quenching process in the Cu60(Zr or Hf)30Ti10 alloys. The high [10] M. Imafuku, S. Sato, H. Koshiba, E. Matsubara, A.

Inoue,

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stability of the Cu-rich nanocrystalline cubic phases leads to the Mater. Trans. JIM 2000, 41, 1526.
coexistence with the glassy phase in the nanometer scale. The [11] J. Saida, T. Osuna, , A. Inoue, M. Ohnuma, J. Mater. Res.
formation of Cu-rich nanocrystalline particle is attributed to the 2003, 18, 2013.
excess of Cu content for the single glassy phase formation. It is [12] M. Kasai, J. Saida, M. Matsushita, T. Osuna, E. Matsubara,
also suggested that the Ti element stabilizes the nanocrystalline A. Inoue, J. Phys. Condens. Matter 2002, 14, 13867.
phases. The primary crystallization phases were characterized [13] M. Kasai, E. Matsubara, J. Saida, M. Nakayama,
and we found the difference of the primary crystallization K. Uematsu, T. Zhang, A. Inoue, Mater. Sci. Eng. A 2004,
process between the alloys. The nano bcc CuZr phase is 375-377, 744.
precipitated with remaining the Cu-rich nanocrystalline phase [14] K. Uematsu, Master Thesis, Tohoku University, 2002, 51.
in the Cu60Zr30Ti10 alloy. In contrast, the glassy and Cu-rich [15] J. Saida, T. Osuna, M. Ohnuma, E. Matsubara, A. Inoue,
nanocrystalline phases are transformed to the orthorhombic Sci. Tech. Adv. Mater. 2003, 4, 311.
Cu8Hf3 phase in the Cu60Hf30Ti10 alloy at the first exothermic [16] A. Inoue, Mater. Sci .Eng. A 1997, 226-228, 357.
reaction. The as-cast Cu60Zr30Ti10 alloy has high fracture [17] A. Inoue, Acta Mater. 2000, 48, 279.
strength and Young's modulus. It is noted that the fracture
strength is improved in the primary devitrified alloy, which is
achieved by the unique structure consisting of two different
nanocrystalline phases.
Effect of Equal Channel Angular
Pressing on Microstructure and
Experimental MechanicalPropertiesofIFSteel**
Cu60(Zr or Hf)30Ti10 ternary alloys with ribbon and cylindrical shapes were
produced from alloy ingots prepared by arc melting high-purity metals of By Hyoung Seop Kim,* Won Sun Ryu,
99.999 mass% Cu, 99.9 mass% Zr, 99.9 mass% Hf and 99.9 mass% Ti in a purified
argon atmosphere. The structure and thermal property were studied for of the Milos Janecek, Seung Chul Baik and Yuri Estrin
melt-spun ribbon alloys by X-ray diffraction (XRD) with Cu-Ka radiation
operated at 40 kV±30 mA and differential scanning calorimeter (DSC) with a
heating rate of 0.67 K/s. The microstructure was examined by high-resolution Severe plastic deformation by equal channel angular
transmission electron microscopic (HREM) observation using field-emission pressing (ECAP) is a particularly promising processing route
