Scripta Materialia 53 (2005) 863–868

www.actamat-journals.com

Fabrication of bulk nanocrystalline Fe–C alloy by spark

plasma sintering of mechanically milled powder
H.W. Zhang, R. Gopalan, T. Mukai, K. Hono *

National Institute for Materials Science, 1-2-1 Sengen, Tsukuba 305-0047, Japan

Received 17 May 2005; received in revised form 30 May 2005; accepted 31 May 2005
Available online 28 June 2005

Abstract

Fully dense bulk nanocrystalline Fe–0.8wt.%C alloy was synthesized by spark plasma sintering of mechanically milled Fe–C
nanocrystalline powder. The sample sintered at 600
C was composed of 150 nm ferrite grains with nanocrystalline cementite
dispersoids, whose compression yield strength, fracture strength, and plastic strain were 1900 MPa, 3500 MPa, and 40%, respectively.
 2005 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Mechanical milling; Nanocrystal; Spark plasma sintering; Severe plastic deformation; Fe–C

1. Introduction theoretical density. Numerous traditional consolidation

Various unconventional properties such as ultrahigh
strength, high hardness, superplasticity and unique mag-
netic properties were reported for nanocrystalline mate-
rials whose grain size is less than 100 nm [1]. During the
past two decades, many techniques have been developed
to synthesize nanocrystalline materials, including inert
gas condensation and consolidation [2], severe plastic
deformation [3], crystallization of amorphous solid [4],
electrodeposition [5], and surface mechanical attrition
treatment [6–9]. However, producing industrially useful
bulk materials with the microstructure on a nanometer
scale is still a challenge for materials engineering. One
of the widely used promising methods to produce com-
mercial bulk nanomaterials with a grain size of less than
100 nm is ball milling accompanied by a subsequent
consolidation process. Due to the metastable nature of
the nanocrystalline materials, the consolidation process
must be able to eliminate extensive grain growth and
retain the nanoscale grain size while obtaining a near
*
Corresponding author.
E-mail address: kazuhiro.hono@nims.go.jp (K. Hono).
techniques, such as hot pressing [10], hot isostatic press-
ing [11] and hot-extrusion [12] can yield nearly fully
dense compacts [13]; however, recrystallization and
grain growth during high temperature consolidation
processes retard the synthesis of nanocrystalline micro-
structure. Although shock wave compaction [14] can
densify powders without substantial change in micro-
structure and composition, this is not a suitable method
for industrial applications. An artifact-free bulk nano-
crystalline Cu with a good combination of strength
(770 MPa) and ductility (30%) was developed very re-
cently by mechanical milling and in situ consolidation
[15]; however, the uncontrollable sample shape and size
may restrict its engineering applications. A process that
can be applied to produce bulk nanocrystalline materials
at moderate temperature with low applied load and fast
consolidation speed is necessary for potential engineer-
ing applications.
Spark plasma sintering (SPS) can achieve a rapid
heating rate with a pulsed electrical discharge that is
required to densify powders rapidly without substantial
grain growth. The SPS method has been used previously
to consolidate a large variety of ceramic and metal

1359-6462/$ - see front matter  2005 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.scriptamat.2005.05.039
864 H.W. Zhang et al. / Scripta Materialia 53 (2005) 863–868

