You are on page 1of 13

Acta Materialia 50 (2002) 16391651

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
Department of Intelligent Materials Engineering, Osaka City University, Osaka 558-8585, Japan
Department of Mechanical Systems Engineering, Kanazawa University, Kanazawa 920-5667, Japan
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


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

explore their specific properties in comparison with
Interesting physical and mechanical properties ordinary coarse grain materials by using the stan-
of bulk nanostructured (the grain size d is less than dard specimens. Equal-channel angular pressing
100 nm) and ultra-fine grained (UFG) materials (d (ECAP) [2,3] is a technique which allows us to
is of 100500 nm) [1] are in focus of many investi- achieve extremely large imposed strains through
gations during last decade. The possibility to pro- intensive simple shear in bulk samples. During
duce massive UFG specimens via severe plastic ECAP, the significant grain refinement occurs
deformation makes them attractive for engineering together with dislocation hardening, resulting in
the spectacular enhancement of strength of a work-
ing material [14]. However, many modern engin-
* Corresponding author. Tel./fax: 00-81-6-6605-2179. eering applications require a rather sophisticated
E-mail address: (A. combination of physical and mechanical properties
Vinogradov). [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 carefully designed so that to ensure its structural
fatigue properties by strengthening, i.e. by increas- stability and to eliminate or delay strain localiz-
ing the yield stress and tensile strength, one can ation as long as possible. One more problem arises
obtain an excellent endurance limit in the high-cyc- in the development of ECAP materials owing to
lic fatigue (HCF) regime, but the low-cyclic fatigue the fact that SPD results in the dramatic decrease
(LCF) properties and resistance to crack propa- of thermal stability of a working material [1,12] in
gation may be reduced considerably due to the loss view of increasing driving force towards recovery
of ductility [6], as has been observed in severely and recrystallization when the imposed strain
plastically deformed (SPD) materials [6,7]. The increases.
enhancement of both LCF and HCF properties is Several ways towards structure stabilization of
possible, in principle, if one improves the tensile SPD materials can be proposed: (a) annealing
strength together with ductility that is not easy to below recrystallization temperature [7,8]; (b) using
achieve via plastic deformation and a judicious of other than wavy slip materials [7]; (c) solid sol-
compromise has to be found. It has long been ution strengthening [7]; (d) particle strengthening.
recognized that SPD is capable of producing strong While the first three approaches have been
materials with rather good ductility. Nevertheless, explored to some extent (although, in our opinion,
the vast majority of experimental data show that there is still a great need in more systematic data),
the fine-grained SPD materials are less ductile than the effect of precipitation is unclear to date. The
their coarse grain counterparts. This explains why positive effect of precipitation hardening on the
the low cyclic fatigue performance of ECAP thermal stability of ECAP materials has been
materials appears to be below expectations. The shown, for example, using the model CuZrO2
other reasons include their low structural stability, composite [13]. Since the cyclic behaviour of
susceptibility to cyclic softening and early strain ECAP pure copper has been investigated in more
localization. A high cyclic softening rate in ECAP detail than that of other materials [69], we chose
metals, indicating a high degree of structural insta- a commercial precipitation hardened copper based
bility under load, plays an important role in fatigue alloy CuCrZr for the present study. This alloy
degradation [68]. Several causes have been pro- is traditionally used in applications where a combi-
posed in the literature to account for this phenom- nation of high mechanical strength, heat resistance
enon [6]: (1) dislocation recovery and recovery of and electrical (or thermal) conductivity is
highly disturbed grain boundaries, (2) grain coars- demanded (electrodes for point welding, heat
ening, recrystallization and abnormal grain growth exchangers, fusion reactors, etc. [5]). Thus, the
promoted by cyclic stresses, (3) strain localization present work has a triple purpose. The first is to
in the large-scale shear bands appearing during assess the mechanical properties and, particularly,
mechanical testing and microcracking. According fatigue performance of this practically important
to [9], grain growth resulting in local softening CuCrZr alloy subjected to significant grain
serves as a precursor of strain localization, which refinement and strengthened through ECAP. The
tends to develop in the regions where the resistance second is to explore the possibility to enhance the
to plastic flow is lower. From acoustic emission thermal stability and fatigue resistance of ECA-
measurements and surface observations, it has been processed metals through subsequent precipitation
supposed [10,11] that the shear bands appear very hardening. The third is to optimize the electrical
rapidly as a result of local plastic instabilities and mechanical properties by varying tempera-
initiated along the non-equilibrium grain bound- turetime conditions of the post-ECAP aging.
