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Acta Materialia 60 (2012) 860871

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The formation of supersaturated solid solutions in FeCu

alloys deformed by high-pressure torsion
A. Bachmaier a,, M. Kerber b, D. Setman b, R. Pippan a
b

a
Erich Schmid Institute of Materials Science, Austrian Academy of Sciences, Jahnstr. 12, A-8700 Leoben, Austria
Research Group Physics of Nanostructured Materials, University of Vienna, Boltzmanngasse 5, A-1090 Vienna, Austria

Received 18 July 2011; received in revised form 4 October 2011; accepted 23 October 2011
Available online 14 December 2011

Abstract
Fully dense bulk nanocomposites have been obtained by a novel two-step severe plastic deformation process in the immiscible FeCu
system. Elemental micrometer-sized Cu and Fe powders were rst mixed in dierent compositions and subsequently high-pressuretorsion-consolidated and deformed in a two-step deformation process. Scanning electron microscopy, X-ray diraction and atom probe
investigations were performed to study the evolving far-from-equilibrium nanostructures which were observed at all compositions. For
lower and higher Cu contents complete solid solutions of Cu in Fe and Fe in Cu, respectively, are obtained. In the near 50% regime a
solid solution face-centred cubic and solid solution body-centred cubic nanograined composite has been formed. After an annealing
treatment, these solid solutions decompose and form two-phase nanostructured FeCu composites with a high hardness and an enhanced
thermal stability. The grain size of the composites retained nanocrystalline up to high annealing temperatures.
2011 Acta Materialia Inc. Published by Elsevier Ltd. Open access under CC BY-NC-ND license.
Keywords: High-pressure torsion; Solid solubility extension; FeCu alloy

1. Introduction
Due to novel properties of materials fabricated out of
typically immiscible alloys, like high thermal and electrical
conductivity and excellent magnetic properties (i.e. high
magnetoresistance and coercivity), a long-standing interest
in the preparation of such alloys exists [13]. The formation
of metastable phases in alloy systems with a negative heat
of mixing as well as positive heat of mixing has been intensively investigated in recent years [36]. Since the 1990s, the
formation of metastable single-phase solid solutions with
nanocrystalline grain sizes for mechanically alloyed Fe
Cu powders has been studied extensively by several
research groups [713]. The FeCu system, a spinodal type
system, is nearly immiscible in equilibrium at room temperature and up to 600 C and has a positive heat of mixing
[14]. Due to mechanical alloying, the potential to extend
Corresponding author. Tel.: +43 3842 804 314; fax: +43 3842 804 116.

E-mail address: [email protected] (A. Bachmaier).

the mutual solubility of Fe and Cu has been widely

reported due to friction and strong impacts of the steel
balls on the powder grains. The formation of face-centred
cubic (fcc) single-phase solid solutions is observed for
FexCu1x alloys with a Fe content x < 60 at.%, two-phase
alloys consisting of a fcc and a body-centred cubic (bcc)
phase are formed for a Fe content of 60 < x < 80 at.%
and bcc single-phase solid solutions are obtained for a Fe
content of x > 80 at.% [810]. The mixing occurs on the
atomic level in the milled alloys, which was conrmed by
Mossbauer spectroscopy [8,11]. The crystallite size in the
milled powders is reported to be 20 nm or even smaller.
Decomposition of the unstable FeCu solid solutions
occurred due to annealing treatments as reported in several
studies [1012].
In this study, a new approach to obtain fully dense
homogeneous bulk FeCu composites by high-pressure
torsion (HPT) deformation is presented. Sauvage et al.
showed that by HPT deformation the production of a
non-equilibrium Cu supersaturated solid solution in a

1359-6454 2011 Acta Materialia Inc. Published by Elsevier Ltd. Open access under CC BY-NC-ND license.
doi:10.1016/j.actamat.2011.10.044

