Phase TransformationInduced Grain Refinement in Rapidly

Solidified Ultra-High-Carbon Steels

K.P. COOPER and H.N. JONES III

Superplastic forming offers a promising approach for reducing the cost of high-performance metal
components with complex shapes. Severe thermomechanical deformation is one method for producing
the fine grain structure needed to permit superplastic forming economically. Our approach to generating
fine-grained microstructures is by cyclic heat treatment of rapidly solidified material. First, a metastable
structure is produced by rapid quenching of the liquid metal. Then, solid-state phase transformations
at modest temperatures are employed to refine this structure. In the ultra-high-carbon steels (UHCS)
studied, the brittle as-cast structure of martensite and austenite was transformed, after cyclic heat
treatment, to a ductile mixture of 1-m ferrite and 0.25-m carbide. Varying the heat-treat temperatures
by 100 C within the transformation range had little effect on the scale of the microstructure. Higher
C resulted in coarser carbide spheroids, addition of Al refined the microstructure, and the finest mean
carbide size was obtained with an intermediate level (5 pct) of Cr. Refinement of the martensite plates
retained austenite via cyclic tempering and austenitization was found to be the key step in the overall
mechanism for phase transformation-induced grain refinement in rapidly solidified UHCS.

I. INTRODUCTION yield parts of near-net shape with desirable properties at

SEVERAL processing routes are available for the manu-
facture of precision parts, but they often involve an undesir-
ably slow or complex series of steps. A method of near-net-
shape forming that is increasingly being explored involves
fewer processing steps comprised of producing particulate
material with a desired fine-scale microstructure and hot
pressing the particle aggregate into the final geometry in a
single step. Alloys that exhibit superplastic behavior are
ideal candidates for this method of processing. In principle,
high-performance structural components having complex
shapes such as gears, wear rings, piston rings, shaft seals,
compressor hubs, and guided missile aft-closures can be
fabricated economically. One class of alloys in which super-
plasticity has been demonstrated is ultra-high-carbon steels
(UHCS).[1] When these steels are processed to produce sub-
m spheroidized carbide within a ferrite matrix of a few
microns grain size, high room-temperature strength and duc-
tility and excellent high-temperature formability via super-
plastic deformation are likely.[1] Conventionally processed
UHCS are brittle at room temperature due to the presence
of proeutectoid carbide along the grain boundaries. The ther-
momechanical processing techniques developed by Sherby
and co-workers[2,3,4] involve breaking up this carbide net-
work and producing a fine-scale microstructure. Thermome-
chanically processed UHCS exhibit engineering strains in
excess of 20 pct at room temperature at tensile stress levels
above 800 MPa.[5]
Unfortunately, the extensive hot and warm working neces-
sary to produce the fine microstructures in UHCS is expen-
sive and places limits on product geometry. However, if
fine-scale microstructures could be produced in powdered
UHCS, then hot pressing, involving superplastic flow, should
K.P. COOPER, Metallurgist, and H.N. JONES III, Materials Engineer,
are with the Naval Research Laboratory, Materials Science and Technology
Division, Washington, DC 20375. Contact e-mail: cooper@anvil.nrl.navy.mil
Manuscript submitted December 3, 2001.
competitive costs. This approach was attempted by several
researchers[6,7,8] using gas atomized powders. They all
reported superplastic behavior but at low consolidation rates.
Efforts to refine the microstructures through thermal treat-
ments alone were met with limited success.[9] In all cases,
the initial microstructures of the material were not suffi-
ciently fine scale to permit direct superplastic forming.
Results from these studies made it clear that if rapid consoli-
dation of UHCS is to be achieved, then the ferrite and carbide
grain sizes must not exceed 1 to 2 m. For the grains to be
able to slide past each other and to rotate with respect to
one another to achieve superplastic deformation, they need
to be sufficiently fine scale.
Our studies attempted to overcome some of the limitations
mentioned previously by employing a much higher cooling
rate process, chill-block melt spinning, than achieved in
liquid metal atomization. According to Kavesh,[10] cooling
rates by melt spinning are estimated to range between 105
and 108 K sec1. When quench rates approach these values,
extended solid solutions and other metastable microstruc-
tures are possible.[11] The goal of this research work was to
produce a fine-scale size and spherical morphology in UHCS
through rapid solidification and cyclic heat treatment alone.
Preliminary results indicated that fine-grain structures were
possible by this approach.[12] The rapid solidification route
to grain refinement was reasonably successful with ternary
Al-Cu-Si alloys. Grain sizes of Al were a few microns across
and the -Al2Cu and (Si) phases were sub-m in size.[13]
Most of the previous work on UHCS employed alloy
chemistries that resulted in the formation of dispersed car-
bide of composition near the binary Fe3C. Deliberate alloy-
ing of the carbide phase was avoided in order to prevent
hardening it and thus impeding plastic flow.[3] It has been
shown, however, that alloying with Cr can help to stabilize
the carbide while still permitting high flow rates.[14] Unless
such a means is employed to stabilize the carbide particle
size, significant coarsening can occur which can impede