aries in a fashion similar to inhomogeneous plastic Hence, in addition to attempts to improve the
deformation of metallic glasses. Being a specific fatigue performance we intend to produce the SPD
case of plastic instability and intensive damage, material which will be heat resistant and will
shear banding is quite undesirable regardless of its posses a satisfactory electric conductivity. The lat-
precise microscopic mechanism. Therefore, when ter issue is important because obtaining a high
fatigue is of major concern, the material should be enough conductivity is not straightforward in plas-
A. Vinogradov et al. / Acta Materialia 50 (2002) 16391651 1641

tically deformed metals since their electrical from 5104 to 1102. The hysteresis loop shape
properties decrease usually with plastic straining was evaluated by the Bauschinger energy para-
and hardening [14,15]. Emphasis is placed on the meter [16] bE (4saplS) / S where sa is the
cyclic response under strain-controlled conditions peak stress amplitude and S is the area of the hys-
since this kind of testing provides valuable infor- teresis loop. A larger value of bE corresponds to a
mation regarding the mechanisms of plastic defor- pointer hysteresis loop and to the larger Bausch-
mation and because these conditions are most dif- inger effect. The invariability of bE serves as a
ficult to sustain for pre-deformed metals. A special measure of stability of the hysteresis loop. The
attention is paid to the effect of processing includ- fatigue tests were performed at the same average
ing the number of ECA-passes and the aging con- cyclic strain rate of 1102 s1 in ambient air at
ditions on mechanical properties. room temperature. The constant stress amplitude
was applied in HCF tests. The tensile tests were
performed on the same testing machine with a con-
2. Experimental procedure stant strain rate of 103 s1. The ordinary commer-
cially produced Cu(0.91.3)Cr alloy (Yamaha
Before ECAP the Cu0.44Cr0.2Zr billets (the Corp.) with mean grain size of 26 m was used as
concentration of alloying elements is given in a reference material. The standard industrial
wt.%) of 1415175 mm were solution treated at thermo-mechanical treatment of this CuCr alloy
1040C for 30 min and quenched in 5% water sol- includes drawing, quenching from 980C and age-
ution of NaCl. After quenching, the samples had ing at 450500C for 1.52 h.
the Vickers microhardness of 50 kgf/mm2. Mul- A 200 kV transmission electron microscope
tiple pressing through intersecting at 90 square (TEM) equipped with an energy depressive X-ray
channels was performed from 1 to 12 times with spectrometer (EDS) was employed for structural
0.4 mm/s velocity at room temperature via the so- characterization of the samples prior to and after
called route Bc when the sample was rotated fatigue as well as after various heat treatments. The
through 90 clockwise about working axis between specimen surface after tensile and fatigue tests was
subsequent passes. To provide the uniformity of observed by scanning electron microscopy (SEM)
simple shear along the intersection plane, the to detect the traces of plastic deformation, strain
required boundary conditions [2,3] have been ful- localization and microcracking.
filled by minimizing the contact friction and ensur- To obtain maximum strength after intensive pre-
ing a hydrostatic pressure in the deforming region. straining during ECAP and to explore the effect of
The homogeneity of deformation was verified after precipitation hardening on fatigue of ECAP
each ECA-pass by observing the fiducial lines materials, the specimens were subjected to iso-
which had been scratched prior to pressing on the thermal aging at different temperatures. Differen-
side faces of the billet in the direction perpendicu- tial scanning calorimetry (DSC, Rigaku 8230)
lar to the working axis. The shear strain imposed helped to evaluate the thermal stability of ECAP
during each ECA-pass equals two. structure and to monitor the phase transformations
The samples for mechanical testing were shaped under linear heating with a constant heating rate of
by spark erosion to have a nearly square cross-sec- 20 K/min. An empty platinum cell was used as a
tion of 22 mm2 and a gauge length of 10 and 3 reference and the second DSC run served as a base
mm for tensile and fatigue tests, respectively. The line. The results of DSC helped to determine trial
specimen axis was aligned with the direction of aging temperatures as discussed below. Aging was
extrusion. All specimens were mechanically and performed using either an ordinary vacuum furnace
electrolytically polished before testing. The LCF or the Shinku-Riko furnace allowing rapid heating
experiments were carried out on a universal Instron and precise temperature control in vacuum to min-
hydraulic frame under plastic strain-control in imize possible effects from heating rate that is
fully-reversed tensioncompression at constant particularly important for flash annealing at rela-
plastic strain amplitudes, pl pl / 2, ranged 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-
Fig. 1. The enthalpy release rate during linear heating of the
ized for real-time monitoring of strain localization ultra-fine grain CuCrZr alloy subjected to 12 ECA-passes.
