SOMIYA Award 2015 memorial review paper

Trans. Mat. Res. Soc. Japan 40[4] 309-318 (2015)

Recent Findings in Superior Strength and Ductility of Ultrafine-Grained Materials

Ruslan Z. Valiev1,2*, Yuntian Zhu3,4

1 Institute of Physics of Advanced Materials, Ufa State Aviation Technical University, 12 K. Marx str., Ufa, 450000, Russia
2 Laboratory for Mechanics of Bulk Nanomaterials, Saint Petersburg State University, 28 Universitetsky prospekt, Peterhof,
Saint Petersburg, 198504, Russia
3 School of Materials Science and Engineering, Nanjing University of Science and Technology, Nanjing 210094, China
4 Department of Materials Science and Engineering, North Carolina State University, Raleigh, NC 27695, USA

* Corresponding author: rzvaliev@mail.rb.ru

 

Key words: ultrafine-grained materials, severe plastic deformation, strength and ductility, mechanical properties

ABSTRACT enabled by SPD.

Over the last two decades it was well documented
that the formation of ultrafine-grained (UFG) structures
with the grain sizes in submicron (< 1 µm) or nanometer
(< 100 nm) range in metallic materials increases strength
but typically also leads to decrease in ductility. However,
recent studies demonstrated that extraordinarily high
strength and enhanced ductility can be obtained in the
UFG metals and alloys when it is possible to control not
only grain sizes but also the formation of various
nanostructured elements, such as nanoparticles,
nanotwins and grain boundary structures (states) by
means of severe plastic deformation (SPD) techniques.
These new trends applied to different metallic materials
with superior strength and high ductility are considered
and discussed in the present paper.
1. INTRODUCTION
In recent years there has been growing interest in
UFG materials produced by SPD processing, as
demonstrated by the increasing number of publications
with high citations [1] as well as numerous specialized
conferences, workshops and symposia on the subject
(www.nanospd.org).
The critical feature of SPD, in which heavy straining
is applied under high pressure with accumulated strains
ε in excess of ~4-6, makes it possible to produce
ultrafine grains (UFG) with sizes smaller than 1000 nm
[2-5]. Processing by SPD may also lead to a dissolution
of second phases, precipitation, amorphization and other
processes, producing various nanostructural features
such as deformation twins, non-equilibrium grain
boundaries, dislocation substructures, solute segregation
and clusters [6, 10]. These changes in the inner
make-up of the material may affect the deformation
mechanisms and, consequently, change the material
properties in a fundamental way. As a result, new
structural and functional metals and alloys having
superior and unique properties have been developed by
SPD processing [4, 5, 7-9].
Over the last decade there has been extensive
research into the mechanical properties of UFG
materials as well as their origin and relationship to
fundamental physics. This report gives a critical
overview of this research with special attention directed
to the extraordinary strength and ductility that are
2. NANOSTRUCTURES FROM SPD PROCESSING
The processing of metals through the application of
SPD has now become a major tool for producing bulk
solids with ultrafine grains [2, 7]. Several different SPD
processing techniques are available [3-5] but most
attention to date has concentrated on the two procedures
of equal-channel angular pressing (ECAP) [11, 16] and
high-pressure torsion (HPT) [12-19] and for
fundamental studies processing by HPT is especially
attractive because it produces materials having smaller
grain sizes and higher fractions of high-angle boundaries
[2, 12, 18, 19].
Grain boundaries in nanostructured materials affect
their properties in very significant ways and quite often
the UFG metals are referred to as “interface-controlled
materials”. Different types of grain boundaries are
formed by SPD processing and they may be classified as
[2, 7]
• Low- vs. high-angle boundaries;
• Special vs. random boundaries;
• Equilibrium vs. non-equilibrium boundaries
with strain-distorted structures.
In addition, SPD may also produce other structural
features in alloys, such as second-phase particles,
nanotwins, and solid segregations at the grain
boundaries. Such modification of the make-up of the
material at the nano scale can have a strong effect on the
material properties. The use of advanced imaging and
structural characterization techniques over the past
decade has brought about the discovery of three
significant nanostructural features of SPD-processed
alloys [8, 10, 16-19], which give rise to their remarkable
mechanical and functional properties. These are outlined
below.
Nanotwins. A high density of nanotwins produced by
SPD was found to increase both the strength and
ductility of nanostructured metals and alloys. Figure 1
shows a transmission electron microscopy (TEM) image
of UFG Cu after equal-channel angular pressing (ECAP)
and cryorolling at the liquid nitrogen temperature; twins
10–20 nm in width are clearly visible [17]. To promote
the formation of nanotwins, the following intrinsic
material properties and external deformation conditions
are required [16]: 1) a relatively low stacking fault

309
SOMIYA Award 2015 memorial review paper
310 Recent Findings in Superior Strength and Ductility of Ultrafine-Grained Materials
energy, 2) a low deformation temperature, 3) a high
strain rate. It should be noted that there is an optimum
grain size range conducive to deformation twinning [16,
20-22]. This optimum grain size for the formation of
deformation twins is affected by both intrinsic properties
of the material mentioned above, and it can be estimated
using the equation [16]:
(1)
√ and accumulate dislocations not only causing higher
where γ is the stacking fault energy, a is the lattice
parameter, υ is Poisson’s ratio, G is the shear modulus
and dm is the optimum grain size.
Figure 1. Typical bright-field TEM images of a grain
with high density of deformation nanotwins in UFG Cu
subjected to ECAP and subsequent cryogenic rolling
[17].
Clusters and segregations. It was found by 3D atom
probe tomography that SPD may hinder the formation of
precipitates in age hardenable alloys and instead
promote clustering and segregation of alloying elements
[10, 23-26]. For example, the data in Figure 2 [26] show
that segregations at grain boundaries make up clusters
~3–5 nm wide in the age hardenable Al alloy 7075.
Moreover, the concentration of alloying elements may
be an order of magnitude higher at grain boundaries than
in the grain interior [8,23, 25, 26].
