Acta Materialia 50 (2002) 16391651

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Structure and properties of ultra-fine grain CuCrZr alloy

produced by equal-channel angular pressing
A. Vinogradov a,*, V. Patlan b, Y. Suzuki b, K. Kitagawa b, V.I. Kopylov c
a
Department of Intelligent Materials Engineering, Osaka City University, Osaka 558-8585, Japan
b
Department of Mechanical Systems Engineering, Kanazawa University, Kanazawa 920-5667, Japan
c
Physical-Technical Institute of National Academy of Science of Belarus, Minsk 220141, Belarus

Received 9 October 2001; received in revised form 9 November 2001; accepted 26 November 2001

Abstract

The structure, thermal stability and properties are investigated of a CuCrZr alloy with ultra fine grains (UFG) of
160 nm diameter produced by severe plastic deformation through equal-channel angular pressing (ECAP). Special
attention is paid to optimization of multi-functional thermal, electrical and mechanical properties of this alloy by aging
after ECAP. Fatigue life and cyclic response under strain-controlled experiments are investigated aiming at clarification
of mechanisms of plastic deformation and fracture in the precipitation hardened ECAP materials. It is shown that the
precipitation strengthened UFG structure remains stable both under elevated temperatures as high as 500C and under
cyclic loading at room temperature. Substantial improvement of fatigue life is evidenced in comparison with conven-
tional coarse-grain materials. The appearance of cyclic softening is noticed and its nature is discussed in terms of
dislocationparticle interaction and possible dissolution of precipitates during fatigue. 2002 Acta Materialia Inc.
Published by Elsevier Science Ltd. All rights reserved.

Keywords: Copper alloys; Severe cold working; Mechanical properties; Fatigue

1. Introduction applications and creates new opportunities to

Interesting physical and mechanical properties
of bulk nanostructured (the grain size d is less than
100 nm) and ultra-fine grained (UFG) materials (d
is of 100500 nm) [1] are in focus of many investi-
gations during last decade. The possibility to pro-
duce massive UFG specimens via severe plastic
deformation makes them attractive for engineering
* Corresponding author. Tel./fax: 00-81-6-6605-2179.
E-mail address: alexei@imat.eng.osaka-cu.ac.jp
Vinogradov).
explore their specific properties in comparison with
ordinary coarse grain materials by using the stan-
dard specimens. Equal-channel angular pressing
(ECAP) [2,3] is a technique which allows us to
achieve extremely large imposed strains through
intensive simple shear in bulk samples. During
ECAP, the significant grain refinement occurs
together with dislocation hardening, resulting in
the spectacular enhancement of strength of a work-
ing material [14]. However, many modern engin-
eering applications require a rather sophisticated
(A. combination of physical and mechanical properties
[5] and these requirements can be quite contro-

1359-6454/02/$22.00 2002 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.
PII: S 1 3 5 9 - 6 4 5 4 ( 0 1 ) 0 0 4 3 7 - 2
1640 A. Vinogradov et al. / Acta Materialia 50 (2002) 16391651
versial. For example, in attempts to improve the
fatigue properties by strengthening, i.e. by increas-
ing the yield stress and tensile strength, one can
obtain an excellent endurance limit in the high-cyc-
lic fatigue (HCF) regime, but the low-cyclic fatigue
(LCF) properties and resistance to crack propa-
gation may be reduced considerably due to the loss
of ductility [6], as has been observed in severely
plastically deformed (SPD) materials [6,7]. The
enhancement of both LCF and HCF properties is
possible, in principle, if one improves the tensile
strength together with ductility that is not easy to
achieve via plastic deformation and a judicious
compromise has to be found. It has long been
recognized that SPD is capable of producing strong
materials with rather good ductility. Nevertheless,
the vast majority of experimental data show that
the fine-grained SPD materials are less ductile than
their coarse grain counterparts. This explains why
the low cyclic fatigue performance of ECAP
materials appears to be below expectations. The
other reasons include their low structural stability,
susceptibility to cyclic softening and early strain
localization. A high cyclic softening rate in ECAP
metals, indicating a high degree of structural insta-
bility under load, plays an important role in fatigue
degradation [68]. Several causes have been pro-
posed in the literature to account for this phenom-
enon [6]: (1) dislocation recovery and recovery of
highly disturbed grain boundaries, (2) grain coars-
ening, recrystallization and abnormal grain growth
promoted by cyclic stresses, (3) strain localization
in the large-scale shear bands appearing during
mechanical testing and microcracking. According
to [9], grain growth resulting in local softening
serves as a precursor of strain localization, which
tends to develop in the regions where the resistance
to plastic flow is lower. From acoustic emission
measurements and surface observations, it has been
supposed [10,11] that the shear bands appear very
rapidly as a result of local plastic instabilities
initiated along the non-equilibrium grain bound-
aries in a fashion similar to inhomogeneous plastic
deformation of metallic glasses. Being a specific
case of plastic instability and intensive damage,
shear banding is quite undesirable regardless of its
precise microscopic mechanism. Therefore, when
fatigue is of major concern, the material should be
carefully designed so that to ensure its structural
stability and to eliminate or delay strain localiz-
ation as long as possible. One more problem arises
in the development of ECAP materials owing to
the fact that SPD results in the dramatic decrease
of thermal stability of a working material [1,12] in
view of increasing driving force towards recovery
and recrystallization when the imposed strain
increases.