and microcrack nucleation during fatigue. The
computer controlled broad-band (501000 kHz)
AE apparatus has been described in detail in DSC peak is visible around 350C. The second
[11,17]. During data processing, the artificial maximum is achieved near 440C. These findings
false signals from the laboratory equipment were are in line with former detailed investigations of
identified and removed using a pattern recognition precipitation kinetics in binary CuCr, CuZr and
technique. For each AE signal crossing the thres- ternary CuCrZr alloy [18], where it was found
hold, the Fourier power spectral density function that in the as-quenched specimen, Cr precipitates
was calculated. The averaged spectrum of the pre- appeared first at about 440C and then Cu3Zr pre-
recorded background noise was subtracted from cipitation occurred separately at about 520C. In
the AE spectra and then the AE energy, E, and the the cold-worked specimen, the order of precipi-
median frequency were calculated (the details of tation was reversed, that is, Cu3Zr and Cr appeared
data processing are given in [17]). Formerly the at about 370C and 425C, respectively. The two
same approach was applied effectively to investi- precipitation temperatures observed in the ternary
gate the strain localization and crack nucleation in alloy agreed well with those of the respective
ECAP Cu during tensile tests and fatigue binary alloys. We should point out that the precipi-
[10,11,17]. tation kinetics in the present CuCrZr alloy
appears to be somewhat more complex than that
described in [18], and one more pronounced peak
3. Results is visible around 500C.
Three aging temperatures 375, 425 and 500C
3.1. Microhardness, electric conductivity, were chosen upon the DSC results and the
thermal stabi1lity and aging conditions annealing time was estimated from the Vickers
microhardness measurements performed after
The significance of aging for deformation-pro- holding the probe samples in the furnace for differ-
cessed Cu-based alloys has been well understood ent periods of time. At first, the effect of the num-
for optimization of both strength and electrical ber of ECA-passes was explored on the resultant
conductivity [14,15]. The DSC curve of the ECAP hardness. The samples were heated up to the
specimen, Fig. 1, reveals the complexity of multi- desired temperature within 1 h and cooled down
stage structural transformations in CuCrZr under to room temperature within about 4 h after holding
linear heating. The enthalpy release peak, which at 375C up to 15 h. Fig. 2 demonstrates that (1)
can be associated with recrystallization, starts at a ECAP gives rise to substantial strengthening which
rather high temperature of 525C and its maximum tends to saturate after six pressings, and (2) further
is reached around 650C. The onset of the first hardening is achieved after aging so that the HV
exothermal reaction is noticed about 220C and the magnitude reaches 232 kgf/mm2, which is mark-
A. Vinogradov et al. / Acta Materialia 50 (2002) 16391651 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
Fig. 2. Vickers microhardness HV of ultra-fine grain CuCr
Zr as a function of number of ECA-passes in the as-fabricated Finally, for mechanical testing the 12-pass
state and after aging at 375C, 15 h. 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
edly higher than 165 kgf/mm2 in the commercially shown Figs. 1, 3 and 4 the samples heat treated at
manufactured CuCrZr specimen. The improve- 375C should be regarded as under-aged and the
ment of HV in comparison with that in the ordinary samples heat treated at 425 and 500C are nearly
CuCr alloy (HV of 150 kgf/mm2) is even more peak-aged. As will be shown below, the structure
pronounced. remains fine-grained after annealing at 500C and
The dependence of HV on the aging temperature even at 600C for 1h. For the sake of comparison
is illustrated in Fig. 3 for the specimens subjected we should mention that the structure of pure
to 8 and 12 ECA-pressings. One can see that the (99.9699.98%) ECAP Cu is quite unstable, and a
temperature Th, at which the maximum HV magni- rapid grain growth occurs at temperatures lower
tude is achieved, depends on the amount of pre- than 120C or even at room temperature [2,12].
