Journal of Crystal Growth 70 (1984) 497—506 497

North-Holland, Amsterdam

RAPIDLY SOLIDIFIED ALLOYS MADE BY CHILL BLOCK MELT-SPINNING PROCESSES

H.H. LIEBERMANN
Metglas Products — Allied Corporation, 6 Easlmans Road. Parsippany, New Jersey 07054, USA

Rapidly solidified metals and alloys prepared by a variety of processing techniques have held great fundamental and technological
promise since their discovery. Chill block melt-spinning (CBMS) processes are used to make rapidly solidified microcrystalline and
amorphous alloy ribbon, flake, etc. Fundamentals of CBMS processes and the rapidly solidified products which are formed are
discussed in the light ofrecent advances. Special regard is given to ribbon geometric defects (edge serrations, surface asperities, etc.).
Photomicrographs ofCBMS ribbon solidification microstructures are used to compare local solidification rates, especially in the vicinity
of ribbon defects.

1. Introduction both processes. In the free jet process, molten alloy

is ejected under gas pressure from a nozzle to form
The solidification of molten metals and alloys into a free melt jet which impinges on the substrate sur-
continuous filament or ribbon has been practiced for
nearly a century using various methods [1]. Early EJECTION MELT CRUCIBLE
GAS
SYSTEM
need to economically prepare these materials in fila-

mentary
tion
work form.
technology
on the Materials
casting
such as aspects
ofmetallic of rapidsatisfied
solidfilaments
solution solidifica-
extension,
the ROTATING
~ MOLTEN ALLOY
REE MELT
HEATING
JET
microstructural refmement, and the occurrence of
SUBSTRATE PUDDLE
metastable phases were not recognized until some WHEEL RIBBON
twenty years ago [2]. Present day processing and
materials research have lead to the development of
rapidly solidified materials with novel microstructu-
res, compositions and properties. ~FREE JET MELT—SPINNING~~
A process which is widely practiced to manufac- (FJMS)
ture continuous rapidly solidified ribbon is chill

molten alloy is brought into contact with a rapidly GAS CRUCIBLE

moving
block melt-spinning
substrate surface.
(CBMS), A in
molten
whichalloy
a stream
puddle
of PRESSURE
EJECTION _____ HEATING
MELT
tinued melt impingement; this puddle serves as a
forms on the moving substrate, resulting from con- ROTATING SYSTEM
local reservoir from which ribbon is continuously
formed and chilled. The most common substrate SUBSTRATE RIBBON
surfaces described in the literature are the inside of WHEEL ______

drums [3] or wheels [4,5], the outside of wheels /

[6—11],and belts [9]. Because ofits practicality, the
most commonly used substrate is a rapidly rotating
wheel. Two common CBMS techniques are free jet
4 PLANAR FLOW CASTING
(PFC)
melt-spinning (FJMS) [6—8]and planar flow casting Fig. 1. Schematic representations of the free jet melt-spinning
(PFC) [9,10]. Fig. 1 shows a schematic diagram of (FJMS) and planar flow casting (PFC) processes.

0022—0248/84/$03.00 © Elsevier Science Publishers B.V.