A. Bachmaier et al. / Acta Materialia 60 (2012) 860871

CuFe composite was possible [15,16]. Many structural

defects are incorporated in a material during severe plastic
deformation (SPD) processes, which is accompanied with a
higher dislocation density, a higher vacancy concentration
and the continuous formation of new grain boundaries [15
18]. A CuFe composite with an inhomogeneous layered
nanostructured microstructure was produced, where nanoscaled Fe clusters dissolved into the Cu matrix.
Instead of a lamentary composite starting material,
micrometer-sized Fe and Cu powders are used, which is
similar to the mechanical alloying process. Nevertheless,
the product after mechanical alloying is a powder and further processes like compaction and sintering are necessary
to obtain bulk specimens. One emerging disadvantage is
that the nanocrystalline structure can be lost during these
treatments and decomposition of the supersaturated solid
solutions occurs during annealing. Furthermore, an
increase of the impurity content is unavoidable. The advantage of the HPT process is that the end product is directly
available as a massive bulk material. Up to now it was
impossible to generate homogeneous nanocrystalline
supersaturated FeCu composites by HPT or equal angular
channel pressing micrometer-sized powder consolidation.
One of the goals in this study was to nd a way to overcome these problems. If nanocrystalline supersaturated
FeCu composites with homogeneous microstructures
can be produced by HPT deformation, it would be an easy
way to produce such composites, which are also very interesting materials for magnetic applications. Fcc supersaturated solid solutions are ferromagnetic for a Fe content
of x > 15. Furthermore, nanocrystalline FeCu composites
with small amounts of Cu should exhibit large magnetostrictive eects [1921].
2. Experimental
Commercial copper powders (99.9% purity, 170 + 400
mesh) and iron powders (99.9% purity, 100 + 200 mesh)
were used as starting materials. These micrometer-sized
powders were mixed in dierent ratios to obtain powder
mixtures with nal alloy compositions of Fe100xCux
(x = 15, 30, 50, 85). The powder mixtures were precompacted and deformed in our large HPT tool which can be
used to deform samples up to a diameter of 50 mm and a
thickness of about 10 mm. Afterwards, new smaller HPT

861

samples were cut out of the previously deformed sample.

Therefore, the sample was cut at a radius of 5 and
15 mm, a cylindrical rod was turned from the cut part
and slices of 0.8 mm thickness were cut from this rod.
These new HPT samples were deformed a second time.
The reason for this special procedure will be discussed
later. The single steps of the sample production are illustrated in the schematic sketch in Fig. 1. Further information about HPT deformation and a detailed description
of the HPT equipments are given in Refs. [2224]. A list
of the deformation parameters of both processing steps
for all samples deformed in this study is given in Table 1.
Dierent deformation parameter sets were used for sample
processing in order to generate a nanostructure relatively
quickly, taking into account the limitation of the torque
of the larger HPT device.
All microstructural investigations were performed at a
radius of 10 mm of the HPT sample after the rst deformation step and at a radius of 3 mm after the second deformation step in the tangential direction with a scanning
electron microscope (SEM) type LEO 1525 using backscattered electrons. The direction of the SEM observations is
also shown in Fig. 1. Vickers microhardness measurements
were performed on a BUEHLER Mircomet 5100 using a
load of 500 g. Indents were made across the radii of the
samples with a distance of 0.25 mm between the indents
on the 8 mm diameter disks after the cutting procedure
described above. After the rst processing step, nearly constant hardness values were measured across the radii of the
samples and the mean values of 32 indents over the radii of
the samples are given. In contrast, mean values of 16
indents starting from a radius of 2 mm to the outer edge
of the sample are reported after the second processing step
in this study, which corresponds to the saturation region.
X-ray diraction measurements were taken with an AXS
BRUKER D8 system in BraggBrentano h2h geometry
using Co (Ka) radiation using a spot size of 0.5 mm and
rotating the sample around the surface normal to compensate for possible texture eects. Furthermore an atom
probe analysis has been carried out on the Fe50Cu50 sample. Bars with a dimension of 0.3  0.3  3 mm were cut
out of the HPT deformed sample. A two step electrochemical polishing procedure was used to get nally tips situated
at a radius of 3 mm referred to the HPT sample. The atom
probe analysis was conducted on a LEAP 3000X HR from

Fig. 1. Schematic sketch of the individual sample production and deformation steps: from the sample (diameter of 50 mm) deformed in the rst HPT
deformation step, new samples (diameter of 8 mm) are cut and further HPT deformation is conducted.

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A. Bachmaier et al. / Acta Materialia 60 (2012) 860871

Table 1
Deformation parameters of the rst and second deformation steps for all
deformed samples in this study.
(1) Deformation step

Fe85Cu15
Fe70Cu30
Fe50Cu50
Fe15Cu85

(2) Deformation step

#
Rotations

Thickness
(mm)

(mm)

#
Rotations

Thickness
(mm)

(mm)

10
10
20
20

9.5
9.5
9.6
11.5

50
50
50
50

50
100
200
100

0.5
0.6
0.5
0.5

8
8
8
8

Cameca, formerly Imago Scientic Instruments. The sample was measured with a pulsed laser with a frequency of
250 kHz, a temperature of 40 K and a laser pulse energy
of 0.5 nJ. The software package IVAS 3.4.3 from Cameca
was used for reconstruction of the probed volume and the
data analysis.
Dierential scanning calorimetry (DSC) with a Perkin
Elmer DSC-7 was performed to evaluate the decomposition temperature of the FeCu alloys with 10 C min1 of
heating rate up to a temperature of 590 C on ring samples
(inner diameter 2 mm, outer diameter 3 mm) cut out of the
samples after both deformation steps.
3. Results
3.1. Formation of supersaturated solid solutions
After powder mixing to obtain the dierent compositions (Fe85Cu15, Fe70Cu30, Fe50Cu50 and Fe15Cu85) and
precompaction of the powder mixtures directly in the