METALLURGICAL AND MATERIALS TRANSACTIONS A U.S. GOVERNMENT WORK VOLUME 33A, SEPTEMBER 20022789
NOT PROTECTED BY U.S. COPYRIGHT
 Table I. Nominal Compositions of Alloys Investigated
Composition (Wt. Pct)
Alloy C Al Cr
165 1.5 2.0 0.0
166 2.0 2.0 0.0
179 1.5 2.0 2.0
189 2.0 2.0 2.0
232 3.0 2.0 2.0
233 2.0 0.0 2.0
257 2.0 2.0 5.0
258 2.0 2.0 10.0
259 2.5 2.0 2.0
flow.[15] Minimal microstructural coarsening during defor-
mation is another requirement for superplastic behavior. In
this work, the alloying approach was expanded to using
higher levels of C and Cr as well as employing Al. Increasing
the C content lowers the martensite start, Ms , temperature
and increases the strength of the steel. Addition of Cr raises
the A1 transition temperature, expands the ferrite field, and
prevents graphitization. Addition of Al also raises the A1
temperature.[1] The research plan was to precipitate the car-
bide phase from a rapidly solidified supersaturated austenite
solid solution and achieve grain refinement via judicious
thermal cycles.
II. EXPERIMENTAL PROCEDURE
Ultra-high-carbon steels containing varying amounts of
pure C, Al, and Cr were arc melted under argon and cast
into elongated bars. Alloy designations and their nominal
compositions in weight percent are given in Table I. A
20-g slice cut from the bar was placed in a quartz crucible,
induction melted, and melt spun on a Cu-Be alloy wheel
spinning with a surface velocity of 50 m s1. The resulting
melt spun ribbon was about 2-mm wide and 20-m thick.
Melt spinning was done in a partial helium gas environment
to avoid oxidation of the ribbon. For Alloy 189, a portion
of the ribbon was quenched in liquid nitrogen (LN2) to
complete the martensite reaction.
Cyclic heat treatment involved three stages illustrated in
Figure 1, which also includes, for reference, the eutectoid
(A1) and eutectic (Te) transformation temperatures for the
binary Fe-C system. The heat treatments were done on small
quantities of ribbon (about 1 g), which were first sealed in
quartz capsules that were evacuated and back filled with
partial atmosphere of helium. In the first stage, designated
HT1, the as-cast sample was given an initial tempering treat-
ment below the A1 temperature for 60 minutes. In the second
stage, designated HT2, the HT1-treated sample was austeni-
tized above A1 but below Te for 4 minutes and water quenched
to room temperature. In the third stage, designated HT3, the
HT2-treated sample was given a final tempering treatment
below A1 for 60 minutes. For all alloys investigated, HT1,
HT2, and HT3 temperatures were held constant at 600 C,
850 C, and 600 C, respectively. For Alloy 189, the HT1
and HT2 temperatures were varied to investigate the effect
of heat-treat temperature on the microstructure and its scale.
HT1 was varied as 400 C, 500 C, and 600 C and HT2
was varied as 825 C, 850 C, and 900 C.
The phases in the as-cast and LN2-quenched ribbons were
2790VOLUME 33A, SEPTEMBER 2002
Fig. 1Schematic diagram showing the heat-treatment cycles given to
as-cast UHCS melt-spun ribbons.
identified using standard X-ray diffraction (XRD) analysis.
For microstructural analysis, the ribbon samples were
mounted in stainless steel clamps and their cross sections
were ground and polished, the final polish being with 0.5-m
diamond paste. The polished samples were lightly etched
with very dilute (0.2 pct) Nital solution and examined in
a high-resolution scanning electron microscope (HRSEM).
Microstructural evaluation involved identification of the
phases present and determination of their size and shape.
The spheroidized carbide phase was evaluated for mean size,
aspect ratio, and volume fraction. Foils of Alloy 189 ribbon
samples were prepared using ion milling and examined in the
transmission electron microscope (TEM). Martensite plate,
ferrite grain, and carbide phase were identified and their
sizes determined in the TEM.
Because our rapid melt-spinning process produced a
highly wrinkled ribbon, samples for a tension test could not
be prepared and tensile strength could not be measured.
However, by simply bending and folding a portion of the
ribbon onto itself, we were able to make a qualitative deter-
mination of the ductility of the material. If the sample frac-
tured readily, i.e., as soon as it was bent, it was considered
friable. If it fractured after folding it through 180 deg 2, it
was considered brittle. If it did not fracture after repeated
180 deg folds, it was considered ductile. The bend and
fold test was useful because it was a way to determine
the presence of brittle or ductile phase constituents. An
indication of the grain structure and the extent of deformation
during fracture were obtained by breaking the ribbon sam-
ples in tension (using two vise grips) and observing the
fracture surface in the SEM. This tension test was per-
formed only on Alloy 189 ribbon samples.
III. RESULTS
Microstructural and XRD analyses of the ribbons showed
that the as-cast structure consisted of a mixture of austenite
METALLURGICAL AND MATERIALS TRANSACTIONS A
 (a)

