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Consolidation of Iron Nanopowder by Nanopowder-Agglomerate Sintering at

Elevated Temperature

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DOI: 10.4150/KPMI.2013.20.1.001

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J. Kor. Powd. Met. Inst., Vol. 20, No. 1, 2013

DOI: 10.4150/KPMI.2013.20.1.001

<PM리뷰>

Consolidation of Iron Nanopowder by Nanopowder-Agglomerate

Sintering at Elevated Temperature
Jai-Sung Lee*, Joon-Chul Yun, Joon-Phil Choi and Geon-Yong Lee

Department of Metallurgy and Materials Science, Hanyang University, Ansan 426-791 Korea
(Received February 12, 2013; Accepted February 25, 2013)

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Abstract The key concept of nanopowder agglomerate sintering (NAS) is to enhance material transport by controlling
the powder interface volume of nanopowder agglomerates. Using this concept, we developed a new approach to full
density processing for the fabrication of pure iron nanomaterial using Fe nanopowder agglomerates from oxide powders.
Full density processing of pure iron nanopowders was introduced in which the powder interface volume is manipulated
in order to control the densification process and its corresponding microstructures. The full density sintering behavior of
Fe nanopowders optimally size-controlled by wet-milling treatment was discussed in terms of densification process and
microstructures.
Keywords: Iron nanopowder, Agglomerate sintering, Full densification, Microstructure
································································································································································································································

1. Introduction for the application of nanopowders to the pressureless

sintering method.
The potential application of nanoscale materials as The authors’ group reported that nc Ni-Fe powder
novel structural or functional engineering materials largely compacts sintered conventionally underwent the densifi-
depends on the consolidation of powders into bulk nanos- cation process strongly depending on the state of powder
cale solids. The retention of the metastable microstruc- agglomeration [4]. The consolidation was incomplete due
ture in the course of this consolidation process is mandatory to a severe influence of particle agglomeration. While
for preserving the often superior mechanical, magnetic, intra-agglomerate porosity could be eliminated almost
or catalytic properties of the material [1]. Various authors completely, inter-agglomerate porosity largely proved to
showed that pressure-assisted sintering proves particularly resist densification. Consequently, full densification of
adequate for both reaching full density and preventing nanopowder compact even at elevated temperature could
grain growth [2]. be achieved by optimizing the agglomerate size through
Besides the fabrication of nanoscale materials into either high-pressure compaction or reducing agglomerate
engineering components by hot pressing or sinter forg- size.
ing, another promising objective is the application of Based on these experimental findings, recently, Lee et
nanoscale powders to the net-shaping technique as pow- al. [5-7] have suggested a new technology for fabricat-
der injection molding. In this case pressureless sintering ing net-shape PM parts utilizing cost-effective Fe based
at elevated temperature is required. It is well known that nanopowders. These Fe based nanopowders produced by
agglomeration reduces the achievable packing density, hydrogen reduction of ball-milled Fe base oxide mixture
causes difficulties in mixing, and severely inhibits densi- are characteristics of agglomerated nanopowder structure
fication [3]. Since the tendency for cohesion between [8-11]. The sintering studies revealed that the densification
particles increases with decreasing particle size, the prob- process of such nanopowder agglomerates strongly depending
lem of particle agglomeration may be principal obstacle on the agglomerate size can reach full density even by

*Corresponding Author : Jai-Sung Lee, TEL: +82-31-400-5225, FAX: +82-31-406-5170, E-mail: jslee@hanyang.ac.kr

