r being -0.4 to -0.5 except -0.32 for Alloy D. The
primary phase. slope is relatively larger than the theoretical value9~
 Transactions 'Sri, Vol. 21, 1981 (645)

Fig. 6. Variation of the value A that is the primary arm

spacing at a cooling rate of 1 K/s, as a function of
composition.

Fig. 8. Secondary arm spacing of some alloy ingots at a

cooling rate of 1 K/s.

Fig . 7. Secondary arm spacing d2 of some alloy ingots as a

function of cooling rate V.

of -1 /3. The secondary arm spacing at a given cool-

ing rate is illustrated as a function of nickel content in
Fig. 8.

Iv. Discussion
Fig. 9. A portion of the liq uidus and solidus of the Fe-Ni
One of the aims of the present work is to obtain binary system.
parameters predicting the segregation ratio and den-
drite arm spacings of multi-component alloy castings
and ingots. For this purpose, we need a precise phase the diffusion of solutes in solid is neglected, we can
diagram for the alloy system concerned, but the phase express the solidification path as follows;
diagrams of binary iron-nickel and ternary iron-chro-
miun-nickel systems differ significantly among inves- far
S = l
s
CNi
(''CCr --k - -
(1-kCr)/ (l-kNI)
.........(2)
tigators. In Fig. 9, a portion of the binary iron- NiC0i
nickel phase diagrams is shown. It is clear that, where Co and Cs denote the initial and solidifying
besides the liquidus and solidus temperatures them- solid concentrations of element j (j = Cr, Ni ), respec-
selves, the solidification range at a given composition tively, and k3is the equilibrium distribution coefficient
differs significantly among three diagrams. for element j. Furthermore, on the above assump-
Since S~value is near unity in the composition range tion, the values of li 3 and S;, which are tabulated in
concerned in the present work, the solidification range Table 1, can be written as functions of only the equi-
can be within a few degrees Kelvin. The solidifica- librium distribution coefficient as follows;
tion range of the phase diagram presented by Jenkins
et al.'°~ is greater than 20 K, while that of Schiir- K; = k3 ...........................(3)
mann and Brauckmanns~ does not exceed a few degrees log S; = n(1-k)-log k~ ...............(4)
Kelvin. Moreover, the solidus of the binary iron-
nickel phase diagram for the construction of the ter- where n is a constant. From these relations, even
nary iron-chromium-nickel phase diagram of Jen- though the equilibrium distribution coefficients for the
kins et al. passes through a minimum below that of the solute elements in the concerned alloy are not known,
liquidus. there are some clues to determining them. From
Eqs. (3) and (4), a relation is found between S~ and
1. Microsegregation K~, as shown experimentally. On the other hand,
Assuming that solute redistribution in a dendritic- when the solidification path for a ternary alloy is
ally solidifying alloy follows Scheil's equation and that known, we can calculate the equilibrium distribution

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(646) Transactions ISIJ, Vol. 21, 1981

coefficients directly from the phase diagram.

When solid state diffusion of chromium and nickel
occurred appreciably during and after solidification
and reduced the inhomogeneity of the elements in the
solid, the lengths of arrows in Fig. 4 should be shorter
than those in the case of no solid state diffusion. The
directions of arrows, however, are considered to be
nearly coincident with those of solidification paths,
because the diffusion coefficients for chromium and
nickel in solid iron are comparable.
Equilibrium distribution coefficients for chromium
and nickel in alloys exclusive of high nickel and high
chromium alloys were calculated from the solidifica-
tion paths shown in Fig. 4 and from the phase diagram
given by Schurmann and Brauckmann, the values Fig. 10. Relation between the corrected equilibrium dis-
being summarized in a column k; in Table 1. The tribution coefficient and S~ value.
value of k3 is expected to be a little smaller than the
value of K3 as a result of solute diffusion in solid.
Each of the alloys with lOwt%Ni around and at
which Schurmann and Brauckmann concentrated
their efforts on determining the phase diagram has
K3 value slightly greater than k; value, but the others
have relatively large differences between the former
and the latter. Values of S; for these alloys are also
apparently different from the values calculated by
substituting k~values and 0.25 as n value into Eq. (4).
These facts imply that some of k1 values determined
from the phase diagram are incorrect. Based on the
values of K~ and S~, corrected equilibrium distribution Fig. 11. Relation between the corrected equi librium dis-

coefficients, k; , were estimated and given in Table 1. tribution coefficient and K~ value.