Several ways towards structure stabilization of
SPD materials can be proposed: (a) annealing
below recrystallization temperature [7,8]; (b) using
of other than wavy slip materials [7]; (c) solid sol-
ution strengthening [7]; (d) particle strengthening.
While the first three approaches have been
explored to some extent (although, in our opinion,
there is still a great need in more systematic data),
the effect of precipitation is unclear to date. The
positive effect of precipitation hardening on the
thermal stability of ECAP materials has been
shown, for example, using the model CuZrO2
composite [13]. Since the cyclic behaviour of
ECAP pure copper has been investigated in more
detail than that of other materials [69], we chose
a commercial precipitation hardened copper based
alloy CuCrZr for the present study. This alloy
is traditionally used in applications where a combi-
nation of high mechanical strength, heat resistance
and electrical (or thermal) conductivity is
demanded (electrodes for point welding, heat
exchangers, fusion reactors, etc. [5]). Thus, the
present work has a triple purpose. The first is to
assess the mechanical properties and, particularly,
fatigue performance of this practically important
CuCrZr alloy subjected to significant grain
refinement and strengthened through ECAP. The
second is to explore the possibility to enhance the
thermal stability and fatigue resistance of ECA-
processed metals through subsequent precipitation
hardening. The third is to optimize the electrical
and mechanical properties by varying tempera-
turetime conditions of the post-ECAP aging.
Hence, in addition to attempts to improve the
fatigue performance we intend to produce the SPD
material which will be heat resistant and will
posses a satisfactory electric conductivity. The lat-
ter issue is important because obtaining a high
enough conductivity is not straightforward in plas-
 A. Vinogradov et al. / Acta Materialia 50 (2002) 16391651
tically deformed metals since their electrical
properties decrease usually with plastic straining
and hardening [14,15]. Emphasis is placed on the
cyclic response under strain-controlled conditions
since this kind of testing provides valuable infor-
mation regarding the mechanisms of plastic defor-
mation and because these conditions are most dif-
ficult to sustain for pre-deformed metals. A special
attention is paid to the effect of processing includ-
ing the number of ECA-passes and the aging con-
ditions on mechanical properties.
2. Experimental procedure
Before ECAP the Cu0.44Cr0.2Zr billets (the
concentration of alloying elements is given in
wt.%) of 1415175 mm were solution treated at
1040C for 30 min and quenched in 5% water sol-
ution of NaCl. After quenching, the samples had
the Vickers microhardness of 50 kgf/mm2. Mul-
tiple pressing through intersecting at 90 square
channels was performed from 1 to 12 times with
0.4 mm/s velocity at room temperature via the so-
called route Bc when the sample was rotated
through 90 clockwise about working axis between
subsequent passes. To provide the uniformity of
simple shear along the intersection plane, the
required boundary conditions [2,3] have been ful-
filled by minimizing the contact friction and ensur-
ing a hydrostatic pressure in the deforming region.
The homogeneity of deformation was verified after
each ECA-pass by observing the fiducial lines
which had been scratched prior to pressing on the
side faces of the billet in the direction perpendicu-
lar to the working axis. The shear strain imposed
during each ECA-pass equals two.
The samples for mechanical testing were shaped
by spark erosion to have a nearly square cross-sec-
tion of 22 mm2 and a gauge length of 10 and 3
mm for tensile and fatigue tests, respectively. The
specimen axis was aligned with the direction of
extrusion. All specimens were mechanically and
electrolytically polished before testing. The LCF
experiments were carried out on a universal Instron
hydraulic frame under plastic strain-control in
fully-reversed tensioncompression at constant
plastic strain amplitudes, pl pl / 2, ranged
1641
from 5104 to 1102. The hysteresis loop shape
was evaluated by the Bauschinger energy para-
meter [16] bE (4saplS) / S where sa is the
peak stress amplitude and S is the area of the hys-
teresis loop. A larger value of bE corresponds to a
pointer hysteresis loop and to the larger Bausch-
inger effect. The invariability of bE serves as a
measure of stability of the hysteresis loop. The
fatigue tests were performed at the same average
cyclic strain rate of 1102 s1 in ambient air at
room temperature. The constant stress amplitude
was applied in HCF tests. The tensile tests were
performed on the same testing machine with a con-
stant strain rate of 103 s1. The ordinary commer-
cially produced Cu(0.91.3)Cr alloy (Yamaha
Corp.) with mean grain size of 26 m was used as
a reference material. The standard industrial
thermo-mechanical treatment of this CuCr alloy
includes drawing, quenching from 980C and age-
ing at 450500C for 1.52 h.