HPT tool, the precompacted samples with a diameter of

50 mm were HPT deformed for 1020 rotations. Fig. 2
shows the microstructure of the Fe70Cu30 and Fe85Cu15
samples after the deformation at a lower and at a higher
magnication. Due to the lower scattering factor of the
Fe phase, the Cu-rich regions appear brighter in the backscatter electron mode and the Fe and Cu regions can be
easily distinguished. Continuous bands of Cu-rich regions
(thickness 12 lm) are embedded in the Fe matrix and
the Cu and Fe phases are not homogeneously distributed
in the case of the Fe85Cu15 alloy. The thickness of the Cu
bands is about ten times smaller than the particle size of
the Cu powder in the initial state but the distance between
the Cu bands diers a lot. From the micrograph with the
higher magnication, an average grain size of 300 and
200 nm for the Fe and Cu phases in the Fe85Cu15 composite can be estimated using the backscattered electron mode.
In the Fe15Cu85 composite, similar grain sizes are observed
(300 nm for Cu, 300 nm for Fe). In the Fe70Cu30 composite, the Cu and Fe phase can also be dierentiated very easily. From the micrograph with the higher magnication, Fe
and Cu grains with a similar grain size of 300 nm and
200 nm can be seen. In the Fe50Cu50 composite, the grain
sizes in the Cu and Fe phase are again similar (about
300 nm for Cu and 400 nm for Fe).
In Fig. 3, the nal microstructures of the Fe85Cu15,
Fe70Cu30, Fe50Cu50 and Fe15Cu85 samples after the second
processing step are shown. Compared to the obtained
microstructures after the rst processing step, the grain size
is signicantly reduced in all four samples. In the Fe85Cu15,
Fe50Cu50 and Fe15Cu85 samples an apparent homogeneous
microstructure is obtained. The Fe15Cu85 sample shows a

Fig. 2. SEM micrographs (backscattered electron mode) showing the microstructure of the Fe85Cu15 and the Fe70Cu30 after the rst deformation step with
a low and high magnication recorded at a radius of 10 mm in the tangential direction. Fe-rich regions appear darker in the image, Cu regions brighter.

A. Bachmaier et al. / Acta Materialia 60 (2012) 860871

863

Fig. 3. SEM micrographs (backscattered electron mode) showing the nal microstructure after both processing steps in all alloys (Fe85Cu15, Fe70Cu30,
Fe50Cu50, Fe15Cu85) recorded at a radius of 3 mm in the tangential direction. The magnication is the same in all images.

somewhat larger grain size compared to the other microstructures but still a nanocrystalline microstructure is
obtained. In the Fe70Cu30 sample, an inhomogeneous layered microstructure can be seen. The darker regions are
Fe-rich regions whereas the brighter regions are Cu-rich
regions. Very thin Fe layers with a thickness signicantly
below 50 nm are drawn trough the Cu matrix and vice
versa. The grain size is nanocrystalline as well.
The mean microhardness values of the samples after the
rst and second processing step can be seen in Fig. 4. The
rst step of the HPT deformation leads to a hardness of
187 HV for the composite with the highest Cu content.
Decreasing the Cu content increases the hardness after
the rst processing step up to a value of 341 HV for the
Fe85Cu15 composite. After the second processing step,
microhardness values increased nearly twice in all samples.
Between the Fe50Cu50 and Fe70Cu30 samples, nearly no
hardness dierence exists.
From the micrographs, it is not possible to distinguish
between Fe and Cu phases in the case of the Fe85Cu15,
Fe50Cu50 and Fe15Cu85 samples. Therefore, X-ray diraction investigations were performed to study the occurring
phases after the rst and second deformation step at the
positions mentioned earlier. In Fig. 5, X-ray diraction
patterns for all four alloy compositions after the rst and
second deformation step are shown. In the X-ray diraction pattern of the Fe85Cu15 alloy, peaks of the fcc Cu
phase and the bcc Fe phase are visible after the rst deformation step (Fig. 5a). Peaks from the composite phase are
not visible within the resolution of the diractometer but

Fig. 4. Microhardness of the FeCu samples after the rst and second
deformation step. Mean values of 32 indents over the radii of the samples
after the rst processing step and mean values of 16 indents starting from a
radius of 2 mm to the outer edge of the samples after the second
processing step are given.