powder materials to high densities [16]. The SPS method microhardness test was conducted by means of a Mitu-
was used very recently to synthesize nanocrystalline toyo Mvk-H2 model microhardness testing machine
Fe–Al with a near theoretical density with controlled with a load of 50 gf (0.49 N) at a time of 10 s.
grain growth [17]. The unique boundary cleaning effect
of the SPS process makes the powder handling more
convenient [18]. 3. Results and discussion
In the present investigation, we selected Fe–C powder
as the precursor to fabricate dense bulk nanocrystalline Fig. 1(a) shows a TEM bright field image and its cor-
materials by means of the SPS method, because a recent responding selected area electron diffraction (SAED)
study showed that the Fe–C nanocrystalline microstruc- pattern obtained from the Fe–C powder that were
ture that was produced by mechanical milling exhibits mechanically milled for 100 h. The microstructure of
strong resistance to grain growth by heating [19]. In the as-milled powder is composed of randomly oriented
addition, the Fe–C system has been used in a wide range nanograins of body-centered cubic Fe. The histogram of
of industrial applications and is not susceptible to media the grain size distribution, Fig. 1(b), is characterized by
pollution during mechanical milling with stainless steel a normal logarithmic distribution with a narrow size
balls. distribution of 1–5 nm. The mean grain size is approxi-
mately 2 nm. This microstructural feature is very
similar to that of the mechanically milled pearlite
2. Experimental reported by Ohsaki et al. [19]. Their high resolution
TEM observation revealed that little dislocation stays
Fe–0.8wt%C alloy powder was prepared by ball mill- within the grains of the nanocrystalline ferrite, and their
ing iron (99.99% purity) and graphite powder (99.999%
purity) in a Fritsch P-6 planetary ball mill. Stainless steel
media (10 mm in diameter) were used with a ball to a
charge ratio of 10:1. Powder handling was conducted
in an argon glove box to avoid contamination. Milling
was conducted at 250 rpm for 100 h, with an intermedi-
ate halt for 2 h after every 20 h milling to reduce the
temperature rise. The as-milled Fe–C powder was
packed in a graphite die with an inner diameter of
10 mm and was densified by a SPS apparatus, Sumi-
tomo Coal Mining Company Model 1050, in a vacuum
of <10 3 Pa at a load of 5.5 kN (70 MPa) for 10 min.
Temperatures of 400, 500 and 600
C were selected to
compare the consolidation behavior, mechanical prop-
erties, and constituent phases. A thermocouple placed
in the middle part of the graphite die was used to control
the temperature during the SPS treatment. The end-
products of approximately B10 mm · 5 mm were pol-
ished with SiC paper to remove surface contamination
from the graphite die and foil before conducting struc-
tural and property characterization. The density was
determined by the Archimedes method with water as a
liquid medium. The constituent phases in the as-milled
powders and SPS samples at various temperatures were
examined by X-ray diffraction using CuKa radiation.
The grains size and the microstrain in the Fe–C alloy
under different treatments were estimated by the Scherrer
function based on the experimental full-width at a
half-maximum on each diffraction peak [20]. Micro-
structural examinations were conducted by transmission
electron microscopy (TEM) using Philips CM200. Com-
pression tests were performed at a quasi-static strain
rate of 1 · 10 4 in an Instron machine using rod samples
of B2.5 mm · 5.0 mm. Because of this sample size Fig. 1. TEM observations of mechanical milled Fe–C alloy and the
limitation, only compression tests were performed. The corresponding grain size distributions.
 H.W. Zhang et al. / Scripta Materialia 53 (2005) 863–868
three-dimensional atom probe (3DAP) analysis showed
that carbon atoms were strongly segregated at the grain
boundaries, and only approximately 1.0 at.%C was dis-
solved within the ferrite grains. Since the nanocrystalline
ferrite in Fig. 1 has very similar features to that in the
previous work, a similar carbon distribution is expected
in the present sample.
The as-milled Fe–C powder was consolidated subse-
quently into bulk samples by SPS at 400, 500 and
600
C, respectively, for 10 min. The average grain size
in the various stages of the samples estimated by XRD
is summarized in Table 1 together with the values of
microhardness and relative density. A relative density
of 98.5% and an average microhardness of 6.2 GPa were
achieved in the sample sintered at 600
C (see Table 1).
The relative density and the average microhardness de-
creased with decreasing temperature. Sintering at
400
C and 500
C led to relative densities of 78% and
89%, respectively, and the average microhardness of
2.5 GPa and 5.97 GPa, respectively. Compression true
stress–strain plots of the samples sintered at 500
C and
600
C are shown in Fig. 2. The sample sintered at
500
C shows a yield strength of around 2000 MPa and
a failure strength of 2200 MPa after work hardening with
a plastic strain of 0.05. The sample sintered at 600
C
shows a yield strength of 1900 MPa and a failure strength
of 3500 MPa with a large plastic strain of about 0.40.
XRD profiles of the samples are shown in Fig. 3.
Compared to the broad diffraction peaks from the
as-milled Fe–C powder, sharper diffraction peaks are
Table 1
Grain size and lattice strain estimated by X-ray diffraction and Vickers
hardness and relative density of the samples
Grain Lattice Hardness Relative
size [nm] strain [%] [GPa] density [%]
As-milled 5 ± 0.2 0.766 ± 0.08 – –
400
C SPS 34 ± 5.3 0.278 ± 0.06 2.5 ± 1.2 78
500
C SPS 57 ± 8.2 0.237 ± 0.058 5.97 ± 1.0 89
600
C SPS 151 ± 15 0.124 ± 0.008 6.2 ± 0.3 99
Fig. 2. Compressive true stress–strain curves of 500
C and 600
C
SPS treated samples.
865
Fig. 3. XRD profiles of the Fe–C alloys before and after SPS
treatment at 400, 500 and 600
C.
observed in the SPS samples together with the diffrac-
tion peaks that are attributed to the presence of cement-
ite, indicating that grain growth, release of the
microstrain, and precipitation of cementite occurred
during the SPS process. Table 1 summarizes the grain
sizes and the microstrains of the samples estimated from
the XRD results.
Fig. 4 shows the TEM observations and the corre-
sponding grain size distributions of the samples sintered
at (a) 400
C, (b) 500
C, and (c) 600
C. The micro-
structure of the sample sintered at 400
C (Fig. 4(a)) is
characterized by an uniformly distributed nanometer-
scale ferrite and cementite, whose random orientations
are confirmed by the continuous diffraction rings in
the SAED pattern. The dark field image excited by the
cementite spot indicated by the arrowhead shows that
nanoscale cementite particles precipitate along the grain
boundaries of the nanoferrite. The grain size distribu-
tion indicates a narrow range of 5–100 nm with a mean
value of 30 nm, which is very close to the XRD measure-
ment result in Table 1 (34 nm). Compared to the sample
sintered at 400
C, larger grains are visible in the sample
sintered at 500
C (Fig. 4(b)), in which the constituent
phases were confirmed to be the same as those in the
sample sintered at 400
C. The corresponding SAED
pattern illustrates that these grains also show random
orientations. The dark field image excited by the cement-
ite spot (indicated by the arrowhead) indicates that the
amount of cementite precipitates increased in this sam-
ple compared to the one sintered at 400
C. The histo-
gram shows a rather broad grain size distribution of
10–250 nm with an average value of 50 nm. Large
ferrite and cementite grains are observed in the sample
sintered at 600
C (Fig. 4(c)). The grain size distribution
has a wide range of 50–450 nm, with an average size of
about 150 nm.
This work has demonstrated that fully dense bulk
Fe–C alloys with a grain size of 150 nm containing a
high density of cementite dispersoids can be produced
866 H.W. Zhang et al. / Scripta Materialia 53 (2005) 863–868
Fig. 4. TEM observations and the corresponding grain size distributions of (a) 400
C, (b) 500
C and (c) 600
C SPS treated samples.
from mechanically milled nanocrystalline ferrite powder
by SPS at a modest load of 70 MPa in a very short time.
The sample sintered at 600
C exhibited a good combi-
nation of strength and ductility (yield strength of around
2000 MPa, plastic strain of 40%) and uniform strain
hardening leading to a failure strength over 3500 MPa.
Nanocrystalline metals and alloys exhibit an en-
hanced yield strength following the Hall–Petch effect.
Table 2 summarizes the mechanical properties reported
in ultrafine grained iron and nanocrystalline irons pro-
duced by various methods. The yield strength of the
severely deformed ultrafine grained Fe is less than
800 MPa with plastic strains of 20–30% [21,22]. How-
ever, powder-consolidated Fe [23–25] and Fe–C nano-
crystalline alloys [26–28] show much higher strengths
ranging from 1600 MPa to 2500 MPa, but their plastic
strains are less than 10%. One of the main reasons for
the low ductility is the poor sample quality, for example,
resident porosities, impurities and poor metallurgical
bonding between particles. In the SPS process, good
metallurgical bonding between particles can be achieved
by the pulsed field activation process, which is known to
have an efficient oxide removal effect [18]. In addition,
densification to a near theoretical density can be
achieved in the SPS process for a sort sintering time with
only 10% of the load that is required for hot pressing.
These advantageous intrinsic properties of the SP
sintered materials result in good ductility with a plastic
strain of around 40%. However, localized shear defor-
mation inside shear bands usually causes limited ductil-
ity as well as the diminishing of strain hardening in
nanocrystalline metallic materials [31]. Most of the
nanocrystalline (<100 nm) and ultrafine-grained (<300
nm) Fe and Fe alloys were reported to show little or
no strain hardening, or even strain softening, in which
the shear banding was attributed to the dominant defor-
mation mechanism [21–30]. The present uniform strain
hardening effect as well as the plastic strain over 40%
in the compressive stress–strain curve of the sample sin-
tered at 600
C may imply that the deformation mecha-
nism would not be dominated by the inhomogeneous
deformation inside shear bands. The absence of local-
ized shear deformation in the present nanocrystalline
Fe–C alloy might be partially attributed to the cementite
precipitates inside the grain and along the grain bound-
aries. These would act as the obstacles of dislocation
 H.W. Zhang et al. / Scripta Materialia 53 (2005) 863–868 867