The values of S3 and K3 are plotted against corrected

values, k', in Figs. 10 and 11, respectively, where the
K~-k' plot is given by K3=0.92k7-0.01 and the S3-k;
curve is expressed by Eq. (4), where n value is equal
to 0.25. Solidification paths calculated by using
corrected values as the values of k in Eq. (2) are in
very good agreement with the results illustrated in Fig.
4. This evidence also indicates that k' values given
in Table 1 are accurate enough to be used as the
equilibrium distribution coefficients.
When the primary phase is r, the equilibrium dis-
tribution coefficient for nickel increases to get nearer
unity with increasing chromium and nickel contents
and that for chromium decreases with increasing chro-
mium content. It is of interest to note the direction
of the arrow of Alloy C that forms o as the primary
crystal. As solidification proceeds in this alloy, nickel
is rejected into interdendritic liquid, whereas chro-
mium is concentrated in solid. All the arrows exclu-
sive of this one take the directions from the left-below
to the right-above in the figure and show " like man-
ner " microsegregation for the solute elements.
Now that equilibrium distribution coefficients k'
have been known over a wide range of composition,
the solidus isotherms given by Schurmann and Brauck-
mann in Fig. 4 can be modified using k7 values and
the liquidus isotherms. The results are shown in Fig.
4 by broken lines. Obtained solidus isotherms deviate
remarkably from those presented by Schurmann and
Brauckmann in the chromium rich and nickel rich
region where the primary crystal is r.
2. Dendrite Arm Spacings
1. Primary Arm Spacing
Okamoto and Kishitake11 have proposed an equa-
tion to predict primary arm spacings of dendrites in
binary alloys as follows ;
d1= a[-m(1-k)DC0/V]"2 ...............(5)
where d1 is the primary arm spacing, a is a constant
that is smaller than unity, m is the liquidus slope, k is
the equilibrium distribution coefficient for a solute, D
is the diffusion coefficient of a solute in the liquid, Ca
is the initial solute content, and V is the cooling rate.
For iron base binary alloys Eq. (5) has been written
as follows;l2~
d 110[mCa(k--1)]1/6
1= -----V /2 - - ...............(6)
where d1, m, V, and Co are given in units of pm,
K/wt%, K/s, and wt%, respectively. Although the
above expression was deduced from a study on binary
alloys, it can be extended to a ternary system using
the gross value of a parameter, mC0 (/c*_ l).13) In
the similar way to the previous work on the iron-
carbon-chromium ternary alloy, the values of the
parameter mCo (k*-1) for the alloys used in the pres-
ent work were calculated on the basis of the modified
ternary phase diagram, ranging from 1.9 to 4.3 K.
The corrected gross equilibrium distribution coeffi-
cient k* was obtained from the experimentally deter-
mined solidification path and the revised iron-chro-

