Reversible grain size changes in ball-milled nanocrystalline

Fe-Cu alloys
J. Eckert, J. C. Holzer, C. E. Krill, III, and W. L. Johnson
W. M. Keck Laboratory of Engineering Materials 138-78, California Institute of Technology, Pasadena,
California 91125
(Received 17 March 1992; accepted 30 April 1992)

Nanocrystalline Fe x Cu 100 -^ solid solutions (x < 60) with single-phase fee structure
have been prepared by mechanical alloying. The average grain size of the powders
(8-20 nm) depends on the composition of the material. Varying the composition changes
the grain size reversibly. This can be explained by the underlying mechanism of plastic
deformation and solution hardening during mechanical alloying coupled with the recovery
behavior of the material.

The technique of mechanical alloying/ball milling
has been used extensively in recent years to synthesize
nonequilibrium phases and states, such as amorphous,
quasicrystalline, and nanocrystalline materials.1"4 The
phase formation by mechanical alloying of binary sys-
tems with a large negative enthalpy of mixing is now
rather well understood,5 but little is known about the
phase formation by mechanical alloying in systems with
a small negative or positive enthalpy of mixing. The
Fe-Cu system is an example of the latter case, since
under equilibrium conditions Fe and Cu are almost com-
pletely immiscible due to a positive enthalpy of mixing.6
Nevertheless, extended solid solubility ranges have been
obtained by thermal evaporation,7'8 liquid quenching, 910
ion implantation,11 and mechanical alloying. 1213
In previous papers we reported on the progress of
alloying the formation ranges, and the thermal stabil-
ity of nanocrystalline FejQiioo-* alloys (10 =£ x «£ 95)
synthesized by mechanical alloying.14'15 Single-phase fee
alloys form for x < 60 and single-phase bec alloys for
x > 80. Both phases coexist for 60 ^ x =£ 80. Upon
annealing, phase separation of the metastable Fe-Cu
solid solutions occurs along with grain growth and
were mixed with epoxy and sliced into 20-50 nm thick
sections with a diamond microtome knife. Composition
analysis by wavelength-dispersive x-ray analysis (WDX)
(JEOL Superprobe 733 operated at 15 kV) revealed only
slight changes in the overall composition of the powders
due to wear debris from the milling tools: less than
2 at. % additional Fe was found even after 24 h of
milling for all compositions.
Figure 1 shows x-ray diffraction patterns for
Fe3OCu7o after different milling times as a typical
example. The elemental lines of Cu and Fe in the
diffraction pattern broaden significantly during milling
and are reduced in intensity. After 8 h the Fe peaks
have completely disappeared and only fee peaks remain.
As the intensity of the elemental x-ray lines is
reduced the diffraction lines of the solid solutions
are displaced compared to the Bragg peaks of pure
Cu and Fe. This indicates that true alloying takes
1 i i
• Cu
Fe30Cu70 Fe
• O

strain release. In this letter we present a detailed study 2 h

of the compositional dependence of the grain size for • o S •
nanocrystalline single-phase fee Fe-Cu solid solutions co
with up to 60 at. % Fe. In particular, it will be shown 1
that the grain size of the alloys changes reversibly w
with changes in composition. This will be discussed c 8 h •
CD
with respect to the underlying mechanism of plastic
deformation during milling.
Elemental Fe and Cu powders with particle sizes of 24 h
=s 100 /nm were mechanically alloyed in a Spex 8000
laboratory mill in argon atmosphere using hardened steel 1 I i 1 i
balls and vial. The ball-to-powder weight ratio was 40 50 60 70 80 90 100
4 : 1 . X-ray diffraction was performed with a Norelco
diffractometer using C u K a radiation (A = 0.1542 nm). 29 (degrees)
For transmission electron microscopy (TEM) (Philips FIG. 1. X-ray diffraction patterns for Fe3OCu7o after different mill-
EM 430 microscope operated at 300 kV) the powders ing times.