strain during fabrication and is higher for the speci- To meet the industrial needs, the Cu-based
mens with smaller pre-strain, i.e. for the 8-pass alloys for electro-mechanical applications must
specimens Th is close to 500C while for the 12- have the electric conductivity sel better than 75
pass specimens Th is 430C. This reflects the fact 80% IACS [15]. As shown in Fig. 4, the as-fabri-
that hardening in CuCrZr occurs due to multi- cated ECAP billets have a very poor electrical per-
stage precipitation which depends on the pre-strain
history. We should mention that the ability of cold

Fig. 4. Vickers microhardness and electric conductivity of

Fig. 3. Vickers microhardness of UFG CuCrZr alloy as a UFG CuCrZr alloy as a function of aging time at different
function of aging temperature. Aging time is 1 h. 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 Fig. 5. Bright-filed TEM images of the structure of the Cu
CrZr alloy after 12 ECA-passes: (a) as-fabricated state,
obtained from a region of 0.8 m diameter. The SAEDP; (b) aged at 375C, 15 h; (c) aged at 500C, 1 h; (d)
thin foil was sectioned from the plane perpendicu- aged at 600C, 1 h; (e) aged at 700C, 1 h; (f) fine precipitates
lar to the working axis. The structure in the as- in the grain-boundary vicinity after aging at 375C, 15 h; (g)
fabricated state appears very uniform and fine. The aged at 375C for 15 h and fatigued at pl / 2 103, (h) aged
appearance of macroscopic strain heterogeneity at 375C for 15 h and fatigued at pl / 2 102.
after large deformations by rolling has been
observed in a CuCr alloy and investigated in allows a uniformity of simple shear through the
detail [27]. It was shown that the shear bands whole working volume. Comprehensive dis-
appear on a free surface of the deformed specimens cussions on structure formation during ECAP in
after true rolling strain of 0.65 depending on the dependence on the straining path and other pro-
aging conditions. We should notice that after a cessing parameters can be found elsewhere
much greater amount of ECAP pre-strain no [1,3,28,29]. The grain size after 8 or 12 ECA-
macroscopic shear bands were apparent on the sur- passes is nearly the same (of 160 nm) in average as
face or in the TEM photos of the material under evaluated from TEM micrographs by the intercept
investigation after 4, 8 or 12 ECA-passes (although method in the as-fabricated state. The SAED pat-
the flow pattern containing elongated grains can be tern consists of rings of diffraction spots demon-
visible after other number of passes through the strating that the grain boundaries have high angles
used route Bc). This seems to be an advantage of of misorientation. The ability of ECAP to produce
ECAP technology which, if performed in accord the UFG structures with high-angle of misorien-
with mechanical conditions stipulated in [2], tations between grains has long been recognized
A. Vinogradov et al. / Acta Materialia 50 (2002) 16391651 1645

and evolution of the distribution of grain bound- in Refs. 18 and 20. The fact that during early stages
aries over the misorientation angle has been sys- of decomposition of solid solution chromium can
tematically investigated in dependence on the form very fine metastable precipitates coherent
straining path [28,29]. The average dislocation with the copper matrix in CuCr alloys has been
density is typically high [1] and close to 10131014 well understood in former detailed TEM investi-
m2 as estimated to the order of magnitude by the gations [20,23,24,26] and is among most important
standard weak-beam technique [30]. With such a for the present study. Transformation of Cr precipi-
high density, close to the limiting resolution with tates to the large and stable b.c.c. particles occurs
ordinary TEM, the chaotic dislocation arrangement at higher temperatures and longer annealing
is energetically unfavorable, and dislocations are times [25].
unevenly distributed so that the small grains in
their central parts are rather free of dislocations and 3.2.3. Microstructure after fatigue
most dislocations are attracted to the grain bound- In the present work, TEM does not reveal any
aries, that suggests the presence of high internal significant difference in the fine structure before
stresses created by grain boundaries. The above and after fatigue of ECAP CuCrZr. Fig. 5g and
estimate of the dislocation density is qualitative 5h show the structure after cycling at pl / 2
rather than quantitative since the TEM technique 103 and 102 correspondingly. Unlike some other
does not take into account the dislocations in grain ECAP materials such as pure Cu and 5056 AlMg
boundaries and does not provide a satisfactory alloy [79], CuCrZr does not exhibit visible
accuracy in quantifying the number of dislocations grain coarsening or changes in the arrangement and
in dense arrays which are observed often in the density of dislocations after fatigue. The average
structure. dislocation density remains high, and no particular
dislocation configurations such as plain arrays,
3.2.2. Microstructure after aging dipoles or walls are observed in the fatigued speci-
It is impressive that the ECAP structure remains mens. As a matter of fact, it becomes much more
fine-grained during heating and aging at tempera- difficult (or even fully fortunate) to observe fine
tures up to 600C, Fig. 5bd. No substantial grain precipitates in the grain interior even at high mag-
growth is noticed. The dislocation density is high nifications (up to 200 000) in both bright and
even after aging at 500C, indicating that the dislo- dark fields.