(b)
Fig. 2X-ray diffraction analysis of Alloy 189 melt-spun ribbon. (a) as-
cast sample showing austenite ( ) as the majority phase. (b) LN2-quenched
sample showing martensite (M) as the majority phase.

and martensite with the carbide phase decorating the prior

austenite grain boundaries. The proportions of austenite and
martensite depended upon the C content. Ribbons with lower
C had more martensite, while ribbons with higher C had
more austenite. Figure 2 shows the XRD traces for the as-
cast and LN2-quenched Alloy 189 ribbon samples. Indexing
the reflections revealed a mixture of austenite ( ) and mar-
tensite (M). As shown in Figure 2(a), austenite is the majority
phase in the as-cast sample. It appears that in this alloy, the
initial solidification structure was austenite that partially
transformed to martensite as the solidified ribbon cooled to
room temperature. Quenching a portion of the ribbon in
liquid nitrogen was an attempt to transform the retained
austenite into martensite. As shown in Figure 2(b), an
increase in martensite did occur in the LN2-quenched sample,
but the transformation to martensite was not complete. The
SEM micrographs of as-cast and LN2-quenched Alloy 189
ribbon samples appear in Figure 3. The as-cast structure
(Figure 3(a)) shows prior-austenite columnar grains or cells
decorated by a continuous thin film of carbide (C). The fine-
scale carbide phase is not present in sufficient quantity to
show in the XRD traces. While martensite plates are not
clearly resolved in the as-cast sample, they are clearly visible
in the LN2-quenched sample. Prior-austenite cells are about
Fig. 3SEM micrographs of Alloy 189 cross sections. (a) As-cast micro-
structure showing columnar austenite grains and carbide (C) at the grain
boundaries. (b) LN2-quenched, showing martensite plates (M) and carbide
(C) at prior-austenite cell or grain boundaries.
0.5-m wide and several microns long. In the LN2-quenched
structure (Figure 3(b)), the carbide phase (C) appears discon-
tinuous and the martensite plates (M) appear to lie across
several prior-austenite cell boundaries. A TEM micrograph
of the Alloy 189 as-cast ribbon appears in Figure 4. It shows
a martensite plate (M) that is about 0.5 m thick and a few
microns long and austenite grains ( ) that are a few microns
in diameter and composed of a few subgrains.
The initial heat treatment, HT1, which was a tempering
cycle, was designed to form a ferrite carbide mixture.