Figure 2. Tomographic image of nanostructure of UFG
Al alloy 7075. Segregations of alloying elements on
grain boundaries and at triple junctions are shown [25].
Nanosized particles and secondary phase precipitations.
In many alloys subjected to SPD after solid-solution
hardening, high densities of nanosized particles appear
[8, 10, 26]. Figure 3 shows an example of nanoparticles
that are ~10–20 nm in size in the UFG Al alloy 6061
after ECAP [27]. The presence of these nanoparticles is
due to dynamic aging and the high density of nucleation
sites generated by entangled dislocations. The small
size and high density of such particles effectively block
strength but also promoting ductility [18, 26-28].
Figure 3. UFG structure of Al alloy 6061 after ECAP in
parallel channels (four passes): nanosized precipitations
in grains are clearly visible in areas A and B at higher
magnification [27].
Thus, UFG metals and alloys produced by SPD
methods are characterized by a number of nanostructural
features which can strongly influence their behaviour. In
many demonstrated cases, the properties induced by
SPD processing are unique to these materials, as will be
shown in the following sections.
3. SUPERSTRENGTH AND HARDENING
MECHANISMS
A primary advantage of SPD processing is strength
enhancement. Even though the well-known Hall–Petch
relation between the yield stress σy and the grain size d,
(2)
may break down for nanomaterials, it commonly holds
for UFG materials produced by SPD. Here σ0 and KHP
are constants for a given material.
The enhancement of strength with grain size
reduction in compliance with Eq. 2 was observed in
many studies (Fig. 4), but for nanosized grains (20–50
nm), this relations reported to be typically violated so
that the Hall–Petch plot deviates from linear dependence
at lower stress values and its slope ky often becomes
negative (the curve 1 in Fig. 4). In recent years, this
problem has been widely analyzed in both experimental
and theoretical studies [29, 30]. At the same time, Hall–
Petch relationship breakdown is not observed in
ultrafine-grained materials with a mean grain size of
100–1000 nm produced by SPD processing. Moreover,
recently it was shown that UFG alloys can exhibit a
considerably higher strength than the Hall–Petch
relationship predict for the range of ultrafine grains [26,
31-33]. The nature of such superstrength was recently
studied in detail for the case of superstrong Al alloys,
namely AA1570 and AA7475 [26, 31] as well as
stainless steel [34] subjected to severe plastic
SOMIYA Award 2015 memorial review paper
Ruslan Z. Valiev et al. Trans. Mat. Res. Soc. Japan
deformation by HPT processing.
Figure 4. The two types of the Hall-Petch slopes within
different characteristic length scales.
TEM studies demonstrated that HPT leads to a
complete transformation of the initial coarse-grained
structure of alloys into the UFG structure. In the alloys
1570 and 7475, homogeneous UFG structures with a
grain size of about 100 nm were formed after HPT as
shown in Fig. 5. It was also determined that HPT
processing has an observable effect on the value of the
crystal lattice parameter α of Al alloys. For example, in
the AA1570, its value after straining was reduced
considerably in comparison with the initial state, from
4.0765 ± 0.0001 Å to 4.0692 ± 0.0003 Å, which results
from the formation of Mg segregations at grain
boundaries [26, 31].
Fig. 5. A typical TEM dark-field image of the UFG 1570
alloy with a corresponding SAED (a), a bright-field
image (b) [26].
Figure 6 shows the results of mechanical testing of
the 1570 and 7475 alloys. It can be seen that the UFG
40[4] 309-318 (2015) 311
alloys processed by HPT at room temperature
demonstrate record strength that more than twice
exceeds the level of strength of the material subjected to
standard hardening.
Figure 6. Engineering stress–strain curves for AA1570
and AA7475 in UFG and coarse-grained states [26].
Figure 7 illustrates the data for a number of Al
alloys presented in the form of the Hall–Petch relation in
which the yield stress (σ0.2) is plotted against the inverse
square root of the grain size (d−1/2) for a UFG AA1100
produced by accumulative roll bonding (ARB)-rolling
and consequent heat treatment [35] as well as for an
ECAP-processed Al–3 % Mg alloy [36]. For the Hall–
Petch relation in the AA1100 [35], the following
parameters were set: σo = 6.0 MPa and ky = 105 (for the
grain sizes in μm); for the ECAP-processed Al–3 % Mg
alloy [36], σo = 62 MPa and ky = 149. Figure 7 also
shows the data obtained for the coarse-grained and UFG
AA1570 and AA7475.
Figure 7. The Hall–Petch relation for the Al alloys 1100
[35] and Al–3 % Mg [36] and data on the yield stresses
of the UFG alloys 1570 and 7475.
From the available data, it is seen that the σy values
for the coarse-grained solution-treated alloys are close to
the results for the Al–3 % Mg alloy. However, for the
UFG states in the 1570 and 7475 alloys with a grain size
of 100–130 nm, the value σy is considerably higher than
that calculated from the Hall–Petch relation.
The Hall–Petch plots for UFG commercially pure
(CP) Ti (A-70, similar to Grade 4) and Armco-Fe have
SOMIYA Award 2015 memorial review paper
312 Recent Findings in Superior Strength and Ductility of Ultrafine-Grained Materials
shown similar tendencies [37-39].
Thus, the new phenomena of ‘superstrength’ of
nanostructured metals and alloys produced by SPD can
be observed for various materials reflecting the 'positive'
slope of the Hall–Petch relation as demonstrated in Fig.
4 (curve 2). 'Superstrength' in bulk nanostructured
materials can be of different origin. First, it can result
from additional—already known—strengthening
mechanisms, i.e., solid solution strengthening,
precipitation strengthening, and dislocation
strengthening [29, 40]. However, the influence of new
strengthening mechanisms is also possible—these arise
from the change in grain boundary structure and lead to
further strength enhancement [33, 41].