cations are strongly pinned. The grain growth Thus, the following conclusions can be drawn
becomes noteworthy only at temperatures as high from TEM inspections of the ECAP CuCrZr
as 650700C, Fig. 5e, confirming that the DSC specimens: (1) a very fine severely deformed
peak around 650C in Fig. 1 should be attributed ECAP structure is quite stable in terms of grain
to recrystallization and grain growth. The fine size and dislocation configuration at temperatures
chromium precipitates (of 520 nm size) become up to 600C and under cyclic loading at room tem-
visible after aging at 375C predominantly in the perature; (2) fatigue mechanisms cannot be asso-
grain boundary regions or in the vicinity of the ciated with formation of any specific dislocation
boundaries, Fig. 5f. The EDS analysis shows that structure in the fine grains; (3) fine coherent Cr
Cr precipitates first under given aging conditions precipitates can dissolve, in principle, (at least
(in fair agreement with [18,20]), whereas Zr partly) in the Cu matrix during fatigue because of
remains mostly in solid solution. At higher tem- cutting by moving dislocations (see, for example,
peratures such as 425 and 500C, etc., the mor- [31,32] and references therein for details of such
phology of precipitates does not change appreci- mechanism) and this will be further argued from
ably (we noticed some but no substantial the results of mechanical testing.
coarsening of precipitates, which still remain in 3.3. Tensile testing
range of fine 520 nm diameters), however, Zr
containing particles can be found randomly in the Tensile stressstrain curves are shown in Fig. 6.
foil. This is also consistent with the results reported It is worth noticing that the as-fabricated ECAP
1646 A. Vinogradov et al. / Acta Materialia 50 (2002) 16391651

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.
Fig. 6. Tensile stressstrain curves of the ECAP CuCrZr
alloy after various thermo-mechanical treatments in comparison
with reference commercial CuCr. commercial CuCr. The rate of softening is slightly
dependent on the plastic strain amplitude, increas-
ing with increasing pl/2. Nevertheless, the sus-
sample, curve 1, is rather ductileits total elong- ceptibility to softening is very sensitive to the
ation to failure is larger that that for ordinary thermo-mechanical history of the specimens. Fig. 8
quenched and aged CuCr, curve 6. This result is demonstrates the cyclic hardening/softening curves
important because the high ductility is an obvious for different specimens examined at the moderate
benefit for formability, fatigue life and resistance plastic strain amplitude pl / 2 1 103. One
to crack propagation. Aging after ECAP results in can see that the highest softening rate is demon-
precipitation hardening leading to further increase strated by the specimen that has received the larg-
in the yield stress and the ultimate strength of the est amount of pre-strain (12 ECA-passes) and aged
tested materials. As can be seen, after aging of the at 375C. We would like to emphasize that the as-
ECAP specimens their sy and sUTS values increase fabricated but not aged ECAP specimens do not
to 65020 MPa and 70040 MPa correspondingly soften, curve 1 in Fig. 8, despite intensive pre-
and become much higher than in the reference Cu straining. This fact can serve as an evidence for a
Cr specimen (sy390 20 MPa). They are also dominant role played by strengthening particles in
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
Fig. 8. Cyclic hardening/softening curves for CuCrZr and
500C for 1 h, Fig. 7. Progressive cyclic softening CuZr alloys subjected to different thermo-mechanical treat-
occurs at all plastic strain amplitudes applied and ments and tested under the same plastic strain amplitude
in all aged specimens tested including reference pl /2 103.
A. Vinogradov et al. / Acta Materialia 50 (2002) 16391651 1647

cyclic softening of the materials under investi- precipitates. It is therefore less strong and more
gation. Fig. 8 also confirms that by changing aging ductile, Fig. 6, which results in the smaller absolute
conditions one can largely vary the cyclic response value of the fatigue exponent and somewhat longer
of dispersion hardenable alloys after ECAP. low-cyclic fatigue life. It is, however, undoubtedly
Although softening is visible in ECAP CuCrZr, shown that LCF properties of present CuCrZr
it should not be entirely associated with SPD fabri- are in range of practical expectations, and these
cation, because this phenomenon is commonly properties are variable through post-ECAP thermal
observed in commercial CuCrZr and CuCr treatment that helps to obtain a desired compro-
which did not receive such intensive pre-strain. mise in HCF and LCF performance.