mium-nickel phase diagram.
The primary arm spacing obtained for each alloy
ingot was plotted against the value of [mC0(k*-1)]l/s/
V1j2 on a log scale in Fig. 12 together with the line
describing the relationship of Eq. (6). These data
could roughly be classified into two groups: i.e., the
group of closed symbols, which is of as the primary
phase, and the group of open symbols. The alloys
forming r as the primary phase have slightly smaller
primary arm spacings than those forming o as the
primary phase. Figure 6 shows that A value in Eq.
(1) increases slightly with decreasing solute content
so long as the primary phase is r and that the transi-
tion of the primary phase from r to 5 is accompanied
by an abrupt increase in the A value without a dis-
continuous change of the parameter mCo(k*-1). The
latter phenomenon has also been found in iron-car-
bon-chromium alloys.13~ The reason for the abrupt
change in the A value may be attributed to larger
diffusion coefficients of solute elements in the o phase
than in the r phase, the ratio of the two being of the
order of the second power of ten.s,14~
The approximately linear relationship plotted in
Fig. 12 requires the constant, in Eq. (6) greater than
110 pmK113s-"2. It seems that some of the iron base
binary phase diagrams15~ used by Kishitake and
Okamoto in their study are suspicious, as known from
Fig. 9 for the iron-nickel phase diagram. If larger
equilibrium distribution coefficients are used in these
binary alloys, which correspond to narrower solidifica-
tion range, the constant will be larger than the value
given above and the equation will fit the obtained data
more closely.
2. Secondary Arm Spacing
In the case of a binary alloy, secondary arm spac-
ings are expressed by the following equation modified
from Kattamis-Coughlin-Flemings's equation ;9)
D Tolog k 1
2 - 8--- k -1
V ..................(7)
where d2 is the secondary arm spacing, TT0is the liq-
uidus temperature, and B is a constant. It was found
Fig. 12. Primary arm spacing di as a function
[mCo(k*-1)] )]l/6/V1/2for Fe-Cr-Ni alloys.
Transactions ISIJ, Vol. 21, 1981 (647)
that secondary arm spacings of aluminum-copper and
aluminum-silicon alloys were expressed well by this
equation.'° The relation between secondary arm
spacing and cooling rate for the iron-chromium-
nickel alloys differs somewhat from that of Eq. (7) .
In the present work secondary arm spacings of most
alloys were inverse as the 0.4 to 0.5 power of cooling
rate, this index number being larger than the value
of 1/3 that is expected from the equation. A similar
result has also been obtained from the study for an
alloy with 26wt%Cr and 19wt%Ni by Sugiyama
et al.3~ The reason for the result was not made clear
in the present work. For applying Eq. (7) to a
ternary alloy, a gross equilibrium distribution coeffi-
cient should be used. Since how to determine the
gross coefficient, however, was unknown, the parame-
ter, log k/(/c- 1), was calculated by substituting the
value of the corrected gross equilibrium distribution
coefficient k* into k. The values of the parameter for
the alloys whose secondary arm spacings were mea-
sured are in the range from 0.45 to 0.47. This fact
implies that the secondary arm spacing is insensitive
to the alloy composition.
V. Conclusions
Microsegregation and dendrite arm spacings have
been investigated in unidirectionally solidified iron-
chromium-nickel alloys with compositions less than
20wt%Cr and less than 30wt%Ni. The results ob-
tained are summarized as follows:
(1) Primary arm spacings of dendrites in the alloys
are proportional to the square root of the inverse
cooling rate and undergo an abrupt increase with the
change of the primary crystal from r to o.
These spacings are larger than those expected from
the equation that describes the relation of primary
arm spacings to solidification variables and alloy com-
positions in iron base binary alloys. This may be
attributed to the propriety of the binary phase dia-
grams used in deducing the equation.
(2) Secondary arm spacings are inverse as the 0.4
to 0.5 power of cooling rate and are of similar values
for some alloys used for measuring them. This may
be attributed to that the alloys have a similar value of
the parameter, log k*/ (k*-1), that is a main factor
influencing secondary arm spacings.
(3) The equilibrium distribution coefficients for
chromium and nickel were obtained in all the alloys
investigated in the present work. It is found that the
segregation ratio and the solidification path of every
alloy are closely related to the distribution coefficients.
(4) The equilibrium distribution coefficients were
also given from the phase diagram made by Schur-
mann and Brauckmann. The values, except for the
alloys containing about lOwt%Ni, however, differed
apparently from those obtained in the present work.
Acknowledgements
The authors were favoured to have the assistance of
Mr. Kohno who contributed to the accomplishment
of of the experimental program.
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