A 200 kV transmission electron microscope
(TEM) equipped with an energy depressive X-ray
spectrometer (EDS) was employed for structural
characterization of the samples prior to and after
fatigue as well as after various heat treatments. The
specimen surface after tensile and fatigue tests was
observed by scanning electron microscopy (SEM)
to detect the traces of plastic deformation, strain
localization and microcracking.
To obtain maximum strength after intensive pre-
straining during ECAP and to explore the effect of
precipitation hardening on fatigue of ECAP
materials, the specimens were subjected to iso-
thermal aging at different temperatures. Differen-
tial scanning calorimetry (DSC, Rigaku 8230)
helped to evaluate the thermal stability of ECAP
structure and to monitor the phase transformations
under linear heating with a constant heating rate of
20 K/min. An empty platinum cell was used as a
reference and the second DSC run served as a base
line. The results of DSC helped to determine trial
aging temperatures as discussed below. Aging was
performed using either an ordinary vacuum furnace
or the Shinku-Riko furnace allowing rapid heating
and precise temperature control in vacuum to min-
imize possible effects from heating rate that is
particularly important for flash annealing at rela-
tively high temperatures.
1642 A. Vinogradov et al. / Acta Materialia 50 (2002) 16391651
The Vickers microhardness was measured on the
plane perpendicular to the working direction in the
as-fabricated ECAP state after different number of
pressings through the dies and after annealing
under various conditions. The applied load was 500
g, and the loading time was of 15 s. The average
values of at least five successive measurements
were calculated. The electric conductivity prior to
and after annealing at different temperatures and
holding times was measured relative to the inter-
national annealed copper standard (IACS).
The acoustic emission (AE) technique was util-
ized for real-time monitoring of strain localization
and microcrack nucleation during fatigue. The
computer controlled broad-band (501000 kHz)
AE apparatus has been described in detail in
[11,17]. During data processing, the artificial
false signals from the laboratory equipment were
identified and removed using a pattern recognition
technique. For each AE signal crossing the thres-
hold, the Fourier power spectral density function
was calculated. The averaged spectrum of the pre-
recorded background noise was subtracted from
the AE spectra and then the AE energy, E, and the
median frequency were calculated (the details of
data processing are given in [17]). Formerly the
same approach was applied effectively to investi-
gate the strain localization and crack nucleation in
ECAP Cu during tensile tests and fatigue
[10,11,17].
3. Results
3.1. Microhardness, electric conductivity,
thermal stabi1lity and aging conditions
The significance of aging for deformation-pro-
cessed Cu-based alloys has been well understood
for optimization of both strength and electrical
conductivity [14,15]. The DSC curve of the ECAP
specimen, Fig. 1, reveals the complexity of multi-
stage structural transformations in CuCrZr under
linear heating. The enthalpy release peak, which
can be associated with recrystallization, starts at a
rather high temperature of 525C and its maximum
is reached around 650C. The onset of the first
exothermal reaction is noticed about 220C and the
Fig. 1. The enthalpy release rate during linear heating of the
ultra-fine grain CuCrZr alloy subjected to 12 ECA-passes.
DSC peak is visible around 350C. The second
maximum is achieved near 440C. These findings
are in line with former detailed investigations of
precipitation kinetics in binary CuCr, CuZr and
ternary CuCrZr alloy [18], where it was found
that in the as-quenched specimen, Cr precipitates
appeared first at about 440C and then Cu3Zr pre-
cipitation occurred separately at about 520C. In
the cold-worked specimen, the order of precipi-
tation was reversed, that is, Cu3Zr and Cr appeared
at about 370C and 425C, respectively. The two
precipitation temperatures observed in the ternary
alloy agreed well with those of the respective
binary alloys. We should point out that the precipi-
tation kinetics in the present CuCrZr alloy
appears to be somewhat more complex than that
described in [18], and one more pronounced peak
is visible around 500C.
Three aging temperatures 375, 425 and 500C
were chosen upon the DSC results and the
annealing time was estimated from the Vickers
microhardness measurements performed after
holding the probe samples in the furnace for differ-
ent periods of time. At first, the effect of the num-
ber of ECA-passes was explored on the resultant
hardness. The samples were heated up to the
desired temperature within 1 h and cooled down
to room temperature within about 4 h after holding
at 375C up to 15 h. Fig. 2 demonstrates that (1)
ECAP gives rise to substantial strengthening which
tends to saturate after six pressings, and (2) further
hardening is achieved after aging so that the HV
magnitude reaches 232 kgf/mm2, which is mark-
 A. Vinogradov et al. / Acta Materialia 50 (2002) 16391651
Fig. 2. Vickers microhardness HV of ultra-fine grain CuCr
Zr as a function of number of ECA-passes in the as-fabricated
state and after aging at 375C, 15 h.
edly higher than 165 kgf/mm2 in the commercially
manufactured CuCrZr specimen. The improve-
ment of HV in comparison with that in the ordinary
CuCr alloy (HV of 150 kgf/mm2) is even more
pronounced.