Recently, based on experimental studies of materials
obtained by vacuum deposition [42], Firstov et al. [43]
reported a 'positive' slope of the Hall–Petch relation,
where for the grain size range dcr2 < d < dcr1, the
exponent of d in Eq. 2 varied from −1/2 to −1, and for d
< dcr1, the exponent of d was equal to −3 with the
presence of grain boundary segregations.
Obviously, the presence of these two characteristic
grain size values is also valid for nanostructured SPD
materials. Indeed, as it has been already pointed out, the
presence of non-equilibrium grain boundaries is typical
for the majority of SPD-processed materials, but their
influence on mechanical properties becomes
considerable when the grain size is below 500–1000 nm
[44]. When the grain size decreases down to 100 nm and
less, grain boundary segregations provide a significant
contribution to the overall strength. Recently, this topic
was addressed in [26], where it was shown that high
strength of the UFG Al alloys was directly related to the
formation of Mg segregations at grain boundaries
revealed in the alloys by 3D APT technique [25-27].
Because in UFG materials deformation takes place by
dislocations generated at grain boundaries and moving
through a grain to be captured by an opposite grain
boundary, the rate-controlling mechanism is the
‘dislocation–grain boundary’interaction. In this case,
the elevated concentration of solutes in grain boundaries
can suppress emission of dislocations from such
boundaries due to solute drag, and as a result, the stress
needed to emit a dislocation increases.
Recently, this finding was confirmed for the case of
UFG stainless steel 316 produced by HPT at different
temperatures [34]. Earlier, it was found that the HPT
316 steel processed at room and elevated temperatures
demonstrates similar strength despite the difference in
grain size and dislocation density [45, 46]. In [34], it
was shown that the steel, SPD processed at room
temperature, exhibits no pronounced grain boundary
segregations and fits well the Hall–Petch relation
extrapolated to the corresponding grain size. However,
the steel processed at 400 °C was found to contain
complex Si–Cr–Mo grain boundary segregations, and its
strength considerably exceeded the value predicted by
the Hall–Petch law. Similar idea was used to explain
enormous increase (from 1360 MPa to 2230 MPa) in
yield stress of a 316 steel subjected to HPT at room
temperature followed by subsequent annealing at 500 °C
for 1 h [47]. The authors suggested that it can be
explained by the fact that thermal treatment leaded to
formation of grain boundary segregations which became
precursors for G-phase observed in grain boundaries
after further long-term annealing.
These findings on the role of SPD-induced GB
segregations open a way for a new direction in
nanostructural design of SPD-processed materials and
also may be used in grain boundary engineering of the
other types of nanomaterials [5, 48].
This point is in good agreement with the
experimental data and also makes it possible to explain
considerably higher strength values observed in the UFG
alloys in comparison with pure metals. At the same time,
the task of oncoming research is to explore the
segregations and determine which elements, and the
level of their concentrations, produce the most influence
on strength enhancement in bulk nanostructured
materials. This point is also important in answering the
question of the precise origin of very high strength in
nanostructured multiphase alloys that possess the most
strength among metallic nanomaterials, which was
recently discussed in [49].
4. DUCTILITY AND STRATEGIES FOR ITS
IMPROVEMENT
Ductility in metallic materials, which is measured
under tensile deformation mode, is another very
important property for their structural use. It is essential
for metal-forming operations as well as to avoid
catastrophic failure in load-bearing applications during
their service life. Two measures of ductility will be
considered below. First, uniform elongation is the
maximum strain where homogeneous plastic flow
(uniform reduction of cross-sectional area) is still
observed and beyond which a diffuse necking begins.
The uniform elongation is determined by competition
between plastic flow and materials resistivity to
macro-localization of plastic flow (i.e. strain hardening).
It can be important in stretch-metal-forming operations.
The second measure, elongation to failure (often referred
to as total elongation to fracture or engineering strain at
fracture), is a sum of uniform elongation and necking
elongation. The latter is controlled by competition
between localized plastic flow and fracture processes.
The uniform elongation is not affected much by the
sample geometry and size [50, 51], and therefore is more
suitable for use as a measure of ductility, especially for
the study of nanostructured materials where small
samples with various geometries are typically used.
It has been a long-standing goal for materials
scientists to synthesize structural materials with
balanced combinations of high strength and high
ductility. However, during the last decade, it has been
widely demonstrated that a major grain refinement,
down to the nanometer range, may lead to a very high
hardness and strength in various metals and alloys, but
nevertheless, these materials invariably exhibit low
ductility [52-54]. A similar tendency is well known for
metals subjected to heavy straining by other processes
such as rolling, extrusion, or drawing. Strength and
ductility are the key mechanical properties of any
material, but these properties typically have opposing
characteristics. Thus, materials may be strong or ductile,
but they are rarely both. The reason for this dichotomy is
SOMIYA Award 2015 memorial review paper
Ruslan Z. Valiev et al. Trans. Mat. Res. Soc. Japan
of a fundamental nature. Indeed, the strain hardening
mechanisms associated with the accumulation of
dislocations may not be effective in ultrafine grains.
This is generally equally true for SPD-processed
materials. The low strain hardening leads to low
ductility, as discussed below.
Typically, in the nanostructured metallic materials,
deformation localization (necking) occurs at the very
early stage of plastic deformation (1–3 %), followed by
a specimen failure. Various strategies to improve low
ductility of the nanostructured metals and alloys have
been proposed [28, 40, 55]. These strategies could be
divided into two groups which we would define as (1)
'mechanical ’ strategies and (2) ‘ microstructural ’
strategies. The 'mechanical' strategies employ the
mechanical characteristics of the UFG materials such as
their work hardening ability and/or strain rate sensitivity.
These mechanical characteristics can be varied by
changing the testing parameters such as temperature
and/or strain rate. The ‘microstructural’ strategies are
based on the idea of intelligent microstructural design.
For tensile behavior, the uniform strain is usually in
good agreement with the well-known Considère
criterion [56],
( ) (3)
which is a geometric criterion stating that when the work
hardening rate, (dσ/dε), decrease to the level of the flow
stress, σ, macro-localization of plastic deformation
(necking) should occur resulting in a specimen failure.