could be resolved using a high-resolution diractometer

and a highly monochromatic source. This result is consistent with the microstructure of this alloy, which shows a
composite structure in the micrograph consisting obviously
of Fe and Cu (Fig. 2). In general, no peaks from oxides or
other contaminants are observed in all diraction patterns.
After the second deformation step, the X-ray diraction
pattern of the Fe85Cu15 alloy contains only peaks of the
bcc Fe phase although slightly shifted. Therefore, we
assume that supersaturated solid solution of Cu in Fe is
formed after this processing step. Furthermore, both bcc

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A. Bachmaier et al. / Acta Materialia 60 (2012) 860871

Fig. 5. X-ray diraction patterns after the rst deformation step and second deformation step of the Fe85Cu15 alloy (a), the Fe70Cu30 alloy (b), the
Fe50Cu50 alloy (c) and the Fe15Cu85 alloy (d), respectively.

Fe peaks have signicantly broadened due to the reduction

of the mean grain size, as conrmed from the micrographs
of the microstructure after the rst and second deformation
step. Moreover, the intensity of the Fe (1 1 0) peak
increased. The Fe peaks are also shifted to lower angles
compared to those recorded after the rst deformation
step, which might be due to the formation of a Cu solid
solution in Fe. Fig. 5d shows the X-ray diraction pattern
of the Fe15Cu85 alloy. After the rst deformation step, fcc
Cu peaks and a weak Fe (1 1 0) peak are visible. After the
second deformation step, the intensity of the Cu (1 1 1)
peak increased signicantly. The Fe peaks completely disappeared and only Cu peaks remain, and vice versa as in
the case of the Fe85Cu15 alloy. In the Fe15Cu85 alloy, the
Cu (1 1 1) peak is now shifted to lower diraction angles,
which might now be due to the formation of supersaturated
Fe solid solution in the Cu phase. Furthermore, some peak
broadening is also observed, which is again due to the
reduction of the mean grain size.
In the X-ray diraction patterns of the Fe70Cu30 alloy
(Fig. 5b), diraction peaks related to the fcc Cu and the
bcc Fe phase are observed after the rst as well as after

the second deformation step. The intensity of the Cu peaks

increased somewhat after the second deformation step and
the intensity of the Fe peaks is diminished at the same time.
Furthermore, both sets of peaks show a broadening after
the second deformation step. The Cu peaks are also slightly
shifted to lower diraction angles after the second deformation step. Similar results are obtained in the Fe50Cu50
alloy (Fig. 5c). In turn, a two-phase structure consisting
of fcc Cu and bcc Fe is obtained at both deformation steps.
The intensity of the Fe peaks after the second deformation
step is again reduced whereas the intensity of the Cu peak
is slightly increased. Moreover, broadening of the peaks
after the second deformation step is observed as well.
The position of the Cu peaks after the second deformation
step is shifted to lower diraction angles.
Generally, the Cu peaks in the X-ray diraction pattern
of the Fe70Cu30, Fe50Cu50 and Fe15Cu85 samples after the
second deformation step are all shifted to lower diraction
angles. In the case of the Fe85Cu15 sample, the Fe peaks are
shifted to lower diraction angles. A two-phase structure is
maintained in the Fe70Cu30 and Fe50Cu50 sample even after
both processing steps are conducted. Based on the results

A. Bachmaier et al. / Acta Materialia 60 (2012) 860871

from the X-ray diraction experiments it might be assumed

that for Cu contents >30 wt.%, Cu supersaturated solid
solutions are formed even if a complete single-phase structure is not obtained. For Fe contents >85%, Fe supersaturated solid solutions are achieved. A quantitative phase
analysis was not done as the strongest composite peaks
form close to the high-intensity peaks of Fe and Cu. These
peaks are quite broadened and additionally there is still a
Ka2 component in the incoming radiation causing considerable overlap. For the present case the disappearance of
the peaks of the initial phases are good indicators of the
creation and loss of the solid solution.
Atom probe analysis on the Fe50Cu50 sample was conducted to evaluate the possible formation of supersaturated
solid solutions in the two-phase structures and to map the
distribution of Fe and Cu atoms in a volume of
65  66  285 nm3 (Fig. 6a). Cu atoms are displayed in
green and Fe atoms in blue, respectively. The Cu as well
as the Fe concentration prole across a smaller analyzed
volume is shown in Fig. 6b. Grain sizes of both phases
around 10 nm can be estimated from this plot. The Cu as
well as the Fe concentration prole exhibits gradients
which might indicate FeCu interdiusion. The Cu concentration in the Fe phase is up to 25 at.% and the Fe concentration in the Cu phase is up to 20 at.%. Under
equilibrium conditions, the mutual solubility of Fe and
Cu is normally less than 0.1 at.% at room temperature.
Therefore, these data conrm that the formation of Fe
supersaturated solid solutions as well as Cu supersaturated
solid solutions is simultaneously possible in the two-phase