The dependence of HV on the aging temperature
is illustrated in Fig. 3 for the specimens subjected
to 8 and 12 ECA-pressings. One can see that the
temperature Th, at which the maximum HV magni-
tude is achieved, depends on the amount of pre-
strain during fabrication and is higher for the speci-
mens with smaller pre-strain, i.e. for the 8-pass
specimens Th is close to 500C while for the 12-
pass specimens Th is 430C. This reflects the fact
that hardening in CuCrZr occurs due to multi-
stage precipitation which depends on the pre-strain
history. We should mention that the ability of cold
Fig. 3. Vickers microhardness of UFG CuCrZr alloy as a
function of aging temperature. Aging time is 1 h.
1643
working to accelerate the rate of aging has long
been understood [19] and therefore our result on
SPD CuCrZr is within expectations.
Fig. 4 shows the dependence of Vickers hard-
ness on the aging time. The HV magnitude saturates
at 220225 kgf/mm2 during iso-thermal annealing
at 375C. The higher HV value (of 236 kgf/mm2)
can be reached during short time annealing (from
15 min to 1 h) at 425C. Further annealing at the
same temperature results in gradually decreasing
HV so that the peak-aging conditions can be
defined.
Finally, for mechanical testing the 12-pass
specimens were aged at 375C for 15 h and 425C
for 1 h, and the 8-pass specimens were aged at
425C and 500C for 1 h. Based upon the results
shown Figs. 1, 3 and 4 the samples heat treated at
375C should be regarded as under-aged and the
samples heat treated at 425 and 500C are nearly
peak-aged. As will be shown below, the structure
remains fine-grained after annealing at 500C and
even at 600C for 1h. For the sake of comparison
we should mention that the structure of pure
(99.9699.98%) ECAP Cu is quite unstable, and a
rapid grain growth occurs at temperatures lower
than 120C or even at room temperature [2,12].
To meet the industrial needs, the Cu-based
alloys for electro-mechanical applications must
have the electric conductivity sel better than 75
80% IACS [15]. As shown in Fig. 4, the as-fabri-
cated ECAP billets have a very poor electrical per-
Fig. 4. Vickers microhardness and electric conductivity of
UFG CuCrZr alloy as a function of aging time at different
temperatures.
1644 A. Vinogradov et al. / Acta Materialia 50 (2002) 16391651

formance, sel of 28% IACS, that is absolutely

unacceptable. Subsequent aging at 375C for 15h
improves the electric conductivity significantly, but
not enough. The affordable results with the con-
ductivity up to 81% IACS were achieved when the
12-pass or 8-pass specimens were aged for 1 h in
the infrared furnace with rapid heating to 425C
and 500C correspondingly.
Thus, in concurrence with objectives of the
present study we state that the thermally stable pre-
cipitation hardened UFG material has been manu-
factured through multi-pass ECAP followed by
aging. By varying aging temperatures and time one
can obtain a satisfactory electric conductivity with-
out unaffordable loss of hardness of the CuCrZr
alloy. We shall now confine ourselves to charac-
terization of this UFG material and its fatigue
behavior. A comprehensive description of precipi-
tation kinetics and morphology of precipitates in
CuCr and CuCrZr alloys is available in the rel-
evant literature [18,2026].

3.2. Microstructure

3.2.1. Microstructure of ECAP CuCrZr

Fig. 5a shows a typical microstructure of Cu
CrZr after 12 ECA-passes together with a selec-
ted-area electron diffraction (SAED) pattern
obtained from a region of 0.8 m diameter. The
thin foil was sectioned from the plane perpendicu-
lar to the working axis. The structure in the as-
fabricated state appears very uniform and fine. The
appearance of macroscopic strain heterogeneity
after large deformations by rolling has been
observed in a CuCr alloy and investigated in
detail [27]. It was shown that the shear bands
appear on a free surface of the deformed specimens
after true rolling strain of 0.65 depending on the
aging conditions. We should notice that after a
much greater amount of ECAP pre-strain no
macroscopic shear bands were apparent on the sur-
face or in the TEM photos of the material under
investigation after 4, 8 or 12 ECA-passes (although
the flow pattern containing elongated grains can be
visible after other number of passes through the
used route Bc). This seems to be an advantage of
ECAP technology which, if performed in accord
with mechanical conditions stipulated in [2],
Fig. 5. Bright-filed TEM images of the structure of the Cu
CrZr alloy after 12 ECA-passes: (a) as-fabricated state,
SAEDP; (b) aged at 375C, 15 h; (c) aged at 500C, 1 h; (d)
aged at 600C, 1 h; (e) aged at 700C, 1 h; (f) fine precipitates
in the grain-boundary vicinity after aging at 375C, 15 h; (g)
aged at 375C for 15 h and fatigued at pl / 2 103, (h) aged
at 375C for 15 h and fatigued at pl / 2 102.