The nanostructured metallic materials are usually
characterized by increased strain rate sensitivity even at
low temperatures compared to their coarse-grained
counterparts [28, 54]. Therefore, the Hart criterion [57]
is more appropriate to predict the uniform elongation of
the nanostructured metals and alloys:
( ) (4)
where m is the strain rate sensitivity. It follows from Eq.
4 that the uniform elongation can be enhanced by (1)
increasing the work hardening rate dσ/dε and/or (2) the
strain rate sensitivity m.
Meanwhile, since the mechanical characteristics of
the materials are also determined by their microstructure,
it can be outlined that manipulation with the
microstructure is the major tool to enhance the ductility
of the nanostructured alloys.
In this connection, findings of extraordinarily high
strength and good ductility in several bulk UFG metals
produced by SPD are of special interest [58-61]. It is
important to consider in detail the three different
approaches that were used in the earlier investigations.
In the first study, high-purity (99.996 %) Cu was
processed at room temperature using ECAP with a 90°
clockwise rotation around the billet axis between
consecutive passes in route BC [58]. The strength and
ductility were measured by uniaxial tensile tests, and the
resulting engineering stress–strain curves are shown in
Fig. 8 for the Cu samples tested at room temperature in
the initial coarse-grained condition and in three
processed states [58]. It is apparent that the initial
40[4] 309-318 (2015) 313
coarse-grained Cu with a grain size of about 30 μm has a
very low yield stress with significant strain hardening
and a large elongation to failure. Cold rolling of the Cu
with reduction ratio of 60 % significantly increases the
strength (curve 2 in Fig. 8), but dramatically decreases
the elongation to failure. This result is consistent with
the classical mechanical behavior of metals that are
plastically deformed. The same tendency is true also for
Cu subjected to two passes of ECAP. However, further
straining of Cu to 16 passes of ECAP (curve 4 in Fig. 8)
simultaneously increases both the strength and ductility.
Furthermore, the increase in ductility is much more
significant than the relatively minor increase in strength.
Thus, the data shown in Fig. 8 for ECAP-processed Cu
clearly demonstrate an enhancement of strength as well
as ductility with accumulated deformation due to an
increase in the number of passes from 2 to 16 [58]. This
is a very remarkable result that for the first time was
observed in metals processed by plastic deformation.
Accordingly, this effect was termed the ‘paradox of
strength and ductility in SPD-processed metals,’ and the
principles of this paradox are illustrated in Fig. 9, where
it is apparent that conventional metals lie within the
lower shaded quadrant [58]. As shown in Fig. 9, for Cu
and Al, cold rolling (the reduction in thickness is marked
by each datum point) increases the yield strength but
decreases the elongation to failure [62, 63]. The
extraordinary combination of high strength and high
ductility shown in Fig. 9 for the nanostructured Cu and
Ti after SPD processing clearly sets them apart from the
other coarse-grained metals.
Figure 8. Tensile engineering stress–strain curves for Cu
tested at 22 °C with a strain rate of 10−3 s−1: The
processing conditions for each curve are indicated [58].
In recent years, similar tendencies have been
reported in a number of metals, including Al [64, 65],
Cu [66], Ni [67], and Ti [58, 61], after SPD processing
via ECAP, HPT, and ARB. Concerning the origin of this
phenomenon, it has been suggested that it is associated
with an increase in the fraction of high-angle grain
boundaries with increasing straining and with a
consequent change in the dominant deformation
mechanisms due to the increasing tendency for the
occurrence of grain boundary sliding and grain rotation
[58, 68].
SOMIYA Award 2015 memorial review paper
314 Recent Findings in Superior Strength and Ductility of Ultrafine-Grained Materials
Fig. 9. The paradox of strength and ductility in metals
subjected to SPD: the extraordinary combination of high
strength and high ductility in nanostructured Cu and Ti
processed by SPD (two upper points) clearly sets them
apart from conventional coarse-grained metals (lower
points relating to metals of 99.5–99.9 % purity) [58].
Another approach to enhance ductility is based on
introduction of a bimodal distribution of grain sizes [60,
69]. In [60], nanostructured Cu was produced through a
combination of ECAP and subsequent rolling at the
liquid nitrogen temperature prior to heating to a
temperature of ~450 K. This processing route resulted in
the formation of a bimodal structure of micrometer-sized
grains, with a volume fraction of around 25%, embedded
in a matrix of nanocrystalline grains. The material
exhibited an extraordinarily high ductility but also
retained a very high strength. The reason for this
behavior is that while the nanocrystalline grains provide
strength, the embedded larger grains stabilize the tensile
deformation of the material. Other evidences for the
importance of grain size distribution come from
investigations on Zn [70], Cu [69], and Al alloys [71].
Furthermore, the investigation of Cu [69] showed that
bimodal structures may increase the ductility not only
during tensile testing but also during cyclic deformation.
This observation is also important in improving the
fatigue properties of materials.
The third strategy is associated with the
microstructural modification that may not only increase
the strength at expense of ductility (or to increase
ductility sacrificing strength), but also improve both
ductility and strength [72]. Given that the low ability for
strain hardening in nanostructured materials is caused by
the limitations for accumulating dislocations and other
defects in nanostructured materials, these strategies are
based on modifying the nanostructural features to
promote accumulation of dislocations [54]. This idea
was successfully realized in a commercial Al–Zn–Mg–
Cu–Zr alloy [28] and an Al–10.8 % Ag alloy [59]
subjected to ECAP and subsequent artificial aging. The
principle of this approach is illustrated in Fig. 10 for the
Al–Ag alloy, where the Vickers microhardness is plotted
against the aging time at 373 K for samples in a
solution-treated (ST) condition and after cold rolling
(CR) and ECAP [59]. For the ST condition, the hardness
is initially low but increases with aging time to a peak
value after 100 h (3.6 × 105 s). For the CR condition, the
hardness is higher, but there is only a minor increase
with aging. The hardness is even higher after ECAP and
further increases with aging to a peak value after 100 h.