865

structure. In contrast, no complete single-phase supersaturated solutions were obtained in Ref. [16], although it was
shown that Fe clusters with a nanometer size are dissolved
in Cu during HPT.
3.2. Thermal stability
In the following section, the thermal stability of the single-phase supersaturated solid solutions of the Fe85Cu15
and Fe15Cu85 samples are investigated. The samples are
annealed at three dierent annealing temperatures for 1 h
in air. To monitor a possible thermal decomposition process, the samples are investigated by X-ray diraction after
each annealing step. Furthermore, DSC measurements are
conducted to determine the temperature of the decomposition process. Fig. 7 shows the X-ray diraction patterns of
the Fe85Cu15 and Fe15Cu85 alloys after annealing for 1 h at
290 C, 440 C and 620 C and after the second deformation step without an annealing treatment as a reference
(indicated as RT in the plot). After annealing for 1 h at
290 C, the diraction pattern of the Fe15Cu85 alloy sample
consists of just Cu peaks. Not even an indication of peaks
belonging to the bcc Fe phase is visible, showing that it is
still fully resolved in Cu. Moreover, the width of the Cu
peaks decreases, which might be due to thermal relaxation
of the structure. With annealing at 440 C, the bcc Fe phase
peaks appear, which is a clear sign of the decomposition of
the initial single fcc Fe15Cu85 phase into an fcc Cu and bcc
Fe phase. After annealing at 620 C, the X-ray diraction
pattern does not change very much. Fcc Cu as well as

Fig. 6. Atom probe data of the Fe50Cu50 alloy after both deformation steps: (a) three-dimensional reconstructed volume (65  66  285 nm3) where Cu
atoms are displayed in green and Fe atoms in blue, respectively. (b) Cu concentration prole (green) and Fe concentration prole (blue) across the Cu/Fe
interfaces. (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

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A. Bachmaier et al. / Acta Materialia 60 (2012) 860871

Fig. 7. X-ray diraction patterns of the Fe15Cu85 alloy (a) and the Fe85Cu15 alloy (b) sample recorded in the as-deformed condition (both deformation
steps) and after annealing for 1 h at 290 C, 420 C and 620 C.

bcc Fe peaks are now visible, indicating that decomposition into a two-phase structure has occurred at annealing
temperatures higher than 440 C. With increasing annealing temperature, the Cu peaks are continuously shifted to
higher diraction angles, which are a further indication
for the decomposition of the structure. The single-phase
supersaturated solid solution is remained in the Fe85Cu15
alloy sample until annealing temperatures below 440 C.
After annealing at 440 C for 1 h, Cu peaks appear in the
X-ray diraction pattern. Therefore, decomposition of
the initial single bcc Fe85Cu15 phase into fcc Cu and bcc

Fe occurs. At an annealing temperature of 620 C, bcc Fe

and fcc Cu peaks are visible. Moreover, the slight shift of
the Fe peaks to lower diraction angles is reversed with
increasing annealing temperature, which is again a further
indication for the decomposition of the single-phase structure. Small thermal relaxation of the structure might also
occur in this alloy at low annealing temperatures.
As an example, the microstructural evolution of the
Fe15Cu85 sample with increasing annealing temperature is
shown in Fig. 8. Compared to the as-deformed condition,
no signicant dierence is visible between the microstruc-

Fig. 8. SEM micrographs (backscattered electron mode) showing the microstructure of the Fe15Cu85 alloy in the initial condition (RT) and after annealing
for 1 h at 290 C, 420 C and 620 C recorded at a radius of 3 mm in the tangential direction.

A. Bachmaier et al. / Acta Materialia 60 (2012) 860871

tures in the sample annealed at 290 C and 440 C. From

the micrographs, no distinction between Fe and Cu grains
can be made although a two-phase structure has already
formed at 440 C as conrmed by X-ray diraction. At
annealing temperatures of 620 C, grain growth has
occurred and grains with a size above 100 nm are visible.
The microstructural evolution of the Fe85Cu15 sample is
similar. Until annealing at the highest annealing temperature, no dierence between the as-deformed and annealed
microstructures is visible. No change in the grain size is
observed after annealing for 1 h at 290 C and 440 C
and from the micrographs it is not possible to distinguish
between Fe and Cu grains. Only at the highest annealing
temperature does marginal grain growth occur as well.
In Fig. 9, the microhardness as a function of annealing
temperature of the Fe85Cu15 and Fe15Cu85 samples is plotted. In the Fe85Cu15 sample, the hardness increases with
increasing annealing temperatures in the beginning. The
hardness of the as-deformed sample is 639 HV whereas
the hardness after annealing at 290 C and 440 C is 642
and 675 HV, respectively. At the highest annealing temperature, the hardness decreases and has a somewhat lower
value compared to the as-deformed condition (576 HV).
First of all there is a slight increase in the hardness in the
Fe15Cu85 sample during annealing. The hardness of the
as-deformed sample is 327 HV and the hardness after
annealing at 290 C is 330 HV. At 440 C a higher hardness
value of 337 HV compared to the initial condition is measured but at the highest annealing temperature the hardness decreases to 277 HV. In both samples, the measured
hardness values are higher compared to the as-deformed
condition if decomposition of the supersaturated solid
solution has occurred. At the highest annealing temperature, the hardness of both samples decreased, which is
due to the occurrence of marginal grain growth during
the annealing treatment, as shown for example for the
annealed Fe15Cu85 sample in Fig. 9.