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 33A, SEPTEMBER 20022791


Fig. 4Bright-field TEM image of as-cast Alloy 189 ribbon showing
martensite (M) plate surrounded by austenite grains ( ).
Fig. 5SEM micrograph of Alloy 166 ribbon cross section showing graph-
ite phase (G) in a ferrite matrix after the initial tempering treatment, HT1,
at 600 C.
The heat-treat time of 60 minutes was deemed sufficient to
achieve this structure. The SEM and XRD confirmed the
presence of ferrite carbide in all alloys except in Alloy
166. In Alloy 166, which had 2 pct each of C and Al and
no Cr, a ferrite graphite (G) mixture formed after HT1,
as shown in Figure 5. Alloy 165 also had no Cr, but C was
sufficiently low to ensure a ferrite carbide mixture after
HT1. Figure 6(a) shows the microstructure obtained after
HT1 in Alloy 189. The carbide phase appears coarsened
and somewhat spheroidized, but still exhibits a degree of
elongation. Elongated carbide particles were 0.1-m across
and several microns long, while spheroidized carbide parti-
cles were 0.06 to 0.20 m in diameter. The ferrite grains
2792VOLUME 33A, SEPTEMBER 2002
could not be resolved in the SEM. However, in the TEM,
ferrite grains ( ) were easily identified and appear to sur-
round elongated, network-type carbides (C) that are several
microns long, as shown in Figure 7(a). Figure 7(b) shows
a dark-field image of the ferrite grain 1. This typical grain
is 0.25-m across and 1-m long.
The goal of the intermediate austenitizing and quench
heat-treat cycle, HT2, was to achieve a fully martensitic
matrix structure with a dispersion of fine-scale spheroidal
carbide. Such a structure was achieved in all alloys with the
exception of the higher Cr alloys. In Alloys 257 (5 pct Cr)
and 258 (10 pct Cr), a ferrite carbide mixture formed.
Figure 6(b) shows the typical microstructure obtained in
Alloy 189 (2 pct Cr) after the HT2 treatment. The martensite
plates could not be resolved in the SEM, but the fact that
this sample was friable, suggests that the matrix phase is
mostly martensite. Also, SEM examination of other alloys
after HT2, for instance, the lower C Alloy 179, showed
martensite plates and fine spheroidized carbides, as demon-
strated in Figure 8. In the as-cast structure (Figure 8(a)), the
martensite plates are coarse with very fine, barely visible,
carbide films (C) at prior austenite grain boundaries. After
HT2 (Figure 8(b)), the martensite platelets are much finer
with finely dispersed spheroidal carbide (C) uniformly dis-
tributed throughout the structure.
The final heat treatment, HT3, which was also a tempering
cycle, was designed to achieve a ferrite carbide mixture
from the fine-grained martensite. Figure 6(c) shows the typi-
cal microstructure obtained after HT3 for Alloy 189 and it
consists of a mixture of ferrite and spheroidized carbide.
The ferrite grains could not be resolved in the SEM, but
were clearly identified in the TEM. The TEM micrograph
in Figure 7(c) shows spheroidized carbide (C) surrounded
by fine-grained ferrite ( ). The dark-field image in Figure
7(d) shows one of the larger ferrite grains (1), which is
0.25-m across and about 1-m long.
Results of the quantitative analysis of the carbide size,
shape, and volume fraction after HT2 and after HT3 treat-
ments for the alloys investigated appear in Table II. In most
alloys, the mean carbide size increases after HT3 from that
obtained after HT2. However, this increase is modest and
varies from 10 to 20 pct. In the higher C samples, Alloys
232 and 259, the carbide size actually decreased. The differ-
ence in the aspect ratio before and after HT3 is well within
the measurement uncertainty (standard deviation) and is not
considered significant. The mean aspect ratio varies from
1.4 to 2.8 after the HT2 cycle and from 1.6 to 2.3 after the
HT3 cycle. These values suggest that the carbides were near
spheroidal with some slightly elongated. The carbide phase
volume fraction increases after the HT3 treatment for all
alloys from that after the HT2 treatment. After the HT3
treatment, the carbide volume varied from 21 to 43 pct. The
carbide volume fraction appears to increase with C content
after both cycles.
The scale of the carbide phase was determined as functions
of HT1 and HT2 temperatures for Alloy 189 and as functions
of C, Al, and Cr contents. These measurements were made
after HT2 and HT3 heat treatments. The temperature and
the alloy content effect results are plotted in Figures 9 and
10, respectively. The plots show data points for mean particle
size and the standard deviation. The plots show data points
for mean particle size and the standard deviation. The plots
METALLURGICAL AND MATERIALS TRANSACTIONS A
Fig. 6SEM micrographs of Alloy 189 cross sections. (a) HT1 heat treated, showing coarsened carbides, some elongated, some spheroidal, in a ferrite
matrix. (b) HT2 heat treated, showing fine-scale carbide spheroids in a martensite matrix. (c) HT3 heat treated, showing spheroidized carbide in a ferrite matrix.

in Figures 9(a) and 9(b) show the dependence of carbide
size on HT1 and HT2 temperatures, respectively. Both car-
bide sizes (after HT2 and after HT3) appear to be unaffected
by HT1 and HT2 temperatures. Any variations are small
and well within the error bar. Carbide size is slightly larger
after HT3 compared to that after HT2, which was observed
earlier. Plots in Figures 10(a) through (c) show the depen-
dence of carbide size on C, Al, and Cr, respectively. Carbide
size after both HT2 and HT3 increases with increase in C
but decreases with addition of Al. The trend in carbide size
with increase in Cr appears to have a minimum. Carbide
size was smallest, 0.12 m, in the intermediate (5 pct) Cr
content sample. An examination of the microstructure of
Alloy 257 ribbon after HT3 (Figure 11) shows a bimodal
distribution for the carbide phase.
A summary of the qualitative determination of the fracture
mode from the bend and fold tests is given in Table III.
With the exception of the high C Alloy 232 and the high
Cr Alloy 258, the as-cast ribbons were brittle, reflecting a
structure that was mostly martensitic. Except for Alloy 166,
which has higher C and no Cr, all HT1-treated ribbon sam-
ples were somewhat ductile, reflecting the presence of the
ductile ferrite carbide mixture. With the exception of the
higher Cr Alloys 257 and 258, the HT2-treated samples were