The low-cyclic fatigue life dependence on the
plastic strain amplitude obeys the CoffinManson 3.5. Large-scale shear banding and cracking-
law: epl / 2 ef(2Nf)c with f the fatigue ductility surface observations and AE analysis
and c the fatigue exponent, both are materials con-
stants, Fig. 9. Typically for many other SPD Strain localization in the form of large-scale
materials [7], fatigue life of ECAP CuCrZr is shear bands occurs in the ECAP CuCrZr alloy in
somewhat shorter than that of the reference com- both tensile and cyclic testing, Fig. 10, in a manner
mercial CuCr material that emphasizes a key role similar to that in pure copper or in the non-heat
of ductility in fatigue under strain control. Fatigue treatable 5056 AlMg alloy. The shear bands in
life of the ECAP specimens is the shortest in the cyclic deformation are more pronounced than those
underaged state (aging at 375C). It is worth not- in tension, indicating the strong strain localization
ing, that the slope of the CoffinManson line is the during fatigue. However, there is an important dif-
same for the reference CuCr (c 0.68) and for ference in appearance of the shear bands in UFG
the as-fabricated ECAP alloy, while the fatigue CuCrZr and, for example, UFG pure Cu. While
exponent in the aged ECAP specimens is notably the shear bands may nucleate relatively early dur-
higher (c 0.92 for the 8 ECA-pass CuCrZr ing cycling of UFG Cu [17], the in-situ surface
aged at 500C 1 h) so that at high strain amplitudes observations show that the large shear bands in
greater than 102 the aged ECAP specimen may UFG CuCrZr emerge only in the very late stage
endure longer than its non-aged counterpart or of fatigue shortly before failure. The post-experi-
commercial CuCr. When comparing two different mental SEM observations reveal that the shear
materials, CuCrZr and CuCr, one should also bands are located primarily in the vicinity of frac-
bear in mind that the latter material contains fewer ture surface and their number and density are not
amounts of strengthening secondary phases and 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
Fig. 9. CoffinManson plots for materials under investigation. failure. The simple AE picture shown in Fig. 11
1648 A. Vinogradov et al. / Acta Materialia 50 (2002) 16391651

Fig. 11. AE appearance in the cyclically deformed ECAP Cu


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)
Fig. 10. Shear bands on the surface of CuCrZr (12-pass curve. This is, however, typical for Cu-based
ECAP, aged at 375C for 15 h): (a) tensile test, (b) fatigue at alloys. HCF life of severely deformed and aged
pl / 2 103; (c) fatigue at pl / 2 102. Arrows indicate
the loading axis.
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
in terms of the total number of AE events does CuCrZr is of 285 MPa that is considerably
not allow us to distinguish between these two AE higher than that has been reported in [33,34] for
sources. However, it has been shown in Ref. 17 commercial Cu0.8Cr0.07Zr (Tre fime taux,
for cyclically deforming ECAP Cu that the dis- sy100 MPa), Cu1.98Ni0.32Be alloy (Brush
A. Vinogradov et al. / Acta Materialia 50 (2002) 16391651 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
Fig. 12. Stress amplitude versus number of cycles to failure
cyclically deformed ECAP CuCrZr, i.e. cyc-
(SN curve) of ECAP CuCrZr in comparison with commer-
cial tempers. lic softening cannot be associated with the insta-
bility of severely pre-deformed structure.
Strain localization in the shear bands cannot be
Wellman Hycon 3HP, sy700 MPa), and Cu a cause of softening because these bands in the
0.75Cr (Wieland Werks AG, sy310 MPa). This UFG CuCrZr alloy nucleate only shortly
seems to be an impressive achievement of ECAP before failure.
technology if compared with traditional commer- Not aged ECAP specimens do not soften.
cialized tempering processes and in combination
with high thermal stability and electrical conduc- Furthermore, the TEM observations allow us to
tivity this should promote an engineering appli- suppose that many precipitates, at least the smallest
cation of the ECAP Cu-alloys. 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
4. Discussion and co-workers about local dissolution of cut par-
ticles in the shear bands [31].