(North-Holland Physics Publishing Division)
498 H.H. Liebermann / Rapidly solid(fled alloys made by CBMS
face. In the planar flow method, the melt ejection
crucible is held very close to the moving substrate
surface, which causes the melt to be simultaneously
in contact with the nozzle and the moving substrate.
This entramed melt flow damps perturbations of the
melt stream and thereby improves nbbon geometric
uniformity. The initial quench rate and final ribbon
geometryinFJMSdependonthenatureofthemelt
puddle For example, a puddle which is smooth and
unchanging dunng the course of FJMS typically re
sults in ribbons with well-definededges and surfaces.
Such geometric uniformity is desirable because it
results in a uniform local quench rate through the
ribbon thickness.
2. Melt stream instabilities and ribbon
imperfections
The control of ribbon thickness in CBMS has
been described in terms of the propagation of a
thermal boundary layer through the molten alloy
puddle [7,12,13]. A schematic representation of the
melt puddle given by Kavesh [7] is shown in fig. 2.
In this model, a solid boundary layer forms at the
chill surface and propagates into the melt puddle to
form a ribbon. Alternatively, solidification models
based on momentum boundary layer predominance
[14,15] and a combination of thermal and momen-
tum boundary layers [16] have also been proposed.
A precise description of CBMS ribbon formation is
made difficult by the simultaneous occurrence of
heat transfer and mass transfer. Experimental evi-
dence and the comparison oftheoretical models with
experiment suggest that both of these factors may
determine ribbon thickness.
Imperfections in CBMS ribbon geometry stem
from a variety of sources which include the nature of
the molten alloy stream, the substrate, and the at-
mosphere in which melt-spinning is conducted.
Variations in the molten alloy stream during CBMS
will cause corresponding non-uniformities in the
ribbon product. For example, the relatively easy
destabilization of free cylindrical and planar jets of
molten metals and alloys [17—19]has been shown to
result from a metallic liquid having high surface
tension and low viscosity. Therefore, factors such as
melt ejection nozzle geometric imperfections and
MELT
PUDDLE A
LIQUID
LI
— MOVING SUBSTRATE SURFACE~~
T~
_______________________________
A’ A
~
A
Fig. 2. Schematic diagram showing the propagation of a
boundary layer through an FJMS melt puddle [7].
vibrations imposed upon a free liquid jet [20] can
cause premature disruption of the jet into droplets.
The finite roughness of any real substrate surface in
CBMS can cause perturbation of the molten alloy
puddle when melt-spinning at high speeds. Effects of
geometric roughness elements on the flow of fluid
over an otherwise flat surface have already been
investigated [21,22]. Melt puddle disruption caused
by substrate surface roughness elements can result in
molten alloy droplet spraying and in irregularities in
ribbon width and thickness. In addition, the presence
of foreign contaminant films on the substrate surface
during FJMS can result in complete non-wetting of
the melt on the substrate [23]. Finally, the pertur-
bation of the molten alloy puddle during FJMS has
also been found to depend on whether or not the gas
boundary layer established on the rapidly moving
substrate surface in a gaseous medium has a hyper-
 H.H. Liebermann I Rapidly solid(/Ied alloys made by CBMS 499

~
~

~\ —GAS BOUNDARY
FLOW

\~I \~..—SUBSTRATE------..-
WHEEL

Re < ReC~ut Re > Re*~ul

Fig. 3. Schematic diagram showing the influence of gas boundary layer Reynolds number on FJMS ribbon edge definition.

critical Reynolds number [24], as shown schemati-
cally in fig. 3. Fig. 4 shows the effect ofmelt-spinning
amorphous alloy ribbons in various gaseous atmos-
pheres [25]. In addition to the ribbon edge serra-
tions, melt-spinning in a gaseous environment may
cause increased ribbon surface roughness [26] and
penetration of gas beneath the melt puddle to form
small pockets in the underside of the ribbon [27,28]
as shown in fig. 5 [29]. Such small non-contact areas
result in a local loss of intimate alloy—substrate

ON

Fig. 4. Photograph of approximately millimeter wide amorphous alloy FJMS in various atmospheres.
500 H.H. Liebermann / Rapidly solid(fled alloys made by CBMS

~
•
‘~::“
‘
~
. ~
~
~ :~-~:
~
~
—. ‘ ~ o — . ‘3’... ‘3~ I. ~ ,
~•. . . . - ~. •~. ,~ .“ ~

./ • ‘•

t ~ ~ ‘~ . ~, .,

Q • , .~ .
:.
-
~
*
‘‘~

I—. 0,,~ ~Ip~

Q I.,,,
~ .• •,

~ ~ ,‘. :~ ~ —
__ 4 ,• ,~4 18 8

W
- ~ ‘ 4
*. •, ‘~

‘h” a~’~ ~
•‘
~,
,~ -

I— :• ~•.. ‘ e .

< •. 4*~ ~
cc
8

- •. -~ %-, -

I—. V S
C/) ~ •~ ~8 -,

1 mm
I- -~

Fig. 5. Micrograph showing small depressions in the substrate contact surface of melt-spun amorphous alloy ribbon.