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 33A, SEPTEMBER 20022793

Fig. 7TEM micrographs of heat-treated Alloy 189 ribbon samples. (a) HT1 treated, bright-field image showing elongated carbide (C) surrounding ferrite
grains ( and 1). (b) Dark-field image showing shape and size of ferrite grain 1. (c) HT3 treated, bright-field image showing spheroidized carbide (C)
and ferrite grains ( and 1). (d ) Dark-field image showing shape and size of ferrite grain 1.

extremely brittle or friable. Ductility in the higher Cr alloys
after HT2 treatment was attributed to the presence of fer-
rite carbide instead of martensite carbide. Regardless
of the structure obtained after HT2, all HT3-treated ribbon
samples were ductile, demonstrating the presence of fer-
rite carbide.
Micrographs showing the tension test fracture surfaces
for Alloy 189 ribbon samples appear in Figure 12. Figure
12(a) shows an elongated grain structure, and intragranular,
cleavage-type failure mode highlighting the brittleness of
the as-cast ribbon. Figure 12(b) shows an equiaxed grain
structure and a mildly dimpled fracture surface showing
some ductility in the HT1-treated sample. The structure after
the HT2 treatment is also equiaxed, as shown in Figure
12(c), but the fracture is intragranular and emphasizes the
extreme brittle nature of the sample. After the HT3 treatment,
the grain structure remains equiaxed, as shown in Figure
12(d), and the extensively dimpled, cup-cone fracture sur-
face reflects the good ductility observed in this sample.
IV. DISCUSSION
During chill-block melt spinning of metals and alloys that
solidify with a single crystalline phase, the grains almost
always have a columnar morphology. The grains nucleate
at the surface of the ribbon that is in contact with the spinning
wheel and grow from the wheel-side surface to the upper
free surface. These columnar grains are generally only a few
microns in diameter, but some of them propagate nearly all
the way through the ribbon thickness. In the UHCSs we
studied, the columnar grains were 1 to 2 m in diameter
and the distance they propagated was about 20 m, which
was the average thickness of the melt-spun ribbon. In some
alloys, especially those with higher Cr, columnar grains were
present but did not extend through the ribbon cross section.
In these alloys, the longer dimensions of the grains were no
more than 5 m.
Both Cr and Al are ferrite stabilizers, but the C content
was sufficiently high to promote the formation of metastable
austenite as the initial solidification product. In alloys that
contained Cr, a thin carbide film formed on the austenite
cell boundaries. During subsequent cooling of the solidified
ribbon to room temperature, the austenite partially trans-
formed to martensite. Martensite formed in spite of the fact
that both C and Cr lower the Ms and Mf temperatures, C
having a stronger effect. From Speich and Leslie,[16] we
estimate that C alone, at 2 wt. pct, lowers the Ms to well