transmission electron microscopy (FE-TEM) with an accelerating voltage of
300 kV (JEOL JEM-3000F). The sample for TEM observation was prepared by the
for producing fully dense bulk materials with ultrafine grained
ion milling technique with liquid nitrogen cooling. The compositional analysis microstructure.[1±3] While a significant literature on ECAP is
was performed by nanobeam energy dispersive X-ray spectroscopy (EDX). The available,[4,5] most publications deal with materials having the
nanoscale inhomogeneity was also evaluated by small-angle X-ray scattering
(SAXS) measurement using a pinhole collimation type SAXS instrument fcc structure, particularly Al[6] and Cu[7] based systems. Reports
(RIGAKU PSAXS-3S) with Mo target. The compressive test was performed for on ECAP of bcc materials, such as Fe[8,9] and steel,[10±12] are
a cylindrical shape sample at a strain rate of 5”10±4 /s at room temperature. The
fracture surface is observed by scanning electron microscopy (SEM). The
rather scarce, and the deformation behaviour of these materials
microstructure in the sample for mechanical test is also examined by FE-TEM. under ECAP as well as the attendant evolution of the
Received: October 27, 2004
Final version: November 22, 2004 ±
[*] Prof. H. S. Kim, W. S. Ryu
± Department of Metallurgical Engineering
[1] D. Xu, B. Lohwongwatana, G. Duan, W. L. Johnson, Chungnam National University
C. Garland, Acta Mater. 2004, 52, 2621. Daejeon, 305-764 (Korea)
[2] A. Inoue, W. Zhang, J. Saida, Mater. Trans. 2004, 45, 1153. E-mail: hskim@cnu.ac.kr
[3] D. Wang, Y. Li, B. B. Sun, M. L. Sui, K. Lu, E. Ma, Appl. Dr. M. Janecek
Phys. Lett. 2004, 84, 4029. Department of Metal Physics
[4] A. Inoue, W. Zhang, T. Zhang, K. Kurosaka, Acta Mater. Charles University
2001, 49, 2645. CZ 121 16 Prague 2 (Czech Republic)
[5] A. Inoue, Mater. Trans. JIM 1995, 36, 866. Prof. Y. Estrin
[6] F. R. de Bore, R. Boom, W. C. M. Mattens, A. R. IWW, TU Clausthal
Miedema, A. K. Niessen, in Cohesion in Metals, North- Clausthal-Zellerfeld, 38678 (Germany)
Holland, Amsterdam, 1988, 361. Dr. S. C. Baik
[7] A. Inoue, T. Zhang, T. Masumoto, J. Non-Cryst. Solids Technical Research Lab.
1992, 150, 396. POSCO, Pohang, 790-785 (Korea)
[8] A. Inoue, T. Zhang, T. Masumoto, J. Non-Cryst. Solids [**] This work was supported by the KOSEF-DFG international
1993, 156-158, 473. collaboration program and by DFG under grant Es 74/9. HSK
[9] J. Saida, C. Li, M. Matsushita, A. Inoue, J. Mater. Res. 2001, acknowledges the support of his study leave at TU Clausthal
16, 3389. through the KOSEF-DFG visiting fellowship.