allows a uniformity of simple shear through the
whole working volume. Comprehensive dis-
cussions on structure formation during ECAP in
dependence on the straining path and other pro-
cessing parameters can be found elsewhere
[1,3,28,29]. The grain size after 8 or 12 ECA-
passes is nearly the same (of 160 nm) in average as
evaluated from TEM micrographs by the intercept
method in the as-fabricated state. The SAED pat-
tern consists of rings of diffraction spots demon-
strating that the grain boundaries have high angles
of misorientation. The ability of ECAP to produce
the UFG structures with high-angle of misorien-
tations between grains has long been recognized
 A. Vinogradov et al. / Acta Materialia 50 (2002) 16391651
and evolution of the distribution of grain bound-
aries over the misorientation angle has been sys-
tematically investigated in dependence on the
straining path [28,29]. The average dislocation
density is typically high [1] and close to 10131014
m2 as estimated to the order of magnitude by the
standard weak-beam technique [30]. With such a
high density, close to the limiting resolution with
ordinary TEM, the chaotic dislocation arrangement
is energetically unfavorable, and dislocations are
unevenly distributed so that the small grains in
their central parts are rather free of dislocations and
most dislocations are attracted to the grain bound-
aries, that suggests the presence of high internal
stresses created by grain boundaries. The above
estimate of the dislocation density is qualitative
rather than quantitative since the TEM technique
does not take into account the dislocations in grain
boundaries and does not provide a satisfactory
accuracy in quantifying the number of dislocations
in dense arrays which are observed often in the
structure.
3.2.2. Microstructure after aging
It is impressive that the ECAP structure remains
fine-grained during heating and aging at tempera-
tures up to 600C, Fig. 5bd. No substantial grain
growth is noticed. The dislocation density is high
even after aging at 500C, indicating that the dislo-
cations are strongly pinned. The grain growth
becomes noteworthy only at temperatures as high
as 650700C, Fig. 5e, confirming that the DSC
peak around 650C in Fig. 1 should be attributed
to recrystallization and grain growth. The fine
chromium precipitates (of 520 nm size) become
visible after aging at 375C predominantly in the
grain boundary regions or in the vicinity of the
boundaries, Fig. 5f. The EDS analysis shows that
Cr precipitates first under given aging conditions
(in fair agreement with [18,20]), whereas Zr
remains mostly in solid solution. At higher tem-
peratures such as 425 and 500C, etc., the mor-
phology of precipitates does not change appreci-
ably (we noticed some but no substantial
coarsening of precipitates, which still remain in
range of fine 520 nm diameters), however, Zr
containing particles can be found randomly in the
foil. This is also consistent with the results reported
1645
in Refs. 18 and 20. The fact that during early stages
of decomposition of solid solution chromium can
form very fine metastable precipitates coherent
with the copper matrix in CuCr alloys has been
well understood in former detailed TEM investi-
gations [20,23,24,26] and is among most important
for the present study. Transformation of Cr precipi-
tates to the large and stable b.c.c. particles occurs
at higher temperatures and longer annealing
times [25].
3.2.3. Microstructure after fatigue
In the present work, TEM does not reveal any
significant difference in the fine structure before
and after fatigue of ECAP CuCrZr. Fig. 5g and
5h show the structure after cycling at pl / 2
103 and 102 correspondingly. Unlike some other
ECAP materials such as pure Cu and 5056 AlMg
alloy [79], CuCrZr does not exhibit visible
grain coarsening or changes in the arrangement and
density of dislocations after fatigue. The average
dislocation density remains high, and no particular
dislocation configurations such as plain arrays,
dipoles or walls are observed in the fatigued speci-
mens. As a matter of fact, it becomes much more
difficult (or even fully fortunate) to observe fine
precipitates in the grain interior even at high mag-
nifications (up to 200 000) in both bright and
dark fields.
Thus, the following conclusions can be drawn
from TEM inspections of the ECAP CuCrZr
specimens: (1) a very fine severely deformed
ECAP structure is quite stable in terms of grain
size and dislocation configuration at temperatures
up to 600C and under cyclic loading at room tem-
perature; (2) fatigue mechanisms cannot be asso-
ciated with formation of any specific dislocation
structure in the fine grains; (3) fine coherent Cr
precipitates can dissolve, in principle, (at least
partly) in the Cu matrix during fatigue because of
cutting by moving dislocations (see, for example,
[31,32] and references therein for details of such
mechanism) and this will be further argued from
the results of mechanical testing.
3.3. Tensile testing
Tensile stressstrain curves are shown in Fig. 6.
It is worth noticing that the as-fabricated ECAP
1646 A. Vinogradov et al. / Acta Materialia 50 (2002) 16391651
Fig. 6. Tensile stressstrain curves of the ECAP CuCrZr
alloy after various thermo-mechanical treatments in comparison
with reference commercial CuCr.
sample, curve 1, is rather ductileits total elong-
ation to failure is larger that that for ordinary
quenched and aged CuCr, curve 6. This result is
important because the high ductility is an obvious
benefit for formability, fatigue life and resistance
to crack propagation. Aging after ECAP results in
precipitation hardening leading to further increase
in the yield stress and the ultimate strength of the
tested materials. As can be seen, after aging of the
ECAP specimens their sy and sUTS values increase
to 65020 MPa and 70040 MPa correspondingly
and become much higher than in the reference Cu
Cr specimen (sy390 20 MPa). They are also
greater than sy and sUTS in ordinary commercially
treated CuCrZr specimens, as well as in the as-
fabricated ECAP specimens without aging. The
peak aging is achieved when the specimen is held
at 425C for 1 h, curve 4.