1
2 Jai-Sung Lee, Joon-Chul Yun, Joon-Phil Choi and Geon-Yong Lee
low temperature sintering [4,7,12-14]. The key concept
of the full density nanopowder sintering is based upon
so-called NAS process in which the sintering kinetics is
governed by material transport through the hierarchical
interface structures of the nanopowder agglomerates
[7,13,14]. From studies of the densification process
[4,7,12-14] and the diffusion process [15-17], it has been
found that the hierarchical grain boundaries consisting of
nanograin boundaries and agglomerate boundaries act as
preferred diffusion paths for densification.
This experimental finding provides a breakthrough in
processing full density nanopowders by optimal design of
the agglomerate microstructure. Based on this processing
concept, the authors succeeded in fabricating a nanograin
structured Fe-Ni powder injection molded part with full
density and superior mechanical property due to grain
refinement effect [5-7]. Thus we attempt to apply the
NAS process for fabricating pure Fe nanopowder material
with full density and high strength. The idea of processing
full density Fe nanomaterial on the basis of NAS process is
basically distinguished from many previous studies on the
consolidation of Fe nanopowders [18-20]. In this study, the
full density sintering behavior of Fe nanopowders optimally
size-controlled by wet-milling treatment is discussed in
terms of densification process and microstructures.
2. Experimental Procedure
Fe nanopowder agglomerates with optimal size were
prepared by hydrogen reduction of ball-milled iron oxide
powders and subsequent wet-milling process. Experimen-
tal details have been given elsewhere [5-11]. Briefly,
Fe2O3 (30 µm, 99.9%) powders were ball-milled at a speed
of 300 rpm for 10 hours. The chemical analysis of the
compositions of the oxide powders revealed that there
was nearly no change during milling process. It had
Fig. 1. SEM-micrographs of iron nanopowders fabricated by hydrogen reduction of ball-milled iron oxide powder at 500oC for 2 h.
(a) as reduced iron nanopowder agglomerates and (b) after wet-milling in alcohol.
Journal of Korean Powder Metallurgy Institute (J. Kor. Powd. Met. Inst.)
almost same impurity contents of 0.052% Mg and 0.034%Cr
as the not ball-milled one. After ball milling, they were
dried and reduced at 450oC in hydrogen atmosphere
(99.999%) for 1 hour. Then, in order to suppress particle
coarsening during cooling, the reduced powders were
quenched in the cooling chamber in argon atmosphere
(99.999%) which is directly connected to the furnace.
After cooling, the Fe powders were delivered to the
glove box for further processes where the glove box was
kept very clean and dry in argon atmosphere. To control
the agglomerate size and size distribution, the wet-mill-
ing of as-reduced Fe nanopowder was performed in alco-
hol [5].
For sintering experiment, the powders were compacted
at 250 MPa to reach 46±1% of theoretical density in a
cylindrical shape. To investigate low temperature sinter-
ing behavior, the variation of the relative density during
heat-up and subsequent isothermal sintering was investi-
gated at an intermediate temperature of 700oC with a
heating rate of 10oC/min in hydrogen atmosphere. The
sintering temperature was determined based on the previ-
ous works [4,7,12-14] in that the temperature near 700oC
is used for grain boundary diffusion predominating densi-
fication process of Fe-Ni nanopowders.
The primary objective was to correlate the powder
characteristics and sintering properties with densification
behavior, microstructure and mechanical property. For
this, the sintered specimens were polished and etched
using standard metallographic techniques and photo-
graphed for examining the microstructures by OM, SEM
and TEM observations. Vickers hardness was used for
characterizing its mechanical properties.
3. Results and Discussion
Fig. 1(a) and (b) show the SEM-micrographs of Fe
 Consolidation of Iron Nanopowder by Nanopowder-Agglomerate Sintering at Elevated Temperature
Fig. 2. Densification process of iron nanopowder compact
during heat-up to 700oC with a heating rate of 10oC/min and
subsequent isothermal sintering at 700oC for 4 h in a hydrogen
atmosphere.
nanopowders after wet-milling in comparison with that
for as-reduced state. After wet-milling, the Fe nano-
agglomerate powders consisting of Fe particles with 100
nm in size had an agglomerate size distribution ranging
from 0.5 µm to 5 µm, reflecting a more homogeneous
distribution than that for the as-reduced powders. It is
also observed that the Fe particles with 100 nm in size
are not changed during wet-milling process in this study.
The result of XRD pattern in Fig. 2(c) reveals that the
wet-milled Fe powders consist of pure Fe phase.
Fig. 2 shows the densification process of the wet-
milled Fe nanopowders during heat-up with a heating
rate of 10oC/min and subsequent isothermal sintering at
700oC in a hydrogen atmosphere. It is seen that remark-
able densification occurs at elevated temperature, espe-
cially during heat-up stage reaching near full density of
96.5%T.D. at 700oC. Considering the amount of densifi-
cation occurring during heat-up sintering only, it is
thought that the heat-up sintering process includes entire
stages of sintering Fe nanopowders from early stage to
final stage, mostly intermediate stage of sintering. Three
samples sintered only during heating-up to 600oC, 650oC
and 700oC represent 72%, 88% and 96.5% T.D., respec-
tively.
This result is quite different from the case for large
agglomerate nanopowders which are larger than a few 10
µm and not wet-milling treated powders [4,13]. The authors
reported that the Fe-40 wt%Ni agglomerate nanopowder
compact with about 20 µm in agglomerate size and the
low green density of 48% resulted incomplete densifica-
tion process [4]. This is basically due to a difficult-to-sin-
3
ter bimodal pore distribution, which is due to the
coexistence of intra- and inter-agglomerate pores. In case
of much larger agglomerate powder compact of 500 µm
size with a higher green density of 73%, the densifica-
tion process almost stopped at a certain condition. Larger