1980 J. Mater. Res., Vol. 7, No. 8, Aug 1992 © 1992 Materials Research Society

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place during milling (for details see Ref. 15). Similar
observations have been made for all compositions
investigated. The interpretation of the x-ray results in
terms of a single-phase fee structure has been confirmed
by TEM.14'15
The broadening of the x-ray diffraction lines is due
to a refinement of the crystal size and an increase in
atomic-level strain. To separate both effects we analyzed
the peak broadening as a function of diffraction angle
after correcting for K a 2 intensity and instrumental broad-
ening contributions (for details see Refs. 15 and 16).
Independent of the overall composition, the refinement
of the microstructure during milling is qualitatively
the same for all samples investigated.14'15 The average
grain sizes after 24 h of milling determined from x-ray
diffraction and TEM vary between 8 and 20 nm and are
comparable with the grain sizes reported for other ball-
milled nanocrystalline metals and alloys3'4'17, and with
data reported for Fe-Cu alloys prepared by mechanical
alloying12-13 and inert gas condensation.18 The ultimate
grain size depends on the composition of the material.
This is illustrated in Fig. 2, showing the average grain
size obtained by ball milling for Fe^Cu^o-* powders
after 24 h of milling (filled symbols). Whereas the grain
size can be reduced to only 20 nm for pure Cu, it
decreases to values below 10 nm for Fe-rich fee solid
solutions. This demonstrates that the alloy composition
determines the final grain size. The compositional de-
pendence of the grain size d can be fitted best by
a relation of the type d = 1/(A + Bx), as shown by
the dashed line in Fig. 2. This linear compositional
dependence of l/d has been attributed to solid solution
1 1
1
20 0
\
V
\
1 8—
\
\ -
\ D
E
c 16 —-
S.
a>
N 1 4
a>
10 -
"I
8 --
1 1 1 i
10 20 30
Fe Content
FIG. 2. Average grain size obtained by ball milling for F
powders after 24 h of milling versus Fe content (filled symbols),
and comparison with the grain sizes obtained after changing
the composition and milling for additional 16 h in each step:
(O) Fe 30 Cu 70 /24 h, ( • ) Fe 10 Cu 90 /40 h, (A) Fe 30 Cu 70 /56 h, ( • )
Fe5OCu5o/72 h, and ( X ) Fe 3O Cu 7 o/88 h.
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Communications
hardening effects caused by the segregation of Fe atoms
at stacking faults in the fee lattice.15 The dislocations
become immobile due to the decoration with solute
atoms and no further plastic deformation by dislocation
motion can be accomplished. Hence, the grain size
reaches a steady-state value.
To get further insight into the compositional de-
pendence of the grain size, we investigated the change
in grain size upon changes in composition. Fe3oCu7o
powder was first milled for 24 h and some material was
kept for further characterization. The premilled powder
was then blended with elemental Cu to give an overall
composition of Fei 0 Cu 90 and milled for an additional
16 h. This time interval was chosen to guarantee com-
plete alloying and steady-state conditions during milling.
Subsequently, the composition was changed back to
Fe3oCu7o by adding elemental Fe, then to Fe5OCu5o,
and back again to Fe3oCu7o (each composition was
milled for 16 h). In all cases a single-phase fee alloy
was obtained. The actual composition of the powders
does not deviate significantly from the desired nominal
composition even after 88 h total milling time: less than
1.5 at.% additional Fe due to wear debris was found by
WDX. The grain sizes for the powders with different
composition obtained by this set of experiments (open
symbols in Fig. 2) are nearly identical to the grain sizes
for powders milled continuously for 24 h. Varying the
composition results in reversible changes of the grain
size. Thus, the ultimate grain size of the nanocrystalline
alloys is determined by the composition of the material.
This suggests that a "metastable equilibrium grain size"
can be achieved by mechanical alloying under steady-
i 1
state conditions.
It has been shown that the mechanism of achieving
nanocrystalline powders by ball milling is governed
by the severe plastic deformation introduced during
Fe x 0 U 100-x milling.3'17 The final grain size of the powders saturates
— at a steady-state value and no further refinement occurs.
For pure metals we have suggested that the ultimate grain
size achievable by milling is determined by the minimum
grain size that can sustain a dislocation pileup within
^% 0
-
a grain and by the rate of recovery during milling.4
An estimate for the minimum dislocation separation
in a pileup is obtained from the equilibrium between
the repulsive force between two dislocations and the
externally applied force o-app. The lower bound repulsive
-
1 force / per unit length between two dislocations in a
40 50 60 pileup is given by / = Gb 2 /277(1 - v)£, with shear
modulus G, Burgers vector b, Poisson ratio v, and
(at.%) distance between two dislocations €. 19 Assuming that the
hardness h is about 3crapp and the applied shear stress
Tapp ~ (^app/2), the minimum distance L between two
dislocations is L = 3Gb/v(l - v)hP
Applying these calculations to ball-milled pure met-
als shows that the grain sizes of ball-milled elements can
J. Mater. Res., Vol. 7, No. 8, Aug 1992 1981
Downloaded: 25 Mar 2015 IP address: 203.64.11.45
 Communications

be described by a linear relation between d and L (Fig. 3; 25 1 1 i 1 1

the data for pure metals are taken from Refs. 4 and Typical Error /a
17). Hence, a small grain size itself provides a limit for Al
further plastic deformation via dislocation motion and, 20 - CUD / -

therefore, for further grain size refinement by milling. E •

However, the grain size is also limited by the rate c
1 5-- CD / -
of recovery during milling. It is expected that at least Hf A • /
CD AA
partial recovery can occur during milling, thus limiting N