3.4. Strain-controlled fatigue
Since the cyclic response of the material under
investigation is qualitatively similar for the speci-
mens subjected to different ECAP followed by
aging treatments we shall illustrate most important
features of their cyclic behaviour on the specimens
pressed 8 times through the dies and then aged at
500C for 1 h, Fig. 7. Progressive cyclic softening
occurs at all plastic strain amplitudes applied and
in all aged specimens tested including reference
Fig. 7. Cyclic response of ECAP CuCrZr (8 passes, aged
at 500C, 1 h) tested under different pl / 2. Plastic strain ampli-
tudes are indicated on the graphs.
commercial CuCr. The rate of softening is slightly
dependent on the plastic strain amplitude, increas-
ing with increasing pl/2. Nevertheless, the sus-
ceptibility to softening is very sensitive to the
thermo-mechanical history of the specimens. Fig. 8
demonstrates the cyclic hardening/softening curves
for different specimens examined at the moderate
plastic strain amplitude pl / 2 1 103. One
can see that the highest softening rate is demon-
strated by the specimen that has received the larg-
est amount of pre-strain (12 ECA-passes) and aged
at 375C. We would like to emphasize that the as-
fabricated but not aged ECAP specimens do not
soften, curve 1 in Fig. 8, despite intensive pre-
straining. This fact can serve as an evidence for a
dominant role played by strengthening particles in
Fig. 8. Cyclic hardening/softening curves for CuCrZr and
CuZr alloys subjected to different thermo-mechanical treat-
ments and tested under the same plastic strain amplitude
pl /2 103.
 A. Vinogradov et al. / Acta Materialia 50 (2002) 16391651
cyclic softening of the materials under investi-
gation. Fig. 8 also confirms that by changing aging
conditions one can largely vary the cyclic response
of dispersion hardenable alloys after ECAP.
Although softening is visible in ECAP CuCrZr,
it should not be entirely associated with SPD fabri-
cation, because this phenomenon is commonly
observed in commercial CuCrZr and CuCr
which did not receive such intensive pre-strain.
The low-cyclic fatigue life dependence on the
plastic strain amplitude obeys the CoffinManson
law: epl / 2 ef(2Nf)c with f the fatigue ductility
and c the fatigue exponent, both are materials con-
stants, Fig. 9. Typically for many other SPD
materials [7], fatigue life of ECAP CuCrZr is
somewhat shorter than that of the reference com-
mercial CuCr material that emphasizes a key role
of ductility in fatigue under strain control. Fatigue
life of the ECAP specimens is the shortest in the
underaged state (aging at 375C). It is worth not-
ing, that the slope of the CoffinManson line is the
same for the reference CuCr (c 0.68) and for
the as-fabricated ECAP alloy, while the fatigue
exponent in the aged ECAP specimens is notably
higher (c 0.92 for the 8 ECA-pass CuCrZr
aged at 500C 1 h) so that at high strain amplitudes
greater than 102 the aged ECAP specimen may
endure longer than its non-aged counterpart or
commercial CuCr. When comparing two different
materials, CuCrZr and CuCr, one should also
bear in mind that the latter material contains fewer
amounts of strengthening secondary phases and
Fig. 9. CoffinManson plots for materials under investigation.
1647
precipitates. It is therefore less strong and more
ductile, Fig. 6, which results in the smaller absolute
value of the fatigue exponent and somewhat longer
low-cyclic fatigue life. It is, however, undoubtedly
shown that LCF properties of present CuCrZr
are in range of practical expectations, and these
properties are variable through post-ECAP thermal
treatment that helps to obtain a desired compro-
mise in HCF and LCF performance.
3.5. Large-scale shear banding and cracking-
surface observations and AE analysis
Strain localization in the form of large-scale
shear bands occurs in the ECAP CuCrZr alloy in
both tensile and cyclic testing, Fig. 10, in a manner
similar to that in pure copper or in the non-heat
treatable 5056 AlMg alloy. The shear bands in
cyclic deformation are more pronounced than those
in tension, indicating the strong strain localization
during fatigue. However, there is an important dif-
ference in appearance of the shear bands in UFG
CuCrZr and, for example, UFG pure Cu. While
the shear bands may nucleate relatively early dur-
ing cycling of UFG Cu [17], the in-situ surface
observations show that the large shear bands in
UFG CuCrZr emerge only in the very late stage
of fatigue shortly before failure. The post-experi-
mental SEM observations reveal that the shear
bands are located primarily in the vicinity of frac-
ture surface and their number and density are not
high if compared to that in ECAP Cu. The density
of the shear bands depends strongly on the plastic
strain amplitude and is greater for larger pl/2.