contact which reduceslocal heat transfer and thereby 3. Melt—substrate wetting and ribbon solidification
results in a locally modified solidffication micro-
structure in the ribbon. The melt—substrate interface is of critical impor-
Many of the instabilities cited may alternately be tance in determining the extent to which the molten
attenuated by making the proximity between the melt alloy will wet and spread on the substrate surface.
ejection crucible and jet very close. In this way, the Melt wetting ofthe substrate surface is influenced by
flowing melt is entrained and made resilient against surface films and by the chemical composition si-
perturbation. However, this so-called planar flow milarity between the melt and the substrate ma-
casting (PFC) approach requires accurate control of terials. The work of Bailey and Watkins [30] sug-
the crucible-substrate gap. In any real melt-spinning gests that a tendency for mutual solubiity between
system, the substrate expands during processing and melt and substrate materials would greatly enhance
makes the gap smaller, which can constrict melt flow wetting in a static, isothermal situation. Since aver-
entirely. On the other hand, free jet CBMS has a age ribbon quench rate increaes approximately as the
substantial advantage in that the crucible may be inverse square of ribbon thickness for ideal cooling
situated sufficiently far from the substrate that no [31] ribbon geometry control and uniformity is of
alteration or disruption of melt flow occurs. great importance in the fabrication of a product
having uniform surface roughness. The distance over
 H.H. Liebermann / Rapidly solid(fled alloys made by CBMS
which the ribbon remains in contact with the sub-
strate is also an important process variable which
affects the average ribbon quench rate.
The interfacial heat transfer characteristics
between product and substrate have been mathema-
tically modeled [31—38]and have been found to be
at least partially contingent upon the nature of the
fluid flow in the area of the melt puddle. Since the
average CBMS quench rate is limited by the thick-
ness ofthe ribbon, there is expected to be a maximum
thickness for which a given solidification velocity can
be achieved. An excessively thick ribbon will exhibit
a continuous change in microstructure through its
thickness. This is a result of the change in solidifi-
cation rate through the thickness. The effects of ex-
perimental variables (heat transfer coefficient
between product and substrate, product thickness,
Fig. 6. Transverse section of high purity silicon FJMS on a steel wheel in air [38].
501
etc.) on rapidly.quenched samples have been dis-
cussed by Jones [36] and by Mehrabian [37]. Their
results show that for thin ribbon, the interfacial heat
transfer coefficient becomes dominant in establish-
ing the quench rate. Proper selection of wheel ma-
terial and design are critical factors in determining
the value of the heat transfer coefficient and, hence,
the quench rate.
4. Solidification microstructures
Substrate wetting by the molten alloy during
CBMS is essential in order to produce ribbon having
uniform geometry and to maximize thermal transport
during solidification. As an example of limited
melt—substrate wetting, fig. 6 shows the cross-sec-
1OO~4m
502 H.H. Liebermann / Rapidly solid(fled alloys made by CBMS
tion of a high purity FJMS silicon ribbon cast in air
[38]. The depressions in the ribbon underside are the
result of air boundary layer disruption of the melt
puddle during CBMS, as has already been discussed.
An example of a deviation in the solidification mi-
crostructure by limited melt—substrate contact dur-
ing CBMS is given in fig. 7 [39]. The chill crystals in
the underside of the superalloy ribbon shown are
elongated (lateral heat flow) in a local area at which
there was limited melt—substrate heat transfer (con-
tact) during CBMS. Similarly, fig. 8 shows a greater
extent of branched dendrites in the vicinity of a non-
contact area in the cross-section of superalloy rib-
bon. Microstructural coarsening can also result from
reduced average quench caused by excessive ribbon
thickness. Fig. 9 shows a scanning electron micro-
graph ofthe solidification microstructure at a tear in
Fig. 7. Scanning electron micrograph of the bottom surface ofnickel base superalloy ribbon cast on a copper substrate [39].
the upper surface of thin CBMS superalloy ribbon.
Note the highly striated structurewhich is apparently
free of branched dendrites. Fig. 10 shows a similar
tear in an excessively thick CBMS superalloy ribbon.
The variation in local cooling rate through the
thickness of a superalloy ribbon is illustrated by the
optical micrograph of fig. 11. Note that the micro-
structure changes from equiaxed chill crystal to
highly columnar to branched dendrite solidification
with distance from the substrate contact side of the
ribbon. Similar variations in CBMS superalloy rib-
bon microstructure have been already reported
[39—41].Fig. 12 shows a schematic diagram of the
four solidification microstructure zones which can
occur in the CBMS of some crystalline materials.
The region nearest the sample—substrate interface is
the chill zone and is comprised of fine equiaxed
~ 2.tm
1— -1
 ILH. Liebermann Rapidlt’ solidf/Ied alloys ‘nade by CBMS 503

TOP SURFACE

- v_ ç

NON-CONTACT AREA 15 jim

Fig. 8. Optical micrograph of nickel-base superalloy ribbon FJMS on a copper substrate wheel. Enhanced transition to branched
dendrite structure occurs above the substrate non-contact part of the sample [39].

a.
5pm
____ - . ___
Fig. 9. Columnar solidification microstructure at a tear in the Fig. 10. well-developed branched dendrite structure at a tear in
upper surface of thin FJMS nickel-base superalloy ribbon [39]. excessively thick FJMS nickel-base superalloy ribbon [39].
504 H.H. Liebermann / Rapidly solid~fledalloys made by CBMS

TOP SURFACE

I I (
$
~ ,~‘

I~ $

~O~An~

Fig. II. Optical micrograph showing the cross-section of thick nickel-base superalloy ribbon. The transition from cellular to branched
dendrite structure is clearly seen [39].