867

DSC of the Fe15Cu85 sample shows a broad exothermic

signal extending from 302 C to 585 C during heating
from room temperature to higher temperatures. Integration of the area under the DSC curve yields a total stored
energy of 43.9 J g1 with a peak temperature of 434 C.
Such an exothermic event might be attributed to the transition from the metastable supersaturated phases to the stable two-phase structure, which ts well with the results
obtained from the X-ray diraction experiments. It indicates that the phase separation process is completed when
reaching a temperature above 585 C. In the case of the
Fe85Cu15 sample, a smaller exothermic peak extending
from 300 C to 483 C is observed, with a total stored
energy of 13.1 J g1 and a peak temperature of 385 C.
This is again attributed to the decomposition of the supersaturated phase to the stable elemental Fe and Cu phases,
which starts at approximately the same temperature and is
completed at a somewhat lower temperature of 480 C than
in the Fe15Cu85 sample.
4. Discussion
From the experiments it is concluded that three composition regions can be distinguished in the as-deformed state
after the two-step HPT process: a nanocrystalline fcc
supersaturated Cu phase at high Cu contents, a mixture
of nanocrystalline supersaturated fcc Cu and bcc Fe phase
for medium Cu contents and a nanocrystalline supersaturated bcc Fe phase for low Cu contents. Therefore, the formation of supersaturated solid solutions over the whole
composition range occurs as a result of HPT deformation.
After the rst processing step, however, a two-phase ultrane-grained material is formed. Depending on composition, the grain size of Cu is between 200 nm and 300 nm,
and around 300 nm and 400 nm for Fe. After the second
processing step, a much smaller grain size is reached. The
nanocrystalline grain size obtained in the composites is signicantly smaller compared to pure Fe and Cu deformed
by SPD [25,26].
4.1. Why is a two-step process necessary?
If continuous shearing of the individual Fe and Cu powder components in the composite during HPT deformation
and volume conservation is assumed, their thickness
decreases with increasing applied deformation. If d0
denotes the initial particle size and c is the applied shear
strain, their thickness d1 after HPT deformation can be
estimated for larger c to be
d 1 d 0 =c:

Fig. 9. Microhardness of the Fe15Cu85 alloy and the Fe85Cu15 alloy

sample after annealing for 1 h at 290 C, 420 C and 620 C. Mean values
of 16 indents starting from a radius of 2 mm to the outer edge of the
sample are reported.

If powders with a mean initial particle size d0 of

50 lm (like the Cu powders in this study) are deformed
to a shear strain of c = 100, their thickness or their size
after the deformation is about 500 nm. This result ts very
well to the observed microstructures in the deformed
composite materials where a two-phase structured mate-

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A. Bachmaier et al. / Acta Materialia 60 (2012) 860871

rial is clearly observed in all compositions (Fig. 2). In the

individual components of the composite, an ultranegrained microstructure is formed. With monotonic shear
deformation like in the HPT process and equal channel
angular pressing, very high amounts of deformation are
necessary to reach 2 nm distance between two phases,
which are reported to be a basic requirement in the case
of Fe for alloying of Fe and Cu and to initiate the formation of supersaturated solid solutions in the FeCu system
[14]. Using Eq. (1) and assuming d0 = 50 lm to obtain a
2 nm spacing would require a c of 20000. This is in
principle possible by HPT but it is extraordinarily timeand energy-consuming. The large necessary strain becomes
evident if one considers a lamellar structure and applies
a simple shear in the direction parallel to the aligned
lamellae. Such a shear does not change the lamellar
spacing.
On account of this and to further increase the eectiveness of the deformation process, a novel two-step HPT process was developed (Fig. 10a). After the shear deformation
is applied in one direction, new samples are fabricated out
of these already deformed samples, which are further
deformed by HPT. Due to the cutting process, a rotation
of the shearing direction by 90 is also introduced. The
shear direction and lamellar alignment are now perpendicular to each other. The thickness d2 of the lamella of the
individual components after both HPT deformation steps
can now assumed to be
d 2 d 1 =c2 d 0 =c1  c2