Table 2
Comparisons of the mechanical properties of bulk ultrafine grained and nanocrystalline Fe and Fe–C alloys prepared by different processes
Materials Processing Relative Grain Yield Fracture Plastic Ref.
density size (nm) strength strength strain (%)
(%) (MPa) (MPa)
Fe ECAP 100 150–300 700 700 20 [21]
Fe ECAP 100 200–400 800 800 30 [22]
Fe CC (1.4 GPa, 10 h) + HP (850 MPa, 3 h, 590
C) >99 268 1600 1480 12 [23]
Fe CC (1.4 GPa, 10 h) + HP (850 MPa, 3 h, 500
C) >99 138 2300 2000 4 [23]
Fe CC (1 GPa, 4 h) + HP (750 MPa, 30 min, 410
C) >99 80 2500 2000 6 [24]
Fe–2C HP (200 MPa, 3 h, 580
C) 80 – 1690 1690 1 [26]
Fe–1.87C HP (50 MPa, 25 min, 800
C) 92 75 1215 1544 1 [27]
Fe–10Cu HP (170 GPa, 30 min, 600
C) >99 250 1700 1600 3 [28]
*
Fe–0.8C SPS (70 MPa, 10 min, 500
C) 89 50 2000 2200 8
*
Fe–0.8C SPS (70 MPa, 10 min, 600
C) 99 150 1900 3500 40
ECAP: equal channel angular pressing, CC: cold compaction, HP: hot pressing, SPS: spark plasma sintering.
*
Present investigation.