2794VOLUME 33A, SEPTEMBER 2002 METALLURGICAL AND MATERIALS TRANSACTIONS A


Fig. 8SEM microstructures in Alloy 179 melt-spun ribbon cross sections.
(a) As-cast structure showing coarse martensite plates and faint carbide
films (C). (b) HT2 (HT1 600 C HT2 900 C) heat-treated structure
showing fine martensite plates and spheroidal carbide (C).
below 100 C. The enhanced cooling rate was such that the
eutectoid reaction, which would have produced pearlite, was
METALLURGICAL AND MATERIALS TRANSACTIONS A
bypassed and the ribbon was placed in the martensite trans-
formation regime. The transformation to martensite was not
complete even after quenching in LN2. This suggests that
C and Cr suppressed the Mf temperature well below the LN2
temperature, even after the partition of these elements to the
carbide phase. The ability of Cr to form the carbide phase
instead of graphite was illustrated by the microstructures of
samples that were subsequently heat treated. In fact, we
discovered that with C contents 2 pct and higher, Cr additions
were necessary to avoid the formation of graphite. While
heat-treated microstructures in most alloys were the same
as if they were predicted by the binary Fe-C phase diagram,
microstructural evolution in the higher Cr alloys took a
different path. Instead of forming the friable martensite
carbide mixture after HT2, a ductile ferrite carbide mixture
formed. This is because both Al and Cr expand the ferrite
phase field, and, at the HT2 temperature, the higher Cr alloy
samples were still within the expanded ferrite phase field.
Hence, the product phases remained ferrite and carbide.
Remarkably, the structure after HT2 was fine scale, high-
lighting the ability of Cr to stabilize the carbide and prevent
it from coarsening.
One result of this research was the establishment of certain
parametric ranges. For instance, varying the initial tempering
temperature HT1 and the intermediate austenitizing tempera-
ture HT2 had no significant effect on the final carbide particle
characteristics such as mean size and aspect ratio. Thus, as
long as HT1 was sufficiently high but below the critical A1
temperature, variations in this temperature, within limits,
did not affect the scale of the carbide phase and, by inference,
the ferrite grain size. In the case of the austenitizing tempera-
ture, HT2, we established a range of temperatures above the
critical A1 temperature that had little effect on final carbide
characteristics. These results are encouraging in one
respectthat they suggest that critical control of heat-treat
temperatures may not be necessary during processing. It
must be noted that the heat-treat temperatures that we
selected were fairly low, never exceeding 900 C to synthe-
size the fine-grained material, nor were the heat-treat times
excessive. While the variations in heat-treat temperatures
appear forgiving, it would be worth investigating variations
in time at temperature. If fine-scale final structures are dem-
onstrated with shorter heat-treat times, then the economic
viability of the processing will be enhanced.
As expected, increasing the C content resulted in coarser
carbide. However, C below 2 pct would be unsuitable
because the desired higher strength would not be achieved.
Having 2 pct Al was beneficial because it resulted in reduc-
ing the scale of the microstructure. This supported the claim
that Al can be a grain refiner for UHCS. Our result is
in agreement with the findings of Kum,[17] who reported
reductions in prior austenite grain size and pearlite interla-
mellar spacing with additions of Al in thermomechanically
processed UHCS. The finest mean carbide size was obtained
in the intermediate composition, 5 pct Cr, sample. In fact,
the carbide phase in this sample had a bimodal size distribu-
tion. The coarser carbides appear to decorate ferrite grain
boundaries and they were probably those that formed after
the HT2 treatment. The finer carbides appear within the
grains as precipitates and they probably formed after the
HT3 treatment. The bend and fold test did confirm that these
ribbons were very ductile. Retention of the fine scale of the
VOLUME 33A, SEPTEMBER 20022795
 Table II. Quantitative Analysis of the Carbide Phase for Some of the Alloys Studied (HT1 600 C)
HT2 (850 C) HT3 (600 C)
Alloy Mean Size (m) Aspect Ratio Volume (Pct) Mean Size (m) Aspect Ratio Volume (Pct)
179 0.15 0.07 1.41 0.49 9.8 0.18 0.12 1.67 0.64 23.2
189 0.19 0.07 1.50 0.87 11.5 0.21 0.09 1.72 0.73 37.5
232 0.37 0.30 2.82 2.68 24.1 0.27 0.13 1.68 0.80 35.7
233 0.30 0.18 1.85 1.05 23.2 0.37 0.16 1.59 0.49 38.4
257 0.12 0.05 1.60 0.59 14.9 0.12 0.06 1.77 0.66 21.4
258 0.13 0.06 1.66 0.60 25.8 0.15 0.07 1.58 0.65 31.3
259 0.38 0.20 2.55 1.29 23.2 0.37 0.18 2.27 1.01 42.9