In the preceding section we have underlined the To provide further evidence in favor of precipi-
difference in the cyclic response of as-fabricated tation dissolution during cyclic loading the special
ECAP and aged after ECAP specimens: the former experiment was performed as follows. Two speci-
demonstrates the steady stress amplitude during mens subjected to eight ECA passes were aged at
cycling whereas the latter exhibits notable soften- 375C for 15 h and 425C for 1 h, respectively.
ing which is particularly pronounced at the begin- Then they were subjected to fatigue loading at
ning of fatigue loading. It has been recognized that pl 103 up to the cumulative plastic strain of
cyclic hardening and softening in precipitation 0.8, that is much smaller than the strain when the
strengthened alloys is closely related to the type, shear bands or microcracks could be observed on
morphology and density of second-phase particles. the surface. The specimens were carefully dis-
The geometrical relationship at the precipitate mounted from the grips and annealed once more
matrix interface or coherency between the precipi- under the same conditions, i.e. at 375C and
tates and the matrix is of primary importance for 425C, respectively. After that the specimens were
the resultant properties and mechanisms of fatigued again under the same conditions and their
strengthening and plasticity. Cyclic softening is resultant cyclic response is shown in Fig. 13 in
strongly favored if the precipitates are easily shear- terms of hardening curves and the Bauschinger
able by dislocations, i.e. if they are (1) fine and (2) energy parameter. The significant decrease of the
coherent with the matrix [24]. It has been shown stress amplitude is observed from the onset of the
1650 A. Vinogradov et al. / Acta Materialia 50 (2002) 16391651

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
Fig. 13. Cyclic response of the ECAP (8 pass) CuCrZr explore the fatigue properties of the SPD fabricated
specimen subject to the second aging after fatigue to N=200 alloy containing non-shearable particles. The large
cycles at pl / 2 103 (first and the second aging were perfor- Bauschinger effect in the ECAP materials is of
med under the temperature of 425C and time of 1 h). particular interest as it helps to clarify the mech-
anism of their plasticity and the nature of back
first loading in the same manner as has been stresses. The phenomenological details and the
described in the previous section. The second heat- description of this effect are beyond the scope of
ing tends to remove the effect of prior cyclic defor- the present paper and will be considered in the
mation, resulting in the considerable increase of sa, forthcoming communication.
that occurs most likely due to precipitation harden-
ing. However, the stress amplitude did not recover 5. Summary and conclusions
completely after re-aging and the second straining
occurs at lower stresses than at the beginning of The ultra-fine grain CuCrZr dilute alloy has
the first loading. This can be either owing to some been fabricated by ECAP. It is undoubtedly shown
dislocation annihilation during fatigue or that post-ECAP aging makes the precipitation
annealing, or because the second aging did not hardened ultra-fine grain structure rather stable
restore the initial amount and distribution of pre- under both thermal and mechanical influence. Opti-
cipitates. Since we did not observe the gross mal aging conditions are found to ensure the best
reduction in the dislocation density during fatigue high-cyclic fatigue performance in combination
or isothermal annealing up to 500C, the second with satisfactory good electric properties and ther-
reason seems to be more probable. Furthermore, mal stability. At the same time, the low cyclic
the Bauschinger effect after the intermediate heat- fatigue properties remain high despite some loss of
ing becomes significantly lower than at the end of ductility during fabrication. Strengthening mech-
the first cycling, indicating thereby some dislo- anisms resulting from a combination of intensive
cation recovery. Thus, one can conclude that cyclic cold work through ECAP and subsequent aging
softening of aged specimens is associated with par- have been taken advantage to successfully produce
tial dissolution of precipitates under cyclic plastic the material with desired electro-mechanical
deformation. We should underline that particle dis- properties including sufficient ductility for forming
solution becomes more difficult and the rate of and adequate resistance to fatigue loading. The sig-
softening decreases when the aging temperature nificant improvement of tensile and HCF proper-
increases because of the increasing size of precipi- ties is observed without dramatic sacrificing the
tates. ductility and LCF properties. In view of proven
It has long been recognized from the strain- high thermal stability and affordable electrical con-
based representation of fatigue life that in the low- ductivity, the superior mechanical properties and
cyclic regime at fairly large strains, the plastic fatigue resistance of ECAP CuCrZr open new
strain amplitude is dominant and fatigue life is perspectives for its potential applications.
A. Vinogradov et al. / Acta Materialia 50 (2002) 16391651 1651

The experimental details of cyclic response are [8] Ho ppel HW, Brunnbauer M, Mughrabi H, Valiev RZ, Zhi-
presented and the nature of cyclic softening is lyaev A. In: Proceedings of the Munich Materialsweek,
FRG, 2000 (in press).
investigated in the precipitation hardened ECAP [9] Mughrabi H, Ho ppel HW. MRS Proc 2001;634:B2.1.
CuCrZr alloy. It is shown that the reduction of [10] Vinogradov A. Scripta Mater 1998;39:797.
stress amplitude in the course of fatigue should be [11] Vinogradov A, Patlan V, Kitagawa K. Mater Sci Forum
attributed to the shearing of strengthening particles 1999;312-314:607.
by dislocations and partial dissolution of the par- [12] Gertsman VY, Birringer R. Scripta Metall 1994;30:577.