gliding and grain rotations, which would inactivate the
shear band formation and transmission since lattice
reorientation and grain rotation usually facilitate the
formation of shear bands and their transmission [32].
The appearance of the large strain hardening effect in
this sample indicates that dislocation motions are active
in this two phase nanocrystalline material, which is unu-
sual for the nanocrystalline Fe with a grain size smaller
than 100 nm. Improved work hardening effect due to the
presence of cementite particle was also recently reported
in the ultrafine grained steel with finely dispersed
cementite particles [33]. The enhanced ductility due to
the second phase particles interacting with shear bands
was also reported in bulk metallic glasses [34] as well
as in nanocrystalline metals [35]. Detailed TEM work
is in progress to understand the unique deformation
mechanism that was observed in this two phase bulk
nanocrystalline alloy.
4. Summary
Bulk nanocrystalline Fe–C alloys with a grain size of
150 nm containing a few nanometer cementite disper-
soids were fabricated from the mechanically milled Fe
and graphite powder by SPS. Yield strength of
2000 MPa, fracture strength of 3500 MPa, and a plastic
strain over 40% were obtained. The short processing
period of several minutes and a low applied load of tens
of MPa that are required in the SPS process may enable
possible extension of the technique to industrial
production.
Acknowledgements
This work was supported in part by the Center for
Nanostructured Materials Technology (CNMT) under
the 21st Century Frontier R&D Programs of the Minis-
try of Science and Technology, Korea through the
Korea Institute of Science and Technology and by the
grant-in-aid of scientific research, Priority Area ‘‘Science
of Metallic Glass’’ of MEXT, Japan.
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