The relatively lower values of hardness recorded after
CR in comparison with ECAP are due to the lower
equivalent strain imposed on the sample: These strains
were ~1.4 in CR and ~8 in ECAP, so the microstructure
after CR consisted of subgrains and cell boundaries
having low misorientation angles.
Figure 10 Variation of the Vickers microhardness with
aging time for the Al–10.8 % Ag alloy after solution
treatment (ST), cold-rolling (CR), and ECAP [59].
It was shown, using scanning TEM, that the peak
hardness achieved after ECAP and aging for 100 h is
due to precipitation within the grains of spherical
particles with diameters of ~10 nm and elongated
precipitates with lengths of ~20 nm. The spherical
particles were identified as η-zones consisting of arrays
of solute atoms lying parallel to the (001) planes, and the
elongated precipitates were identified as the platelike γ'
particles. It was shown also that additional aging up to
300 h led to a growth in the γ'′particles and a very
significant reduction in the density of the fine η-zones,
thereby giving a consequent loss in hardening at the
longest aging time recorded in Fig. 10. Introduction of
artificial aging after ECAP has an important influence
on the stress–strain behavior at room temperature, as
demonstrated in Fig. 11, where the tensile stress–strain
curves are shown after ECAP and after ST, CR, and
ECAP with additional aging for 100 h at 373 K: each
sample in Fig. 11 was tested at room temperature at an
initial strain rate of 10−3 s−1 [59]. Thus, ST and artificial
aging give a reasonable tensile strength, an extensive
region of uniform strain and good ductility, whereas CR
and aging give an increased strength but very limited
uniform strain and a marked reduction in the total
ductility. For the ECAP condition, the strength is high in
the absence of aging, but there is a negligible region of
uniform strain and no significant strain hardening. By
contrast, the sample processed by ECAP and aged for
SOMIYA Award 2015 memorial review paper
Ruslan Z. Valiev et al. Trans. Mat. Res. Soc. Japan
100 h shows a similar high strength, a region of strain
hardening and good ductility. In practice, the uniform
strain of ~0.14 achieved in this specimen is similar to
the uniform strain of ~0.17 in the sample after ST and
aging, and the elongation to failure of ~0.40 is
comparable to, and even slightly exceeds, the elongation
of ~0.37 recorded in the ST and aged condition. These
results demonstrate, therefore, the potential for
producing high strength and good ductility in
precipitation-hardened alloys. Furthermore, although the
results documented in Figs. 10 and 11 relate to a model
Al–Ag alloy, it is reasonable to anticipate that it should
be possible to achieve similar results in commercial
engineering alloys where the aging treatments are
generally well documented. Indeed, this approach was
successfully realized also on AA7075 [72] and AA2024
[73].
The next strategy in nanostructural design to
improve strength and ductility relies on introduction of
high density of twins, which could also assist effective
dislocation accumulation inside grains. This was
demonstrated on pulsed electrodeposited Cu where the
extraordinary strength (about 1 GPa) with reasonable
ductility was observed [74]. In SPD-processed materials,
nanotwins can be introduced via low-temperature
processing and/or deformation at high strain rate. The
first way was realized on the example of nanostructured
Cu with twins produced by ECAP followed by
cryogenic drawing and cryogenic rolling [17]. Dynamic
plastic deformation (deformation at high strain rate) in
combination with liquid nitrogen temperature allowed to
increase dramatically the strength of Cu retaining
ductility in [75]. The other approaches involve lowering
stacking fault energy (SFE) to promote partial
dislocation slip [76], the abovementioned low
dislocation density and high-angle grain boundaries
formation and multiple phases and phase
transformations [77].
Figure 11. Tensile plots of stress versus strain at room
temperature for the Al–10.8 % Ag alloy after solution
treatment (ST) or cold-rolling (CR) with aging at 373 K
for 100 h or ECAP without subsequent aging and ECAP
with aging at 373 K for 100 h [59].
It is worth also noting that in the nanostructured
metals processed by SPD, both strength and ductility can
be improved by performing mechanical tests at lower
temperature and/or high strain rate [72, 78]. As an
40[4] 309-318 (2015) 315
example, Fig. 12 displays the tensile engineering stress–
strain curves of UFG Ti with a grain size of 260 nm
tested at room temperature and 77 K [78, 79]. At room
temperature, the Ti has some ductility and a small
uniform elongation, as shown by curve A obtained at a
strain rate of 10−3 s−1. However, at 77 K, the strength of
the material is drastically elevated to ~1.4 GPa. There is
also a simultaneous increase in the elongation to failure,
and this increases with strain rate up to a maximum
close to ~20 %, as shown in Fig. 12 where curves B–D
are for strain rates of 10−3 s−1, 10−2 s−1, and 10−1 s−1,
respectively. These results for strength and ductility are
better than, or at least comparable to, those of Ti alloys
with a high percentage of alloying elements. Here,
pronounced necking is delayed even for this very strong
metal, resulting in a large area under the stress–strain
curve and a generally tough behavior of the material. For
comparison, curve E shows the initial 18 % of strain for
a conventional coarse-grained Ti sample tested at 77 K
[79].
Figure 12. Engineering stress–strain curves for
nanostructured Ti where curve A is for testing at room
temperature at a strain rate of 1 × 10−3 s−1 and curves B–
D for the same Ti tested at 77 K for strain rates of 1 ×
10−3 s−1, 1 × 10−2 s−1 and 1 × 10−1 s−1, respectively; for
comparison, curve E shows the behavior of
coarse-grained Ti over the initial 18 % of strain when
testing at 77 K [79]. The curves are reproduced from
[78].