ADVANCED ENGINEERING MATERIALS 2005, 7, No. 1±2 DOI: 10.1002/adem.200400146  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 43

microstructure and the mechanical properties are not well
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understood. While most of the studies on steel concern ferritic
or pearlitic carbon steels, first reports on ECAP of interstitial-
free (IF) steels having a single phase ferritic microstructure start
cropping up.[13,14] IF steel is a sheet steel product with very low
carbon levels that is widely used for automotive deep-drawing
applications.[15] In this IF steel the micro alloying elements (Ti,
Nb and V) form precipitates with carbon and nitrogen, rather
than being dissolved interstitially in ferrite. The absence of
interstitial solutes and the appropriate texture in these steels
lead to excellent deep-drawability. An investigation of ECAP of
IF steel as a representative of single phase bcc materials would
be not only of general scientific interest, but it may also
demonstrate a practical applicability of this technique for
improving its mechanical properties.
This paper reports the experimental results on microstruc-
tural evolution and the variation of the mechanical properties
of IF steel after different ECAP histories.
Results and discussion: The bcc ferrite structure in the
annealed specimens is characterized by an average grain size
of 250 lm without any preferred orientation. The microstruc-
ture of the material that underwent different numbers of ECAP
passes, for both Route A and Route C, is presented in Figure 1.
Under both routes, ECAP is seen to lead to a continual grain
1 pass
2 passes, Route A 2 passes, Route C
8 passes, Route A 8 passes, Route C
Fig. 1. TEM micrographs showing the evolution of the microstructure for Routes C and A.
44  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Kim et al/Effect of Equal Channel Angular Pressing
Microhardness and Increments, Hv
250 Hardness
200
Route A - E plane
150
Route A - T plane
Route C - E plane
Route C - T plane
100
Hardness Increment per pass
20
0
0 2 4 6 8
Number of Passes
Fig. 2. Room temperature hardness as a function of the number of ECAP passes. Also
shown is the variation of the hardness increment (the difference in hardness before and
after an ECAP pass)
refinement, an elongated grain structure produced in the first
pass being retained throughout all processing cycles.
The TEM micrographs shown in Figure 1 are a representa-
tive selection of the microstructures observed. Already after the
first pressing, the microstructure shows regions with relatively
small grain size. These regions, consisting of parallel bands of
elongated grains with lengths of 1±2 lm and a width of
200±500 nm (cf. Fig. 1) coexist with heavily deformed regions
with no distinct grain structure. The difference in the
orientation of the grains within a band, as determined by the
Kikuchi pattern analysis, was small (a few degrees). While the
area fraction of the regions with developed grains after one
ECAP pass was about 40±50 %, this quantity went up to about
70 % after the second pass (Route C). In addition to the areas of
elongated grains with low misorientation and average length
and width of 1 lm and 300 nm, respectively, seen in the
micrograph, areas with nearly equiaxed grains, about 1 lm in
size (not shown) were observed. After 8 passes via Route C, a
much more homogeneous microstructure with a well pro-
nounced grain pattern had emerged. It is comprised by large
regions (some 90 % of the area) with elongated grains of
average length of 500 nm-1 lm and average width of 200-
300 nm and a minority population (some 10 % of the area) with
more equiaxed grains.
The variation of the microstructure under Route A, also
shown in Figure 1, is characterized by a more pronounced
development of the grain structure than under Route C. Thus,
two ECAP passes via Route A result in some 90 % of the area
showing well developed grains within elongated bands. After 8
Route A passes the entire area exhibits elongated grains of a
significantly smaller size than for 8 Route C passes. The average
length and width of the grains are 500±800 nm and 100±
200 nm, respectively. A comparison of the TEM evidence for
the microstructure evolution under the two routes considered
shows that Route A is more efficient than Route C with regard
http://www.aem-journal.de ADVANCED ENGINEERING MATERIALS 2005, 7, No. 1±2
Kim et al/Effect of Equal Channel Angular Pressing