~4~Ifl!Bihllff~lihii1Ai!hf~VURh/IIUIY ~ of random orientation. A region of columnar

~ C) crystals grow out of the chill zone and ultimately
\~4I~ ~j/~ become dendritic. The presence or absence of each
1~l~I IJI’ I)~1(~/~/i1
/J~~ zone illustrated will largely depend on local cooling
f~ffl flh~91/(I 111
~II(I rate, this being related to the local velocity of the
\JI)1iJJll~JJ~iJ1Jifti ~— B substrate solid-liquid interface during CBMS. Alloy composi-
tion also influences the solidification microstructure
A equiaxed - no preferred orientation which forms.

B columnar - preferred orientation 5. Concluding remarks

The microstructures of materials can be signifi-

C columnar cellular - preferred orientation cantly altered by the conditions under which they are
solidified. These microstructures range from very
coarse dendritic structures with large amounts of
D ~ columnar dendritic - preferred orientation .

segregation, as observed in very large ingots, to the

totally non-crystalline microstructures of rapidly
Fig. 12. Schematic representation of solidification microstruc- solidified melt-spun amorphous alloys [42]. The
tures which may be found in CBMS ribbons, solidification microstructure depends on two key
 H.H. Liebermann / Rapidly solid~fledalloys made by CBMS 505

parameters: the amount of non-equilibrium under- 2.C 0,

cooling in the liquid prior to its solidification and the I

velocity of the liquid—solid interface. These para- 1.8 /Upper Breakdown
meters are controlled by the nature of the solidifi- Dendrites /
cation system, which can alter the number of he- 1.6
terogeneous nucleation sites, and by the rate of heat
extraction which, in essence, controls the velocity of 1.4
the liquid—solid interface. While solidification rates
are frequently reported in terms of liquid cooling 1.2
rates, a more meaningful description would be the ~ Cells + Dendrites
interface velocity [43]; however, it is experimentally ! 1.0
difficult to measure high values of interface velocity .?

in molten alloys. 0.8

At very low interface velocities, no geometrical Lower Breakdown
instabilities occur in liquid—solid interfaces because 0.6
there is time to dissipate thermal gradients generated
by the latent heat of fusion liberated during solidifi- 0.4 Cells
cation. An example of this type of solidification is
observed in directionally solidified eutectic alloys. 0.2
Liquid undercooling increases with decreasing tem-
perature gradient in the liquid ahead ofthe interface. o.o i

Under these conditions, a small geometric pertur-
bation in the interface will cause the formation of
cells and, finally, of dendritic columnar grains. The
regions between these primary dendrites contain
liquid. As an example, fig. 13 shows the results of an
experimental investigation in which the solidification
microstructure of a binary alloy was changed from
cellular to dendritic [46]. The microstructure ob-
served is seen to depend on the solid—liquid interface
velocity, R, the temperature gradient at this interface,
G, and the solute concentration, C
0. Just as the
original liquid—solid interface can form primary
dendrites, secondary dendrites can form from the
primary dendrites. Similarly, tertiary dendrites can
form the secondary dendrites, and so on. Dendrite
arm spacing has been correlated with the overall
solidification rate [44,45] with more rapid solidifi-
cation rates resulting in finer dendrite arm spacings.
Attempts to calculate solidification rates from such
empirical relationships have been made difficult
because of secondary dendrite arm coarsening [43].
The microstructure of melt-spun ribbons may
consist of a variety of these microstructures. Study
of microstructure as a function of ribbon thickness
can reveal the history of the local solidification pro-
cesses. At the liquid alloy—substrate interface there
is a high degree of undercooling and an extremely
0 40 80 120 160 200 240 280
3~’2/sec1/~’2
(-) K/cm
A
Fig. 13. Critical conditions for cellular—dendritic solidification
transition in alloys of tin in lead [46].
high density of heterogeneous nucleation sites. This
region of the ribbon may contain fme equiaxed crys-
tals of random orientation.
As the alloy in contact with the moving substrate
solidifies, there is no longer the large number of
nucleation sites and the temperature gradient will
have diminished. Only those equiaxed grains in the
chill zone having a preferred crystallographic growth
direction aligned with the thermal gradient will grow
into the remaining liquid. During growth of these
columnar crystals, their number decreases and the
cross-section of the remaining crystals increases.
This selective crystal growth process results in a
preferred orientation. Crystals most favorably
oriented will grow most rapidly and survive. In
nickel-base superalloys, for example, the favored
growth direction is (100). Thus, one would expect
(100) type texture in CBMS ribbons. As these
columnar dendrities grow, the temperature gradient
is reduced and the velocity of the liquid—solid inter-
face is also decreased. If this temperature gradient
506 H.H. Liebermann / Rapidly solidified alloys made by CBMS
and velocity are sufficiently diminished, the colum-
nar dendrites will start for form secondary dendrite
arms.
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