Another fundamental concept to control ductility is
based on manipulation with strain rate sensitivity of
material (Eq. 3.5). The UFG Cu with high ductility was
found to have higher strain rate sensitivity, m, which is
defined as {dlnσ/dlnέ} where σ is the applied stress and
έ is the strain rate [58]. Indeed, nanostructured materials
as a rule have small strain hardening rate that means a
limited capability to store dislocations inside grains. The
increased strain rate sensitivity would mean that a
mixture of grain boundary sliding and dislocation slip
operate the plastic flow, thus providing plastic
deformation.
The value of m was equal to ~0.14 for
ECAP-processed Cu taken through 16 passes compared
with a value of m of ~0.06 for ECAP-processed Cu
taken through only 2 passes. A high value for the strain
rate sensitivity indicates viscous flow and renders the
material more resistant to necking and, therefore, more
SOMIYA Award 2015 memorial review paper
316 Recent Findings in Superior Strength and Ductility of Ultrafine-Grained Materials
ductile. Increased strain rate sensitivity was also
revealed in a number of other studies [65, 80, 81]. It was
recently demonstrated that the m-value in the UFG Al
alloys at room temperature can be increased up to 0.24
via manipulation with the chemical composition of grain
boundaries [82] that can lead to the extraordinarily high
ductility at room temperature.
Lastly, there has been confusion and mix-up about
the ductility and plasticity in the academic community.
Ductility is examined through tensile tests, and can be
regarded as a special case of plasticity, i.e. plasticity
under tensile testing. In contrast, plasticity is the
capability of plastic deformation under any deformation
mode such as compression, rolling, etc. Ductility is
determined by the strain hardening rate and strain rate
sensitivity, as discussed earlier, while plasticity is
largely determined by the crystal structure and
availability of slip systems and other plastic deformation
mechanisms such as grain boundary sliding. For
example, cubic systems such as fcc and bcc metals
generally have higher plasticity than hcp systems
because the cubic systems have more slip systems.
Therefore, higher ductility usually means also high
plasticity, but the reverse may not be true. This is
reflected in nanostructured metals, which usually have
low ductility but very good plasticity. For example,
recent works showed that even at limited elongation to
failure values measured by tensile tests, the SPD
materials can demonstrate the same technological
plasticity as their coarse-grained counterparts [83]. This
is attributed to heterogeneity of plastic flow combined
with dislocation glide and grain boundary sliding. This
makes SPD materials to be not only attractive research
objects but also reliable candidates for advanced
industrial applications from technological point of view.
In conclusion, recent results show that grain
refinement by SPD can lead to a unique combination of
strength and ductility in metallic materials. Such
superior mechanical properties are highly desirable in
the development of advanced structural nanomaterials
for the next generation applications [29, 68, 84].
However, the achievement of these properties is
associated with the tailoring of specific microstructures
which, in turn, are determined by the precise processing
regimes and the nature of any further treatments. This
strategy represents the art and science of nanostructuring
for advanced properties using SPD techniques [5, 16,
33].
Acknowledgments
This work was partially supported by the Russian
Federal Ministry for Education and Science (through
R.Z.V. Grant No. 14.B25.31.0017 and Y.T.Z. is partially
funded by the US Army Research Office (W911
NF-12-1-0009), the US National Science Foundation
(DMT-1104667) and by the Nanjing Univ of Sci and
Technol., China. The authors would like to express
sincere gratitude and appreciation to reputable
colleagues from the International NanoSPD Steering
Committee (www.nanospd.org) and in particular, Prof.
Terence G. Langdon, for support and fruitful
discussions.
[1] R.Z. Valiev and T.G. Langdon. IOP Conf. Series:
Mater. Sci. Eng. 63, 011002 (2014).
[2] R.Z. Valiev, R.K. Islamgaliev and I.V. Alexandrov,
Prog. Mater. Sci., 45, 103-189 (2000).
[3] R.Z. Valiev, Y. Estrin, Z. Horita, T.G. Langdon, M.J.
Zehetbauer and Y.T. Zhu, JOM, 58, 33-39 (2006).
[4] Bulk Nanostructured Materials, Ed. by M.J.
Zehetbauer and Y.T. Zhu, Wiley-VCH, Weinheim
(2009).
[5] R.Z. Valiev, A.P. Zhilyaev and T.G. Langdon, Bulk
Nanostructured Materials: Fundamentals and
Applications, Wiley, Hoboken, NJ, USA (2014).
[6] Y.B. Wang, X.Z. Liao, Y.H. Zhao, J.C. Cooley, Z.
Horita and Y.T. Zhu, Appl. Phys. Lett., 102, 231912
(2013).
[7] T.G. Langdon, Acta Mater., 61, 7035-7059 (2013).
[8] Production of multifunctional materials using severe
plastic deformation. International Symposium on
Giant Straining Process for Advanced Materials
(GSAM2010), Ed. by Z. Horita, Kyushu University
Press, Fukuoka, Japan (2010).
[9] Estrin Y and Vinogradov A. Extreme grain
refinement by severe plastic deformation: A wealth of
challenging science. Acta Mater. 2013;61:782-817.
[10] X. Sauvage, G. Wilde, S.V. Divinski, Z. Horita and
R.Z. Valiev, Mater. Sci. Eng. A, 540, 1-12 (2012).
[11] R.Z. Valiev and T.G. Langdon, Prog. Mater. Sci., 1,
881-981 (2006).
[12] A.P. Zhilyaev and T.G. Langdon. Prog. Mater. Sci.,
53, 893-979 (2008).
[13] A.P. Zhilyaev, S. Lee, G.V. Nurislamova, R.Z.
Valiev, and T.G. Langdon, Scripta Mater., 44, 2753
(2001).
[14] A.P. Zhilyaev, G.V. Nurislamova, B.K. Kim, M.D.
Baró, J.A. Szpunar, and T.G. Langdon, Acta Mater., 51,
753 (2003).
[15] J. Wongsa-Ngam, M. Kawasaki, and T.G. Langdon,
J. Mater. Sci., 48, 4653 (2013).
[16] Y.T. Zhu, X.Z. Liao and X.L. Wu, Prog. Mater.