to both the rate with which a grain structure emerges and the

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1000

amount of grain refinement obtained. A continuous grain 8Pass

Route A

refinement observed for both processing routes contrasts a 800 6Pass

non-monotonic evolution of the grain size obtained by Gazder 4Pass

true stress (MPa)

2Pass
et al.[14] for Route Bc using a 120  die with backpressure. 600

The effect of the ECAP history on hardness of the IF steel is 1Pass

400 initial
presented in Figure 2. Hardness measurements were taken on
the extrusion (E) and the transversal (T) planes of the
200
specimens processed by ECAP. As seen from Figure 2, the
hardness increased a lot as a result of the first pass, while 0
subsequent passes led to a continually decreasing hardness 0.0 0.1 0.2 0.3 0.4 0.5

increment. However, it should be stressed that the hardness true strain

did increase throughout all ECAP cycles, and hardness (a)

increments were non zero even for the 8th pass, which
1000
behaviour is quite different from what is observed in other 8Passes Route C
materials. In Al,[6] Cu[7] and steel[11] systems, strength and 800
6Passes

hardness saturated quickly (as early as after two passes). By 4Passes

True Stress, MPa

contrast, extended hardening in the ferrite (bcc) phase was 600
2Passes

found.[8] Interestingly, Shin et al.[11] observed that the hard- 1Pass

ening in the ferrite phase was larger than in pearlite in a two-
phase (ferrite and pearlite) low carbon steel. They concluded
that hardening of the two-phase steel was dominated by that of
soft ferrite having a large volume fraction. No big differences in
hardness between the extrusion and the transversal planes
were observed in the present study, despite the fact that
deformation was directional and a considerable planar
anisotropy in the indent shape was found, cf. also.[8] It should
also be noted that hardness values were almost the same in
samples that underwent Route A and Route C processing, in
spite of considerable differences in microstructure described
above. The general trend in the hardness variation with the
ECAP history shown in Figure 2 is obviously a reflection of the
observed microstructural evolution towards smaller grain size.
Here we report our experimental data on room temperature
tensile deformation of the material processed following Routes
A and C. The deformation curves shown in Figure 3 corre-
spond to the strain rate of 1.4 ” 10±4 s±1. With increasing number
of passes the flow stress level increased and elongation
decreased for material obtained using both processing routes,
which is a general finding for ECAP-processed metallic
materials. A high tensile strength above 800 MPa and a tensile
elongation over 15 % achieved with both ECAP routes can be
regarded as a reasonably good combination of strength and
ductility. It should be noted that the tensile strength reached
was even higher than the strength for Route C specimens under
compression obtained in Ref.[13]. In accord with the trend for the
variation of hardness with the number of passes, the tensile
strength was found to continuously grow throughout the entire
ECAP history, up to 8 passes, for both routes investigated.
Conclusions: IF steel was processed by room temperature
ECAP up to 8 passes using Routes A and C. Unlike Al, Cu and
two-phase steels, IF steel exhibits hardening that persists for at
least up to 8 passes. A good combination of tensile strength and
ductility could be achieved as a result of ECAP processing for
both routes, the differences in the efficiency of the two routes
400 initial
200
0
0.0 0.1 0.2 0.3 0.4 0.5
True Strain
(b)
Fig. 3. Room temperature tensile behaviour of the ECAP-processed material; (a) Route A
and (b) route C.
with respect to strength and ductility being rather insignificant.
However, Route A was found to be superior to Route C as far as
its efficacy with respect to grain refinement is concerned.
Experimental
The material used in this investigation was IF steel with a composition of
0.0026 wt% C, 0.096 wt% Mn, 0.045 wt% Al and 0.041 wt% Ti. The material was
manufactured by the Pohang Steel Company (POSCO, Korea) and had the
following history: After casting, the ingot was size rolled to fabricate the plate
12 mm in thickness, homogenized for 1 h at 973 K and then furnace-cooled. For
ECAP processing, the billet was cut into 12 mm ” 12 mm ” 60 mm workpieces,
which were annealed for 2 h at 973 K, furnace-cooled and finally surface-
polished using 1200 grit SiC paper. After the annealing treatment, the mean
intercept grain size measured by optical microscopy was about 250 lm. The
ECAP processing was conducted up to eight passes at room temperature,
following Routes A and C, that is with no ratation or 180  about the longitudinal
axis between the passes, respectively. The die parameter used, viz. the channel
angle (hc= 90 ), the outer corner angle (ho = 0 ) and the inner corner angle
(hI = 0 ) yield a maximum effective strain of 1.155 for a single pass, which
decreases with increasing strain hardening coefficient.[4] The pressing speed was
2 mm/min, which is slow enough to keep the temperature rise during ECAP to
less than several K [16]. A mixture of MoS2 powder and commercial oil was used
for lubrication between the workpiece and the channel surfaces.
Room temperature tensile tests were carried out using an MTS 810 machine
with a constant cross-head speed of 0.001 mm/s, which corresponds to an initial
strain rate of 1.4 ” 10±4 s±1. The Vickers microhardness was measured using an
Akashi HM0-122 tester by applying a load of 100 g force for 15 s and taking an
average over 7 separate measurements.
As the grain structure after ECAP processing could not be resolved by optical
microscopy due to an extremely small grain size, microstructures were examined