consisted of continuous proeutectoid carbide at prior-

(a)
(b)
Fig. 9Mean carbide size determined after HT2 and HT3 heat treatments
for Alloy 189 as functions of heat-treat temperatures. (a) Initial tempering
temperature, HT1. (b) Intermediate austenitization temperature, HT2.
carbide demonstrated the stability of the Cr-rich carbide
phase. If the fine-scale carbide spheroids serve as pinning
points for the ferrite grains, then the achievement of fine
scale superplastic structures would be accomplished. Greater
that 5 pct Cr resulted in coarser carbide size, which is not
beneficial.
The starting structure in the melt-spun ribbon is very
different from the starting ingot-cast structure of superplastic
UHCS produced by thermomechanical processing,[18] which
austenite grain boundaries surrounding colonies of pearlite.
Both the carbide phase and the pearlite colonies were much
coarser than the phases found in the melt-spun ribbons stud-
ied here. The finest thermomechanically processed micro-
structures, comprised of 0.30-m ferrite and 0.22-m
carbide, were obtained via a very complex processing sched-
ule involving hot and warm working followed by divorced
eutectoid transformation with associated deformation.[18]
This structure exhibited excellent superplastic behavior.
However, the complexity of each stage, the high strain (1.0),
high temperatures (1100 C), and long processing times
make thermomechanical processing an expensive route to
grain refinement.
In our process, we tried to achieve grain refinement by
cyclic transformation of a rapidly solidified metastable
microstructure. The as-cast structure consisted of a mixture
of retained austenite and martensite with carbide decorating
the prior austenite grain boundaries. While the austenite
grain dimensions in the plane of the ribbon were in the
micron range, the grain dimension perpendicular to the rib-
bon was several microns. The elongated or columnar nature
of the grain structure was an outcome of directional heat flow
typical of melt spinning. In general, the shorter dimension of
the austenite grains and of the martensite plates did not
exceed 2 m, which is a very fine scale that is achieved in
as-cast UHCS.
From an analysis of the microstructural evolution after
the various stages of heat-treat cycles, a mechanism for grain
refinement via rapid solidification and phase transformation
is proposed and is illustrated in Figure 13. Neither homoge-
neous nucleation nor microstructural scale is implied by this
schematic representation. In the diagram, the as-cast ribbon
structure is represented by a martensite plate (M) within a
prior austenite cell or grain. Retained austenite (Ret ) is
marked as such. The austenite grain is decorated by a contin-
uous film of carbide (proeutectoid C). At HT1 temperature,
tempering or spheroidization of the martensite plate occurs
resulting in a ferrite grain ( ) having the same dimensions as
the martensite plate and a distribution of carbide precipitates
(spheroidized C). Also, eutectoid transformation of the
retained austenite phase takes place resulting in many
smaller grains of ferrite ( ) and carbide (eutectoid C). The
latter reaction is analogous to the formation of a divorced
eutectoid structure that involves uncoupled growth. In addi-
tion, the carbide film at the prior-austenite grain boundary
coarsens and becomes discontinuous resulting in partially
spheroidized (spheroidized C) and elongated (network C)
carbide phases. Although TEM analysis showed that the

2796VOLUME 33A, SEPTEMBER 2002 METALLURGICAL AND MATERIALS TRANSACTIONS A

 (a)

Fig. 11SEM micrograph after HT3 heat treatment of Alloy 257 (5 pct Cr)
melt-spun ribbon showing bimodal distribution of the carbide phase.

Table III. Qualitative Analysis of Failure Modes from the

Bend and Fold Tests
Alloy As-Cast HT1 HT2 HT3
165 brittle NA NA NA
166 brittle brittle friable ductile
179 brittle ductile friable ductile
189 brittle ductile friable ductile
(b) 232 ductile ductile friable ductile
233 brittle ductile brittle ductile
257 brittle ductile ductile ductile
258 ductile ductile ductile ductile
259 brittle ductile friable ductile

render the material unsuitable for superplastic consolidation.

(c)
Fig. 10Mean carbide size measured after HT2 and HT3 heat treatments
as functions of alloy composition: (a) C content, (b) Al content, and
(c) cr content.
ferrite grain size was in the 1-m range and the bend and
fold test showed that the sample was somewhat ductile,
the semicontinuous, elongated nature of the carbide would
Thus, while a fine-grained ferrite was achieved after HT1,
the carbide morphology was undesirable, necessitating the
subsequent heat-treat cycles.
At HT2 temperature, austenitization of the ferrite car-
bide structure obtained after HT1 occurs with most of the
C going into solution. Dispersed along the austenite grain
boundaries are carbide spheroids resulting from completion
of coarsening and spheroidization of the elongated carbide
present after HT1. Fine-grained austenite is formed because
the finely dispersed pro-eutectoid carbides provide a profu-
sion of nucleation sites as well as pinning sites for retarding
grain growth. A rapid water quench completes the HT2 cycle
preserving the fine scale structure and, during which, the
majority of the austenite grains transform to martensite (M),
with little rejection of C. The martensite plates thus produced
have maximum dimensions no greater than those of the
austenite grains, with most martensite platelets even smaller.
There is little retained austenite after the quench because
the carbide (C) present in the structure prior to quenching
removes enough C from solution to raise the Mf temperature.

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Fig. 12SEM micrographs showing fractured surfaces of Alloy 189 ribbons. (a) As-cast, showing columnar grains and intragranular brittle failure. (b)
HT1 heat treated, showing equiaxed grains, mild pullout, and marginally ductile failure. (c) HT2 heat treated, showing equiaxed grains and intragranular
friable failure. (d ) HT3 heat treated, showing considerable pullout and ductile failure.