Sci., 57, 1-62 (2012).
[17] Y.H. Zhao, J.E. Bingert, X.Z. Liao, B.Z. Cui, K.
Han, A.V. Sergueeva, A.K. Mukherjee, R.Z. Valiev, T.G.
Langdon and Y.T. Zhu, Adv. Mater., 18, 2949-2953
(2006).
[18] Y.H. Zhao, X.Z. Liao, S. Cheng, E. Ma and Y.T.
Zhu. Adv. Mater., 18, 2280-2283 (2006).
[19] Y.H. Zhao, Y.T. Zhu, X.Z. Liao, Z. Horita and T.G.
Langdon, Appl. Phys. Lett., 89, 121906 (2006).
[20] X.L. Wu and Y.T. Zhu, Phys. Rev. Lett., 101,
025503 (2008).
[21] Y.T. Zhu, X.Z. Liao, X.L. Wu and J. Narayan, J.
Mater. Sci., 48, 4467-4475 (2013).
[22] S. Ni, Y.B. Wang, X.Z. Liao, H.Q. Li, R.B.
Figueiredo, S.P. Ringer, T.G. Langdon and Y.T. Zhu,
Phys. Rev. B, 84, 235401 (2011).
[23] G. Nurislamova, X. Sauvage, M. Murashkin, R.
Islamgaliev and R.Z. Valiev, Philos. Mag. Lett., 88,
459-466 (2008).
[24] G. Sha, Y.B. Wang, X.Z. Liao, Z.C. Duan, S.P.
Ringer and T.G. Langdon, Acta Mater., 57, 3123-3132
(2009).
[25] P.V. Liddicoat, X.Z. Liao, Y.H. Zhao, Y.T. Zhu,
M.Y. Murashkin, E.J. Lavernia, R.Z. Valiev and S.P.
Ringer, Nature Comm., 1, 63 (2010).
[26] R.Z. Valiev, N.A. Enikeev, M.Y. Murashkin, V.U.
SOMIYA Award 2015 memorial review paper
Ruslan Z. Valiev et al. Trans. Mat. Res. Soc. Japan
Kazykhanov and X. Sauvage, Scripta Mater., 63,
949-952 (2010).
[27] R.Z. Valiev, M.Y. Murashkin, E.V. Bobruk and G.I.
Raab, Mater. Trans., 50, 87-91 (2009).
[28] Y.H. Zhao, Y.T. Zhu and E.J. Lavernia, Adv. Eng.
Mater., 12, 769-778 (2010).
[29] D.G. Morris, In: Nanostructured Metals and Alloys.
Processing, Microstructure, Mechanical Properties and
Applications, Ed. By S.H. Whang, Woodhead
Publishing Limited, Cambridge (2011) p. 297.
[30] C. Pande and K. Cooper, Prog. Mater. Sci., 54, 689
(2009)
[31] R.Z Valiev, N.A. Enikeev, M.Y. Murashkin, S.E.
Aleksandrov and R.V Goldshtein, Doklady Phys., 55(6),
267 (2010).
[32] R.Z. Valiev and T.G. Langdon, Adv. Eng. Mater.,
12, 677 (2010).
[33] R.Z. Valiev, N.A. Enikeev and T.G. Langdon,
Kovove Mater., 49, 1 (2011).
[34] M.M. Abramova, N.A. Enikeev, R.Z. Valiev, A.
Etienne, B. Radiguet, Y. Ivanisenko and X. Sauvage,
Mater. Lett., 136, 349–352 (2014).
[35] N. Tsuji, In: Nanostructured Materials by
High-Pressure Severe Plastic Deformation, Ed. By Y.T.
Zhu, V. Varyukhin, Springer, Netherlands (2006) p. 227.
[36] M. Furukawa, Z. Horita, M. Nemoto, R.Z. Valiev
and T.G. Langdon, Phil. Mag. A, 78, 203 (1998).
[37] I.P. Semenova, G. Salimgareeva, G. Da Costa, W.
Lefebvre and R.Z. Valiev, Adv. Eng. Mater., 12, 803
(2010).
[38] Y. Ivanisenko, A.V. Sergueeva, A. Minkow, R.Z.
Valiev and H.J. Fecht, In: Nanomaterials by Severe
Plastic Deformation, Ed. By M.J. Zehetbauer, R.Z.
Valiev, Wiley-VCH, Weinheim (2004) p. 453.
[39] M.V. Chukin, N.V. Koptseva, R.Z. Valiev, I.L.
Yakovleva, J. Zrnik and T. Covarik, Vestnik MGTU, 1,
31 (2008).
[40] I. Sabirov, M.Yu. Murashkin and R.Z. Valiev,
Mater. Sci. Eng. A, 560, 1–24 (2013).
[41] J.S.M. Li, In: Mechanical Properties of
Nanocrystalline Materials, Ed. by J.S.M. Li, Pan
Stanford Publ., Singapore (2011) p. 193.
[42] S.A. Firstov, T.G. Rogul, V.T. Marushko and V.A.
Sagaydak, Issues Mater. Sci., 33, 201 (2003).
[43] S.A. Firstov, T.G. Rogul and O.A. Shut, Funct.
Mater., 16, 4 (2009).
[44] R.Z. Valiev, E.V. Kozlov, Yu.F. Ivanov, J. Lian,
A.A. Nazarov and B. Baudelet, Acta Metall. Mater., 42,
2467 (1994).
[45] S. Scheriau, Z. Zhang, S. Kleber and R. Pippan,
Mater. Sci. Eng. A, 528, 2776–2786 (2011).
[46] A.T. Krawczynska, M. Lewandowska, R. Pippan
and K.J. Kurzydlowski, J. Nanosci. Nanotech. 13, 1–4
(2013).
[47] H. Wang, I. Shuro, M. Umemoto, H.H. Kuo and Y.
Todaka, Mater. Sci. Eng. A, 556, 906–910 (2012).