where c1 denotes the applied shear strain in the rst deformation step and c2 is the applied shear strain in the second
deformation step. If now a shear strain of c1 = 100 is
applied in the rst HPT deformation step and a shear
strain of c2 = 100 is applied in the second HPT deformation step, the nal thickness of the individual components
should become 5 nm or lower.
As an example for the eectiveness of the two-step HPT
process, the microhardness of the Fe85Cu15 alloy sample is
plotted in Fig. 10b. After the rst processing step, nearly
constant hardness values were measured across the radii
of the disk. The Cu and Fe phases have nearly reached
their specic saturation microstructure in the whole sample. Only in the immediate vicinity of the center is the
applied c insucient to reach the saturation. However, this
part could not be localized by the hardness measurements.
The spacing between the two phases in the whole sample is
larger than the saturation grain size of the individual
phases. Therefore, the hardness is nearly constant. After
the second processing step, a continuous increase of the
hardness with increasing radii (i.e. increasing strain) is
again observed.
Due to the fast decrease of the lamella spacing of the Fe
and Cu phases the size of the grains in Cu and Fe become
restricted by the fast decreasing lamella spacing. As a consequence the hardness increases with increasing c2, i.e.
increasing radius.

4.2. The formation of supersaturated solid solutions

From free energy curves calculated by the CALPHAD
method [13], it was shown that for a Fe content of
x > 80, the free energy of the bcc structure is smaller
whereas at Fe contents of x < 40, the fcc structure is more
stable. In between, the dierence of the free energy between
both structures is small and the formation of both phases is
favorable. This theoretical result ts quite well with our
obtained structures in the FeCu system.
Dierent mechanisms were proposed in recent years of
how the formation of a solid solution in immiscible systems
with a positive heat of mixing can be explained during
SPD. An explanation was given by Veltl et al. [27]: the driving force to form solid solutions comes from the energy
stored in the grain boundaries in which a considerable
amount of enthalpy can be stored in nanocrystalline metals. Jiang et al. [13], however, showed that the maximum
increase in grain boundary enthalpy is not suciently high
as compared to the free energy of mixing to explain the formation of solid solutions in the FeCu system. Another
explanation is a diusion driven process. Raabe et al.
[28], however, suggested that such a process can be
excluded due to the lack of thermodynamic forces. The
high number of introduced defects during SPD, like the
high dislocation density, is proposed as another mechanism
for the solid solution formation, which can be summarized
as defect-enhanced diusion processes [2931]. The formation of a high number of non-equilibrium vacancies during
SPD has been reported by a lot of researchers. Sauvage
et al. [16] reported a very high vacancy production rate
of 105 s1 during HPT, which would increase the diusion
coecient and furthermore enable the mechanical alloying
of Fe and Cu. Nevertheless, the strain energy induced by
mechanical deformation alone is not sucient, as calculated in Ref. [10]. The defect-enhanced diusion processes
are proposed to be possible in Ref. [28], but the net ux
depends on dierent defect densities and mobilities in the
dierent phases.
Yavari et al. [14,32,33] proposed a dierent explanation
for the occurrence of the formation of fcc solid solution in
the Fe and Cu system. The free energy curve of a Fe component can be raised by the interfacial energy term [14]:
DGint 3cFeCu V m =r

where Vm is the molar volume and r is the radius of the particle. cFeCu is the interfacial energy between FeCu interfaces. Therefore, if small Fe particles are formed the free
energy curve of Fe is raised to higher values. This is accompanied with a change of the comment tangent with the free
energy curve of the Cu phase to higher Fe contents and
therefore to an enhancement of supersaturation. If elemental fragments with small tip radii below 2 nm are formed,
capillary pressure forces the atoms which are on the tip
of the fragments to dissolve. This process continues as long
as such small fragments are continuously created. In
mechanical alloying, the grain size of initial pure Cu fcc

A. Bachmaier et al. / Acta Materialia 60 (2012) 860871

869

Fig. 10. (a) Schematic sketch showing the continuous shearing of the dierent components of the composite in the rst and second deformation step.
Between the dierent deformation steps, a rotation of the sample of 90 is included. (b) Microhardness of the Fe85Cu15 alloy sample after the rst and
second processing steps. Indents are made across the radii of the sample with a distance of 0.25 mm between the indents.