inter-agglomerate pores locating at triple junctions among
agglomerates proved to be responsible for such incom-
plete densification behavior. Such retardation of densifi-
cation process, however, did not take place in smaller
agglomerate sample. According to the previous work
[13], small sized agglomerate nanopowder compacts achieve
steady densification process in which the inter-agglomer-
ate boundary disappears during sintering, leading to
microstructural homogenization.
Based upon the previous works [4,7,12-14], the occur-
rence of full densification during heat-up process in Fig.
2 is closely related to NAS process in which the sinter-
ing kinetics are governed by material transport through
the hierarchical interface structures of the nanopowder
agglomerates. This phenomenon can be explained well
by SEM micrographs which represent microstructural
homogenization occurring during heat-up sintering pro-
cess.
As seen in Fig. 3(a-c), the agglomerates with its initial
size ranging from 0.5 to 5 µm enlarged with increasing
densification process where the growth of Fe nanograins
inside the agglomerates is accompanied. As a result, the
agglomerate boundaries gradually disappeared. Initially
dominant sintering takes place first in the agglomerate,
followed by sintering between neighboring large pow-
ders as locally densified agglomerate powders. When the
neighboring agglomerate powders start to sinter together
at the agglomerate boundaries, then densification process
can proceed continuously. Finally, fully densified homo-
geneous microstructure, as shown in Fig. 3(d), is obtained.
In the aspect of sintering kinetics based on diffusion
process, the powder interfaces consisting of hierarchical
interfaces of agglomerate- and nanograin boundaries act
as diffusion paths for material transport during such rapid
densification process. This argument has been confirmed
by our previous studies using Fe-Ni nanopowder agglom-
erates on densification process during heat-up sintering as
well as isothermal sintering [4-7,12-14] and radiotracer
diffusion behavior [15-17]. It was found that the domi-
nant densification kinetic is governed by grain boundary
Vol. 20, No. 1, 2013
4 Jai-Sung Lee, Joon-Chul Yun, Joon-Phil Choi and Geon-Yong Lee
Fig. 3. SEM-fractographs of iron nanopowder compacts during
heat-up sintering with a heating rate of 10oC/min and furnace-
cooled in a hydrogen atmosphere. (a) as compacted, (b) 600oC,
(c) 650oC and (d) 700oC.
Fig. 4. TEM- and SEM-EBSD micrographs of iron nanopowder
compacts during isothermal sintering in a hydrogen atmosphere
for 0 h and (b) 4 h (arrows denote the micro pores located at
grain boundaries and triple junctions).
diffusion along the hierarchical boundaries.
It is interesting that the pure Fe nanopowder compact
with optimal agglomerate size undergoes remarkable den-
sification during heat-up sintering as well as isothermal
sintering at low temperature of 0.53 Tm of iron. This tem-
perature region is characteristic of grain-boundary diffu-
sion controlled reaction kinetics [21]. In particular, it
should be noted that the densification in isothermal sin-
tering reaches near full density in the range of 96.5%-
99.2%. This indicates that the isothermal sintering pro-
cess in this study corresponds to final stage of sintering
[22]. Fig. 4 shows TEM micrographs for Fe nanopowder
compacts sintered isothermally. With increasing sintering
time, the Fe grains grew from 570 nm at 0 h to 1.3 µm in
Journal of Korean Powder Metallurgy Institute (J. Kor. Powd. Met. Inst.)
size at 4 h. It is also noted that fine pores are mostly
located at triple junctions and grain boundaries. The
results of SEM-EBSD (electronback scatter diffraction)
shown in Fig. 4 compare typical microstructures of two
samples sintered for (a) 1 h and (b) 4 h, showing the
microstructural characteristics of full density Fe nanopo-
wders. The SEM micrographs clearly show that fine
pores exist mostly at grain boundaries and triple junc-
tions in the final sintering stage. The EBSD results also
represent that the microstructure of sintered Fe nanopow-
der consists of different colored Fe grains indicating dif-
ferent crystallographic orientations. This is direct evidence
that the sintered Fe sample in this study is composed of
high angle grain boundary structure.
It is very interesting that fine pores still exist at grain
boundaries and triple junctions even in the final stage of
sintering process in this study. This is a direct evidence
for the fact that nano pores at grain boundaries and triple
junctions affected the heat-up sintering process prevail-
ing the entire densification and grain growth. It is well
known that the pores at the interfaces or triple junctions
act as a barrier against grain boundary migration, leading
to two positive effects on full density of fine grained
powder materials [22]. Due to the pore at interfaces,
enhanced densification process can last until it reaches
final full density even in low temperature sintering. This
is because the grain boundary acting as a high-diffusion
path for material transport in the intermediate sintering at
low temperature could be efficiently incorporated with
the pores in the entire sintering process.
Such enhanced densification process in this wet-milled
Fe nanopowder compact can be also discussed in terms
of the kinetic aspect based on diffusion process. As
reported in the previous investigations [4,12-14], the den-
sification kinetics in the intermediate sintering stage at
elevated temperatures is governed by material transport
process along grain boundaries. Especially, in NAS pro-
cess, atoms diffuse much faster along inter-agglomerate
boundary than nanograin boundary by two orders of
magnitude [15,16]. In this respect, it is thought that rapid
densification during heat-up stage results from enhanced
material transport along the boundaries, especially the
agglomerate boundary.
The fact that residual pores still exist at grain bound-
aries and triple junctions in the final stage of sintering as
 Consolidation of Iron Nanopowder by Nanopowder-Agglomerate Sintering at Elevated Temperature 5