The moment of appearance of the first shear bands
can be reliably identified with a help of acoustic
emission technique [17]. As shown in Fig. 11 the
AE activity becomes notable just before failure
when the stress amplitude begins to fall rapidly and
when the hysteresis loop becomes unstable as
reflected by the rapid increase in the magnitude of
bE. As a matter of caution, we note that the surface
micro-cracks nucleate on the same stage of defor-
mation (see Fig. 10b and c) and their nucleation
is greatly facilitated by shear banding. Both shear
banding and microcracking contribute to the result-
ant AE, giving rise to notable AE activity before
failure. The simple AE picture shown in Fig. 11
1648 A. Vinogradov et al. / Acta Materialia 50 (2002) 16391651
Fig. 10. Shear bands on the surface of CuCrZr (12-pass
ECAP, aged at 375C for 15 h): (a) tensile test, (b) fatigue at
pl / 2 103; (c) fatigue at pl / 2 102. Arrows indicate
the loading axis.
in terms of the total number of AE events does
not allow us to distinguish between these two AE
sources. However, it has been shown in Ref. 17
for cyclically deforming ECAP Cu that the dis-
Fig. 11. AE appearance in the cyclically deformed ECAP Cu
CrZr.
crimination between these two sources is possible
by means of the AE spectral and cluster analysis.
Application of this approach to CuCrZr demon-
strates that two categories of AE signals can be
recognized in the same way as was done in Ref.
17 for Cu. Since the AE features are of minor inter-
est for the present study we shall not deepen the
AE analysis here. It is sufficient to claim that even
a simplified AE analysis proves that shear banding
and microcracking in ECAP CuCrZr take place
only on the late stage of deformation while the
specimen surface remains smooth during in the
longest part of fatigue life.
3.6. Stress-controlled fatigue
To complete the assessment of fatigue perform-
ance it is of interest to consider the results of HCF
testing shown in Fig. 12 for UFG CuCrZr in
context of available literature data for Cu and com-
mercial Cu-based alloys [33,34]. One can see that
ECAP CuCrZr does not show an apparent endur-
ance limit in the range of number of cycles up to
107. There is no any knee or trend to leveling on
the SN (stress versus number of cycles to failure)
curve. This is, however, typical for Cu-based
alloys. HCF life of severely deformed and aged
CuCrZr is much longer than that of its commer-
cial analogue. As can be seen in Fig. 12, the fatigue
limit f defined on the basis of 107 cycles in ECAP
CuCrZr is of 285 MPa that is considerably
higher than that has been reported in [33,34] for
commercial Cu0.8Cr0.07Zr (Tre fime taux,
sy100 MPa), Cu1.98Ni0.32Be alloy (Brush
 A. Vinogradov et al. / Acta Materialia 50 (2002) 16391651
Fig. 12. Stress amplitude versus number of cycles to failure
(SN curve) of ECAP CuCrZr in comparison with commer-
cial tempers.
Wellman Hycon 3HP, sy700 MPa), and Cu
0.75Cr (Wieland Werks AG, sy310 MPa). This
seems to be an impressive achievement of ECAP
technology if compared with traditional commer-
cialized tempering processes and in combination
with high thermal stability and electrical conduc-
tivity this should promote an engineering appli-
cation of the ECAP Cu-alloys.
4. Discussion
In the preceding section we have underlined the
difference in the cyclic response of as-fabricated
ECAP and aged after ECAP specimens: the former
demonstrates the steady stress amplitude during
cycling whereas the latter exhibits notable soften-
ing which is particularly pronounced at the begin-
ning of fatigue loading. It has been recognized that
cyclic hardening and softening in precipitation
strengthened alloys is closely related to the type,
morphology and density of second-phase particles.
The geometrical relationship at the precipitate
matrix interface or coherency between the precipi-
tates and the matrix is of primary importance for
the resultant properties and mechanisms of
strengthening and plasticity. Cyclic softening is
strongly favored if the precipitates are easily shear-
able by dislocations, i.e. if they are (1) fine and (2)
coherent with the matrix [24]. It has been shown
1649
by TEM observations that both these conditions
can be fulfilled in CuCr alloyschromium pre-
cipitates in copper matrix are fine, spherical and
coherent with Cu matrix predominantly on the
early stage of decomposition of the supersaturated
solid solution [24,26]. The following arguments
are put forward to claim that the origin of cyclic
softening after ECAP followed by aging should be
related to the dislocationprecipitates interaction
and cutting of precipitation by moving dislo-
cations primarily.
No substantial reduction in the dislocation den-
sity and no grain coarsening are observed in
cyclically deformed ECAP CuCrZr, i.e. cyc-
lic softening cannot be associated with the insta-
bility of severely pre-deformed structure.
Strain localization in the shear bands cannot be
a cause of softening because these bands in the
UFG CuCrZr alloy nucleate only shortly
before failure.
Not aged ECAP specimens do not soften.
Furthermore, the TEM observations allow us to
suppose that many precipitates, at least the smallest
coherent ones, in the grain interior can dissolve
during cycling as a result of cutting by gliding dis-
locations in line with the suggestion of Hornbogen
and co-workers about local dissolution of cut par-
ticles in the shear bands [31].
To provide further evidence in favor of precipi-
tation dissolution during cyclic loading the special
experiment was performed as follows. Two speci-
mens subjected to eight ECA passes were aged at
375C for 15 h and 425C for 1 h, respectively.