ADVANCED ENGINEERING MATERIALS 2005, 7, No. 1±2 http://www.aem-journal.de  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 45
 before and after ECAP by transmission electron microscopy (TEM) using a the Co-Cu, by small angle X-ray then neutron scattering. The
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Philips CM200 microscope. Samples for TEM were taken from the middle part of
the specimen after ECAP deformation, with the transversal plane of the specimen
unmixing of the alloy reported in the present work was
being the viewing plane in most cases. Thin foils for TEM were prepared by completely unexplored whereas some ternary isothermal
electropolishing in a 6 % HClO4 in methanol solution at ±30 C using a Tenupol 5 sections and isopleths of the Co-Cu-Ni system were available
twin-jet device.
in the literature.[3] The 7Co-70Cu-23Ni (at.%) chemical
Received: September 11, 2004 composition studied was chosen because it is located in the
Final version: November 09, 2004 ternary miscibility gap. Moreover, this system can be compared
with results previously obtained on the Cu-Fe-Ni system.[4] The
± Co-Cu-Ni system is very difficult to study due to the proximity
[1] R. Valiev, Met. Mater. Int. 2001, 7, 413.
of the atomic number of each element of the alloy. So, several
[2] I. Alexandrov, Met. Mater. Int. 2001, 7, 565.
techniques were used in order to characterize the phase
[3] M. Furukawa, Z. Horita, T. G. Langdon, Met. Mater. Int.
transformations occurring in this alloy during an ageing
2003, 9, 141.
treatment: the Anomalous Small-Angle X-ray Scattering
[4] H. S. Kim, M. H. Seo, S. I. Hong, Mater. Sci. Eng. 2000,
(ASAXS), the anomalous scattering around the Bragg peaks
291A, 86.
or Anomalous Wide-Angle X-ray Scattering (AWAXS), the
[5] H. S. Kim, S. I. Hong, M. H. Seo, J. Mater. Res. 2001, 16,
Transmission Electron Microscopy (TEM), the dilatometry,
856.
and the thermomagnetometry.
[6] Y. Iwahashi, M. Furukawa, Z. Horita, M. Nemoto, T. G.
Sample preparation: Single crystals with millimetric grain size
Langdon, Metall. Mater. Trans. 1998, 29A, 2245.
of composition 7Co-70Cu-23Ni (at.%) were prepared using the
[7] S. C. Baik, R. J. Hellmig, Y. Estrin, H. S. Kim, Z. Metallkd.
floating-zone technique at LPCES, Orsay, France, from pure
2003, 94, 754.
metallic powders. The bar was pressed under an isostatic press
[8] B. Q. Han, E. J. Lavernia, F. A. Mohamed, Met. Mat.
until to 2500 bar, and then homogenized for 1 week at 1338 K in
Trans. 2003, 34A, 71.
a mixture of Ar and H2 (15 vol.%), then sliced with a diamond
[9] M. Sus-Ryszkowska, T. Wejrzanowski, Z. Pakiela, K. J.
saw. A second homogenisation (16 h at 1223 K) preceded the
Kurzydlowski, Mat. Sci. Eng. 2004, A369, 151.
water quench. Finally, samples were aged at 823 K in the two-
[10] Y. K. Kim, S. M. Kim, K. S. Lee, J. J. Park, D. H. Shin, Met.
phase field (miscibility gap) of the ternary phase diagram, in a
Mater. Int. 2001, 7, 437.
mixture of Ar and H2 (15 vol.%). The chemical composition and
[11] D. H. Shin, B. C. Kim, Y-S. Kim, K-T. Kim, Acta Mater.
homogeneity of the samples were determined by scanning
2000, 48, 2247.
electron microscopy at 15 keV by X-ray microanalysis,
[12] J. Kim, I. Kim, D. H. Shin, Scripta Mater. 2001, 45, 421.
applying the usual correction (Z, A, F), leading to a precision
[13] J. De Messemaeker, B. Verlinden, J. Van Humbeeck, in
of 0.5 at. % in the Co, Cu and Ni concentrations.
Ultrafine Grained Materials III, TMS 2004, 595.
Samples used, either for ASAXS, AWAXS or TEM experi-
[14] A. A. Gazder, C. H. J. Davies, E. V. Pereloma, ibidem,
ments, were electrochemically thinned with a mixture of 2/3 of
p. 321.
methanol and 1/3 of nitric acid and respectively at room
[15] B. Hutchinson, D. Artymowicz, Iron Steel Inst. Japan 2001,
temperature under a voltage of 2 V and at 223 K with a
41, 533.
stabilized current of 130 mA for a section of 7 mm2.
[16] H. S. Kim, Mater. Trans. 2001, 42, 536.
ASAXS results: The ASAXS pattern, represented in Figure 1.
is composed of two sets of well-defined maxima showing a

Phase Transformations in
Co-Cu-Ni Alloys [100]

By I. Guillon*, C. Servant and O. Lyon

[001]
Two of the binary phase diagrams of the Co-Cu-Ni ternary 000
one, Co-Cu and Cu-Ni, present a miscibility gap in the solid
state. In 1984 and 1985, Wagner and co-workers,[1,2] have
studied some alloys belonging to one of these binary systems,

±
[*] Dr. I. Guillon, Dr. C. Servant and Dr. O. Lyon
LPCES, CNRS, UMR 8648
ICMMO, bât 410, UniversitØ de Paris Sud Fig. 1. Two-dimensional isointensity (in logarithmic scale) A.S.AX.S. pattern (recorded
at 8322 eV) of a 7Co-70Cu-23Ni (at. %) single crystal aged at 823 K, for 4 h, oriented
91405 Orsay Cedex, France parallel to the (010) plane, and showing two families of precipitates piled-up in the
E-mail: colette.servant@lpces.u-psud.fr <100>f.c.c. soft directions.

46  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/adem.200400103 ADVANCED ENGINEERING MATERIALS 2005, 7, No. 1±2