Table 1. The sintering properties of Fe nanopowder agglomerate

compacts isothermally sintered at 700oC
Composition Heating
(h)
time Relative density Hardness Grain size
(%) (Hv) (µm)
0 96.3 210 0.57
0.5 97.6 191 0.64
Fe 1 97.7 176 0.77
2 98.6 167 1.1
4 99 160 1.3

described above, offers a possibility for processing full

density fine-grained powder materials in low tempera-
ture sintering. This is because material transport for den-
Fig. 5. Dependence of hardness on grain size in the Fe
sification process is governed by grain boundary diffusion at nanopowder compact sintered at 700oC.
low temperature where the contribution of volume diffu-
sion to the densification might be ignored comparing to However, these values are higher than the values for con-
that of grain boundary diffusion. Calculating the mean ventional PM steel parts containing carbon content. This
diffusion distances (x=(Dt) ) in grains or at grain bound-
1/2
remarkable strengthening effect of the pure Fe nanopowder
aries under the maximum sintering condition (at 700 C o
without the presence of carbon is well interpreted in
for 4 h), the approximate values are obtained; first, diffu- terms of grain refinement effect. Fig. 5 shows the dependence
sion distance by volume diffusion (x =(D t) ) is about
vol. vol
1/2
of hardness value on grain size which represents Hall-
120 nm in which the volume diffusion coefficient for Petch relationship. It is clearly seen that the hardness
pure Fe system, D corresponds to exp(36-104422.5/
vol values are in a good agreement with a normal Hall-Petch
T+28686100/T ) m /s [23], while that by grain boundary
2 2
relationship. This means that the strengthening effect by
diffusion (x =(D t) ) is about 54 µm where the effec-
gb gb
1/2
grain refinement described above holds in this grain size
tive grain boundary diffusivity, P is equal to 3.42×10−
gb
11
range. These results are indicative of promising applica-
exp(-198 kJ/mol/RT) [24]. Therefore, it is obvious that tions for high strength pure Fe powder materials.
under this low temperature sintering process, the mate-
rial transport via volume diffusion is negligible and rather 4. Conclusion

preferentially via grain boundary diffusion. Therefore, it

is concluded that low temperature sintering of size con-
trolled nanopowder agglomerates provides a break-
through for solving full densification owing to uniform
distribution of fine pores suppressing grain growth effec-
Full density processing of pure Fe nanopowder agglomer-
ates size-controlled by wet-milling during heat-up and
subsequent isothermal sintering at low temperature of
700 C was investigated based upon the concept of NAS
o

tively. process. It was found that the dominant densification

It is interesting that no drastic grain growth takes place
during isothermal sintering at 700 C. As depicted in
o
Table 1, the average grain size was increased by about
1.7 times from 570 nm to 1.3 µm during 4 hours of
sintering. It is intuitive that pore pinning effect is mostly
responsible for such a slow grain growth. To examine
mechanical property, Vickers hardness was measured
after various sintering times and summarized in Table 1
kinetic is governed by grain boundary diffusion along the
hierarchical boundaries and the densification in isother-
mal sintering reached near full density above 99%T.D.
Such a pronounced densification behavior results from
pore pinning effect of fine pores which are located at
grain boundaries and triple junctions even in the final
stage sintering process. No drastic grain growth takes
place during isothermal sintering at 700 C. Pore pinning
o

in comparison with that for the conventional PM materials. It effect is mostly responsible for such a slow grain growth,
is seen that the hardness value decreased with increasing leading to remarkable strengthening owing to grain
sintering time from H of 210 at 0 h to H of 160 at 4 h.
v v refinement effect despite no carbon content. These results

Vol. 20, No. 1, 2013

6 Jai-Sung Lee, Joon-Chul Yun, Joon-Phil Choi and Geon-Yong Lee
are indicative of promising applications for high strength
pure Fe powder materials. It is concluded that low
temperature sintering of size controlled nanopowder
agglomerates provides a breakthrough for solving full
densification owing to uniform distribution of fine pores
suppressing grain growth effectively.
Acknowledgement
This work has been supported financially by the Korea
Research Council for Industrial Science and Technology
(“Development of the Preparation Technology of 0.1-10
µm Sized Metal Powders and Fine-Components for
Micro Electronics”, 2012-00000001921). The authors are
also grateful to colleagues for their essential contribution
to this work.
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