Then they were subjected to fatigue loading at
pl 103 up to the cumulative plastic strain of
0.8, that is much smaller than the strain when the
shear bands or microcracks could be observed on
the surface. The specimens were carefully dis-
mounted from the grips and annealed once more
under the same conditions, i.e. at 375C and
425C, respectively. After that the specimens were
fatigued again under the same conditions and their
resultant cyclic response is shown in Fig. 13 in
terms of hardening curves and the Bauschinger
energy parameter. The significant decrease of the
stress amplitude is observed from the onset of the
1650 A. Vinogradov et al. / Acta Materialia 50 (2002) 16391651
Fig. 13. Cyclic response of the ECAP (8 pass) CuCrZr
specimen subject to the second aging after fatigue to N=200
cycles at pl / 2 103 (first and the second aging were perfor-
med under the temperature of 425C and time of 1 h).
first loading in the same manner as has been
described in the previous section. The second heat-
ing tends to remove the effect of prior cyclic defor-
mation, resulting in the considerable increase of sa,
that occurs most likely due to precipitation harden-
ing. However, the stress amplitude did not recover
completely after re-aging and the second straining
occurs at lower stresses than at the beginning of
the first loading. This can be either owing to some
dislocation annihilation during fatigue or
annealing, or because the second aging did not
restore the initial amount and distribution of pre-
cipitates. Since we did not observe the gross
reduction in the dislocation density during fatigue
or isothermal annealing up to 500C, the second
reason seems to be more probable. Furthermore,
the Bauschinger effect after the intermediate heat-
ing becomes significantly lower than at the end of
the first cycling, indicating thereby some dislo-
cation recovery. Thus, one can conclude that cyclic
softening of aged specimens is associated with par-
tial dissolution of precipitates under cyclic plastic
deformation. We should underline that particle dis-
solution becomes more difficult and the rate of
softening decreases when the aging temperature
increases because of the increasing size of precipi-
tates.
It has long been recognized from the strain-
based representation of fatigue life that in the low-
cyclic regime at fairly large strains, the plastic
strain amplitude is dominant and fatigue life is
controlled by ductility. The high-cyclic fatigue per-
formance is governed, in contrast, by the elastic
portion of the strain range [6,7,32], as would be
expected from the correlation of the fatigue per-
formance with yield properties. It is important that
the optimally aged ECAP CuCrZr alloy takes
maximum advantage of dispersion strengthening
together with grain refinement through severe plas-
tic deformation so that various combinations of
strength and ductility can be achieved for best fit
of the practical demands. As a recommendation of
further research, we believe it is necessary to
explore the fatigue properties of the SPD fabricated
alloy containing non-shearable particles. The large
Bauschinger effect in the ECAP materials is of
particular interest as it helps to clarify the mech-
anism of their plasticity and the nature of back
stresses. The phenomenological details and the
description of this effect are beyond the scope of
the present paper and will be considered in the
forthcoming communication.
5. Summary and conclusions
The ultra-fine grain CuCrZr dilute alloy has
been fabricated by ECAP. It is undoubtedly shown
that post-ECAP aging makes the precipitation
hardened ultra-fine grain structure rather stable
under both thermal and mechanical influence. Opti-
mal aging conditions are found to ensure the best
high-cyclic fatigue performance in combination
with satisfactory good electric properties and ther-
mal stability. At the same time, the low cyclic
fatigue properties remain high despite some loss of
ductility during fabrication. Strengthening mech-
anisms resulting from a combination of intensive
cold work through ECAP and subsequent aging
have been taken advantage to successfully produce
the material with desired electro-mechanical
properties including sufficient ductility for forming
and adequate resistance to fatigue loading. The sig-
nificant improvement of tensile and HCF proper-
ties is observed without dramatic sacrificing the
ductility and LCF properties. In view of proven
high thermal stability and affordable electrical con-
ductivity, the superior mechanical properties and
fatigue resistance of ECAP CuCrZr open new
perspectives for its potential applications.
 A. Vinogradov et al. / Acta Materialia 50 (2002) 16391651
The experimental details of cyclic response are
presented and the nature of cyclic softening is
investigated in the precipitation hardened ECAP
CuCrZr alloy. It is shown that the reduction of
stress amplitude in the course of fatigue should be
attributed to the shearing of strengthening particles
by dislocations and partial dissolution of the par-
ticles.
Experimental data unambiguously show that the
ultra-fine grain CuCrZr alloy processed by
ECAP followed by aging has many advantages
over currently available commercial tempers in
that it permits designs having much higher working
stresses and fatigue resistance, thus providing a
better cost effectiveness.
Acknowledgements
The authors are indebted to M. Kawazoe (YKK
Corporation, Japan) and T. Yamasaki (Doshisha
University, Japan) for their skilful help in TEM
observations. One of the authors (V.K.) wishes to
thank the Japanese Society for the Promotion of
Science for the fellowship awarded that allowed
completing the present work during his staying in
Japan in 20002001.
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