[48] D. Raabe, M. Herbig, S. Sandlöbes, Y. Li, D. Tytko,
M. Kuzmina, D. Ponge and P.P. Choi, Curr. Opin. Solid
State Mater. Sci., 18, 253–261 (2014)
[49] D. Raabe, P.P. Choi, Y. Li, A. Kostka, X. Sauvage,
F. Lecouturier, K. Hono, R. Kirchheim, R. Pippan and D.
Embury, MRS Bull., 35, 982 (2010).
[50] Y.H. Zhao, Y.Z. Guo, Q. Wei, A.M. Dangelewicz,
C. Xu, Y.T. Zhu, T.G. Langdon, Y.Z. Zhou, and E.J.
40[4] 309-318 (2015) 317
Lavernia, Scripta Mat, 59, 627-630 (2008).
[51] D. N. Hanlon, S.M.C. Bohemen, and D. Celotto,
Mater. Sci. Tech. 3, 385-388 (2015).
[52] Y.T. Zhu, B.Q. Han and E.J. Lavernia, In: Bulk
Nanostructured Materials, Ed. by M.J. Zehetbauer, Y.T.
Zhu, WILEY-VCH Verlag GmbH & Co, Weinheim
(2009) p.89.
[53] Mechanical Behaviour of Nanostructured Materials,
Ed. by D.G. Morris, Trans. Tech. Publications,
Uetikon-Zurich (1998)
[54] C.C. Koch, Scripta Mater., 49, 657 (2003).
[55] E. Ma, JOM, 58(4), 49 (2006).
[56] G.E Dieter, Mechanical Metallurgy. McGraw-Hill,
Boston (1986)
[57] E.W. Hart, Acta Metal. Mater., 15, 351 (1967)
[58] R.Z. Valiev, I.V. Alexandrov, T.C. Lowe and Y.T.
Zhu, J. Mater. Res., 17, 5 (2002).
[59] Z. Horita, K. Ohashi, T. Fujita, K. Kaneko and T.G.
Langdon, Adv. Mater., 17, 1599 (2005).
[60] Y. Wang, M. Chen, F. Zhou and E. Ma, Nature,
419, 912 (2002).
[61] R.Z. Valiev, A.V. Sergueeva and A.K. Mukherjee,
Scripta Mater., 49, 669 (2003).
[62] E.R.Parker, Materials Data Book for Engineers and
Scientists, McGraw-Hill, New York (1967).
[63] E.A. Brandes and G.B. Brook, In: Smithells Metals
Reference Book, 7th edn, ChaButterworth–Heinemann,
Oxford (1992) p. 22.
[64] H.W. Hoeppel, J. May, P. Eisenlohr and M. Goeken,
Z. Metallkd., 96, 566 (2005).
[65] J. May, H.W. Hoeppel and M. Goeken, Scripta
Mater., 53, 189 (2005).
[66] F. Dalla Torre, R. Lapovok, J. Sandlin, P.F.
Thomson, C.H.J. Davies and E.V. Pereloma, Acta
Mater., 52, 4819 (2004).
[67] N. Krasilnikov, W. Lojkowski, Z. Pakiela and R.Z.
Valiev, Mater. Sci. Eng. A, 37, 330 (2005).
[68] R.Z. Valiev, Nat. Mater., 3, 511–516 (2004).
[69] H. Mughrabi, H.W. Hoeppel, M. Kautz and R.Z.
Valiev, Z. Metallkd., 94, 1079 (2003).
[70] X. Zhang, H. Wang, R.O. Scattergood, J. Narayan,
C.C. Koch, A.V. Sergueeva and A.K. Mukherjee, Acta
Mater., 50, 4823 (2002).
[71] Y.S. Park, K.H. Chung, N.J. Kim and E.J. Lavernia,
Mater. Sci. Eng. A, 374, 211 (2004).
[72] Y.H. Zhao, X.Z. Liao, S. Cheng, E. Ma and Y.T.
Zhu, Adv. Mater., 18, 2280 (2006).
[73] S. Cheng, Y.H. Zhao, Y.T. Zhu and E. Ma, Acta
Mater., 55, 5822 (2007).
[74] L. Lu, Y.F. Shen, X.H. Chen, L.H. Qian and K. Lu,
Science, 304, 422 (2004).
[75] N. Tao and K. Lu, J. Mater. Sci. Tech., 23(6), 771
(2007).
[76] T. Ungar, L. Balogh, Y.H. Zhao, Y.T. Zhu, Z.
Horita, C. Xu and T.G. Langdon, Acta Mater., 56, 809
(2008).
[77] Y.I. Son, Y.K. Lee, K.T. Park, C.S. Lee and D.H.
Shin, Acta Mater., 53, 3125 (2005).
[78] Y. Wang, E. Ma, R.Z. Valiev and Y. Zhu, Adv.
Mater., 16, 328 (2004).
[79] F. Ebrahimi, G.R. Bourne, M.S. Kelly and T.E.
Matthews, Scripta Mater., 11, 343 (1999).
[80] Y.I. Li, X.H. Zeng, W. Blum, Acta Mater., 52, 5009
(2004).
SOMIYA Award 2015 memorial review paper

318 Recent Findings in Superior Strength and Ductility of Ultrafine-Grained Materials

[81] T. Mungole, P. Kumar, M. Kawasaki and T.G.

Langdon, J. Mater. Res., 29, 2534-2546 (2014).
[82] R.Z. Valiev, M.Yu. Murashkin, A.R. Kilmametov,
B.B. Straumal, N.Q. Chinh and T.G. Langdon, J. Mater.
Sci., 45, 4718 (2010).
[83] E.C. Moreno-Valle, M.A. Monclus, J.M.
Molina-Aldareguia, N. Enikeev and I. Sabirov, Metall.
Mater. Trans. A, 44, 2013–2399 (2013).
[84] M.A. Mayers, A. Mishra and D.J. Benson, Prog.
Mater. Sci., 51, 427 (2006).

(Received October 27, 2015; Accepted October 30, 2015)