The grain structure appears equiaxed, and the untempered
martensite makes the sample extremely brittle or friable a
condition that would be beneficial for comminution of the
ribbon into powder. The refinement of the martensite plates
after HT2 is clearly illustrated in Figure 8. We believe that
this is the key step in the overall mechanism for phase
transformation-induced grain refinement.
The HT3 treatment is a repeat of HT1 and tempering of
the fine-grained martensite into fine-grained ferrite ( ) and
finely dispersed carbide (C) occurs. The largest ferrite grains
were about 1 m in length and the carbide particles were
sub-m in size, the average size being only slightly coarser
than the carbide particles obtained after HT2. Thus, while
the scale of the ferrite grains was not reduced from that after
HT1, the size of the carbide phase was definitely refined
and its shape spheroidized. Although the tempering was
done at a relatively high temperature of 600 C and for 60
minutes, the presence of Cr prevented significant coarsening
of the carbide phase and the presence of the carbide pre-
vented coarsening of the ferrite grains. A ductile fracture
mode and the equiaxed nature of the phase constituents
suggest that this structure may be suitable for superplastic
forming and consolidation.
For the intermediate (5 pct) Cr Alloy 257, the previously
described grain refinement mechanism would not apply
since the HT2 heat treatment produced a ferrite carbide
mixture instead of the fine-scale martensite produced in the
2 pct Cr alloys. In the higher Cr alloys, all we achieved was
thermal cycling within the ferritic region. These alloys need
to be studied further to determine the effects of the tempera-
ture cycles on the scale and morphology of the microstruc-
ture as well as to determine the effect of higher Cr on the
superplastic behavior.
This work has demonstrated that it is possible to produce
a grain-refined ductile structure in UHCS by heat treatment
of a fine-scale, supersaturated initial structure. Because the

2798VOLUME 33A, SEPTEMBER 2002 METALLURGICAL AND MATERIALS TRANSACTIONS A


Fig. 13Schematic diagram showing proposed mechanism for producing
fine-scale microstructures in UHCS via rapid solidification and phase trans-
formation. M is martensite, is retained austenite, and is ferrite.
fine ferrite grains can have similar crystallographic orienta-
tions, the flow properties of the ferrite may be less than
optimum. This is because solid-state phase transformations
generate product phases that demonstrate only a few variants
of well-defined crystallographic orientation relationships
between parent and product phases. Adjacent product phases
can thus exhibit orientations that are closely related to one
another. Boundaries between such closely related grains may
not be as free to slide past one another under an applied
load as are randomly oriented grains. In this work, crystallo-
graphic orientation relationships between adjacent ferrite or
martensite grains were not determined, but in a previous
study involving the binary Fe-1.85 wt pct C, Spanos et al.[19]
reported highly misoriented martensite grains in austenitized
and LN2-quenched melt-spun ribbon sample. The more
extensively transformed microstructures reported here might
be expected to exhibit highly randomized boundaries. Both
the grain size refinement and the randomizing of orientations
should increase the rate of flow under applied load when
the temperature is high enough to permit the creep processes
that make superplastic flow possible.
V. SUMMARY
Rapid solidification and phase transformation processing
of UHCS resulted in ultra-fine (0.2 m), spheroidized car-
bide surrounded by fine-grained (1-m maximum dimen-
sion) ferrite matrix. This fine-scale microstructure was
achieved solely with cyclic heat treatment of melt-quenched
material performed at modest temperatures and without
deformation processing. The minimum attainable ferrite
grain size was limited by coarsening of the dispersed carbide
particles during the second austenitizing heat treatment. The
METALLURGICAL AND MATERIALS TRANSACTIONS A
fine-scale structure achieved by this process exhibited ductil-
ity in a bend and fold test, and it may be a good candidate
for net-shape forming of components via superplastic con-
solidation. We determined that varying the heat-treat temper-
atures within the respective phase fields and over a range
of 100 C did not unduly influence the microstructural char-
acteristics such as scale and distribution. While increasing
C resulted in coarser carbide, adding 2 pct Al resulted in
finer carbide and an intermediate 5 pct Cr gave the finest
carbide size. With the exception of the higher Cr samples,
the key to grain refinement was refinement of the martensite
plates and retained austenite phase. During the intermediate
austenitization step, a high density of nucleation sites were
provided for the fine-grained structure to form.
ACKNOWLEDGMENTS
The authors thank J.D. Ayers for his suggestions and
critical evaluation and R. Vardiman for performing the
TEM work.
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