'IK
the dislocation density.4 Therefore, the final grain size /Zr
10 -
achievable by mechanical attrition is determined by the
R
competition between the mechanical deformation and the "a 1
r
D fee
recovery behavior of the material, and the measured ^i O-J Rh
5 - O bee -
ultimate grain sizes are larger than the calculated L
A hep
values.
This general relation can be extended to the Fe-Cu 1 , i 1 i
alloys investigated by considering solid solution harden- 10 12 14
ing effects upon alloying. Since the shear modulus, the Minimum Distance Lc (nm)
hardness, and the Poisson ratio of the nanocrystalline
FIG. 3. Minimum average grain size obtained by ball milling for
Fe-Cu alloys are not known, some assumptions have to pure metals (open symbols) and FexCuioo-x powders (filled symbols)
be made for calculating L. It has been shown above that versus the minimum distance between two dislocations L in solid
\/d depends linearly on the alloy composition. Hence, it solutions with different compositions. The experimentally determined
seems reasonable to assume a Vegard law-type behavior grain size yields a linear dependence on L and is in general larger
than the theoretical lower bound grain size given by L (dashed line),
for B, h, and v and to calculate weighted average
showing the influence of recovery during milling.
values for the nanocrystalline Fe-Cu solid solutions by
using the data for pure Fe and Cu as reference states.
The Burgers vectors of the alloys can be estimated metals. This suggests that the relation for the ultimate
from the measured lattice parameters of fully alloyed grain size achievable by mechanical alloying/ball milling
powders. With this, the L values given in Table I for might in general be applicable for pure metals and alloys
different compositions were estimated (the data for the subjected to mechanical attrition.
pure elements and the lattice parameters of the alloys In summary, it has been shown that mechanical
were taken from Refs. 4, 14, 15, and 17). The increase alloying of single-phase fee Fe-Cu alloys with up to
in the strength and the hardness upon alloying results in 60 at. % Fe leads to a grain size refinement to the
smaller L values than for pure Cu and, therefore, in a nanometer scale. The ultimate grain size of the powders
smaller final grain size obtained by milling. This can depends on the composition of the material and changes
explain the observed decreases of the fee grain size reversibly with changes in composition. This can be
with increasing Fe content (Fig. 2). Figure 3 shows that explained by the underlying mechanism of plastic defor-
the ultimate grain size of the Fe-Cu solid solutions mation via dislocation motion during milling, including
scales in the same manner with L as the data for pure solution hardening effects. A general relation for the

TABLE I. Comparison of calculated minimum distance between two dislocations L with measured average grain sizes d for Fe^Cu^o-* alloys
(x =S 60) and pure metals. The data for the pure metals are taken from Refs. 4 and 17 and the shear modulus G, the Burgers vector b, the
Poisson ratio v, and the hardness h of the alloys are calculated as described in the text.

G (GPa) b (nm) h (GPa) L (nm) d (nm)

0 49 0.256 0.34 2.3 7.9 20

10 52 0.256 0.34 2.9 6.6 17
20 56 0.257 0.33 3.5 5.7 14
30 59 0.257 0.33 4.2 5.1 12
40 62 0.257 0.32 4.8 4.7 11
45 64 0.258 0.32 5.1 4.5 10
50 66 0.258 0.32 5.4 4.4 10
55 67 0.258 0.31 5.7 4.2 9
100 82 0.248 0.29 8.5 3.4 8

1982 J. Mater. Res., Vol. 7, No. 8, Aug 1992

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 Communications
ultimate grain size of nanocrystalline metal powders
based on the mechanism of plastic deformation during
milling has been inferred. However, much work remains
to be done to get a better insight into the detailed
mechanisms of dislocation motion during mechanical
alloying and their impact on the formation and properties
of nanocrystalline powders.
ACKNOWLEDGMENTS
This work was supported by the United States De-
partment of Energy (DEFG0386ER45242). The authors
are grateful to P. Carpenter for technical assistance and
to Y. R. Abe, R. Birringer, and Z. Fu for stimulating
discussions.
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