[13] Lebedev AB, Pulnev SA, Kopylov VI, Burenkov YuA,
ticles. Vetrov VV, Vylegzanin OV. Scripta Mater 1996;35:1077.
Experimental data unambiguously show that the [14] Ellis TW, Kim ST, Verhoeven JD. J Mater Eng Perform
ultra-fine grain CuCrZr alloy processed by 1995;4:581.
ECAP followed by aging has many advantages [15] Sundberg R, Sundberg M. Thermomechanical processing
over currently available commercial tempers in in theory, modelling and practice. In: Proceedings of an
International Conference organised in celebration of the
that it permits designs having much higher working 75th Anniversary of the Swedish Society for Materials
stresses and fatigue resistance, thus providing a Technology, Stockholm, Sweden, 46 September 1996,
better cost effectiveness. p. 268.
[16] Abel A, Muir H. Phil Mag 1972;26:489.
[17] Vinogradov A, Patlan V, Kitagawa K, Hashimoto S. Phil
Mag (in press).
Acknowledgements [18] Suzuki H, Kanno M. J Jpn Inst Met (Jpn) 1972;36:363.
[19] Smith GC. Progr Metal Phys 1949;1:163.
The authors are indebted to M. Kawazoe (YKK [20] Nagai T, Henmi Z, Sakamoto T, Koda S. Trans JIM
Corporation, Japan) and T. Yamasaki (Doshisha 1973;14:462.
University, Japan) for their skilful help in TEM [21] Henmi Z, Nagai T. Trans JIM 1969;10:305.
[22] Luo CP, Dahmen U, Westmacott KH. Acta Metall
observations. One of the authors (V.K.) wishes to Mater 1994;42:1923.
thank the Japanese Society for the Promotion of [23] Dahmen U, Witcomb MJ, Westmacott KH. Scripta Met-
Science for the fellowship awarded that allowed all 1988;22:1867.
completing the present work during his staying in [24] Rdzawski Z, Stobrawa J. Scripta Metall 1986;20:341.
Japan in 20002001. [25] Stobrawa J, Rdzawski Z. Scripta Metall 1987;21:10.
[26] Kamijo T, Furukawa T, Watanabe M. Acta Metall
[27] Dybiec H, Rdzawski Z, Richert M. Mater Sci Eng A
References 1989;108:97.
[28] Iwahashi Y, Horita Z, Nemoto M, Langdon TG. Acta
[1] Valiev RZ, Islamgaliev RK, Alexandrov IV. Progr Mater Mater 1997;45:4733.
Sci 2000;45:103. [29] Terhune SD, Horita Z, Nemoto M, Li Y, Langdon TG,
[2] Segal VM. Mater Sci Eng A 1995;197:157. McNelley TR. In: Sakai T, Suzuki HG, editors. Proceed-
[3] Segal VM, Reznikov VI, Kopylov VI, Pavlik DA, Maly- ings of the 4th International Conference on Recrystalliz-
shev VF. Processes of plastic structure formation of met- ation and Related Phenomena. The Japan Institute of Met-
als. Minsk: Nauka i Tehnika, 1994, 232 pp. [in Russian]. als; 1999, p. 515.
[4] Kopylov VI. In: Lowe TC, Valiev RZ, editors. Investi- [30] Hirsch PB, Howie A, Nicholson R, Pashley D, Whelan
gations and applications of severe plastic deformation. M. Electron microscopy of thin crystals. London (UK):
NATO ASI Series 3, vol. 80. Netherlands: Kluwer; 2000, Butterworths, 1965, 549 pp.
p. 23. [31] Hornbogen E, zum Gahr KH. Metallography B 1975;181.
[5] Tavassoli AAF. J Nucl Mater 1998;258-263, A:85. [32] Suresh S. Fatigue of materials. UK: Cambridge University
[6] Mughrabi H. In: Lowe TC, Valiev RZ, editors. Investi- Press, 1991, 617 pp.
gations and applications of severe plastic deformation. [33] Leedy KD, Stubbins JF, Singh BN, Garner FA. J Nucl
NATO Science Series, vol. 3/80. Kluwer; 2000, p. 241. Mater 1996;233-237A:547.
[7] Vinogradov A, Hashimoto S. Mater Trans JIM [34] Gadalla AA, Gerold V. Indian J Pure Appl Phys
2001;42:74. 1980;18:383.