phase is reduced in the beginning to a value of about 20 nm

and remains constant at higher milling times. The same
happens with the initial pure Fe bcc phase which gets rened until a grain size of 10 nm before it disappears. Even
if the overall grain size of the solid solution phase is
10 nm, it might be possible that small fragments below
2 nm are formed again and again if the deformation continues. From the calculated energy stored in the Fe/Cu interface for an elemental size of 1 nm, formation of fcc solid
solutions is energetically possible. The same processes
might occur during HPT deformation. Sauvage et al. [16]
showed that Fe clusters with a nanometer size are dissolved
during HPT. The smaller the size of the Fe clusters, the
higher the amount of dissolved Fe in Cu. Nonetheless,
complete single-phase supersaturated solutions were not
obtained in this work. The second processing step oers a
new possibility to quickly obtain grain size regions where
the formation of complete supersaturated solid solutions
in the FeCu system are feasible.
Therefore, the enthalpy contribution of the FeCu interfaces can act as a driving force for the solid solution formation, at least for fcc solid solutions [14,32,33]. It might be
also an explanation for the bcc solid solution formation
during SPD. Additional enthalpy which comes from the
SPD is not included in this calculation. Therefore, the

enthalpy contribution from the interface, together with a

contribution from the deformation, might be large enough
to overcome the positive heat of mixing of this alloy in the
bcc region.
Another explanation is given in Ref. [28]: dislocation
shear driven alloying is proposed to explain the mechanically induced mixing in normally immiscible systems. This
process includes a dislocation-assisted carrier mechanism
with multislip shear transfer on more than one slip system
across heterophase interfaces. This mechanism is also
known as dislocation shue mechanism [34].
4.3. The hardness evolution after annealing
Decomposition occurs during annealing above temperatures of 300 C, which leads to the formation of a nanocrystalline FeCu composite material with an enhanced
hardness and an extraordinary thermal stability. Even at
high annealing temperatures, the nanocrystalline structure
of the composite is retained and hardness values remain
nearly constant. After decomposition, separated fcc and
bcc phases exist in the composite. Due to this structural
conguration, where grains of the one phase may be isolated from the other phase grain growth through boundary
migration is reduced [35]. Another reason for the observed

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A. Bachmaier et al. / Acta Materialia 60 (2012) 860871

high thermal stability may be impurities which are introduced in the latter bulk compacts from the as-received
powders or from contamination during processing. Such
impurities would furthermore retard grain boundary movement. However, due to the relative large initial powder size
the content of impurities should be relatively small.
In general, the hardness of the FeCu composites in the
as-deformed state increases with increasing Fe content
after both processing steps. With a simple rule of mixture,
H composite H Cu  F Cu H Fe  F Fe

the upper bound of the hardness of the composite

(Hcomposite) materials can also be calculated. For HCu and
HFe, which denote the hardness of pure Cu and Fe with
a similar grain size (15 nm), values of 153 and 693 HV
are used [36,37]. FCu and FFe is the fraction of Cu and Fe
in the composite. The predicted hardness values of the
composites calculated with this rule of mixture are lower
compared to the experimental ones in the case of the
Fe85Cu15 and Fe15Cu85 samples. Therefore, solid solution
hardening seems to take place although it is only reported
to occur for Cu(Fe) alloys [38]. The experimental hardness
of the Fe50Cu50 ts well to estimated ones but the experimental hardness of the Fe70Cu30 sample is too low. After
decomposition of the single-phase FeCu composite structure (Fe85Cu15 and Fe15Cu85) and before grain growth during annealing sets in, an enhanced hardness compared to
the as-deformed material is observed. The same behavior
is observed in supersaturated CuCr composites [18]. In this
case, solid solution softening in the as-deformed state was
given as an explanation for the enhanced hardness in the
annealed state. In our case, no solid solution softening occurred in the as-deformed samples. One explanation for the
enhanced hardness after annealing in our study might be
the additional strengthening from the interphase boundaries between the dissimilar bcc and fcc phases, as shown
in Ref. [39], which are formed right after decomposition.
Nevertheless, further investigations regarding the hardness
phenomena have to be conducted to explain the details of
the observed phenomena in future.
5. Conclusion
Bulk nanostructured FeCu alloys are prepared by a twostep HPT deformation process. In all alloys fcc and bcc
solid solutions which are far from equilibrium are formed
with this new two-step SPD technique similar to ball milling. After the rst processing step, an ultrane-grained
two-phase composite material is formed. After the second
deformation step, nanostructured supersaturated solid
solutions were achieved. It was shown that mechanical
intermixing of Fe and Cu is possible with SPD. The decomposition of the supersaturated solid solutions upon annealing is used to produce in situ two-phase nanocrystalline
homogeneous FeCu composites. The FeCu composites
after annealing show an enhanced hardness as well as a
high thermal stability.

The advantages of the newly developed process are an

uncomplicated control of the composition of the alloy,
the possible combination of arbitrary material combinations, the easy production process and a high-quality nal
product which is already in bulk form.
Acknowledgments
The nancial support by the Austrian Science Fund
(FWF):[S10402-N16, S10403, T 512-N20] is gratefully
acknowledged.
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