Acta Materialia 153 (2018) 279e289

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Acta Materialia
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Mechanical properties and optimal grain size distribution profile of

gradient grained nickel
Y. Lin a, b, J. Pan a, H.F. Zhou c, H.J. Gao c, **, Y. Li a, *
a
Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang, 110016, China
b
University of Chinese Academy of Sciences, 19 Yuquan Road, Beijing, 100039, China
c
School of Engineering, Brown University, Providence, RI, 02912, USA

a r t i c l e i n f o a b s t r a c t

Article history: Gradient structured (GS) materials are ubiquitous in biological systems and now increasingly adopted in
Received 27 February 2018 engineering systems to achieve desirable combinations of mechanical properties. However, how to
Received in revised form control and characterize the gradient structure still remains challenging. In the present work, pure Ni
27 April 2018
samples possessing a gradient structure with a change in the grain size up to three orders of magnitude
Accepted 30 April 2018
Available online 3 May 2018
from 29 nm to 4 mm are prepared by electrodeposition, where the degree of grain size gradient is
accurately controlled. The GS Ni samples exhibit a favorable combination of high strength and high
ductility. An optimal grain size distribution profile is discovered which gives rise to a yield strength of
Keywords:
Gradient structured metals
460 MPa and a uniform elongation of 8.9%, the latter even better than that of the coarse-grained Ni.
Grain size distribution Experimental observations and molecular dynamics (MD) simulations reveal that the surface roughening
Degree of gradient of coarse grains and strain localization of nano-grains can be effectively suppressed by the mutual
Strength constraint between nano-grains and coarse grains, leading to the observed superior uniform elongation.
Ductility This work not only reports a promising methodology of producing materials possessing both high
strength and high ductility, but also provides a model for investigating the deformation mechanisms in
GS materials.
© 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

1. Introduction induced plasticity (TWIP) steel via pre-torsion [10], leading to a

Gradient structured (GS) materials are ubiquitous in biological
systems [1e4] and now increasingly adopted in engineering sys-
tems to achieve desirable combinations of mechanical properties
[5e11]. Recently, gradient nano-grained (GNG) Cu prepared
through surface mechanical grinding treatment (SMGT) was re-
ported by Fang et al. [7]. This GNG Cu exhibited a doubling yield
strength and a tensile plasticity comparable to that of the coarse
grained (CG) Cu. Using surface mechanical attrition treatment
(SMAT), similar gradient structure could also be attained in inter-
stitial free (IF)-steel, which rendered a unique combination of extra
strain hardening and high ductility [9]. The extra strain hardening
was attributed to the formation of geometrically necessary dislo-
cations (GNDs) as well as the multiaxial stress state. A gradient
hierarchical nanotwinned structure can be formed in twinning-
* Corresponding author.
** Corresponding author.
E-mail addresses: huajian_gao@brown.edu (H.J. Gao), liyi@imr.ac.cn (Y. Li).
simultaneous improvement of strength and ductility. In addition,
other mechanical properties such as fatigue life [12e14] and wear
resistance [15e19], could also be greatly enhanced in GS materials.
For a deeper understanding of the deformation mechanisms in
GS materials, the relationship between their microstructure and
mechanical properties has been investigated by computer
modeling and numerical simulation [20e23]. Using a crystal plas-
ticity finite element model, Zeng et al. found that there are large
stress/strain gradients in GNG Cu under uniaxial loading [22]. A
gradient variation of GNDs was built up to accommodate the
deformation incompatibility, leading to a sustained strain hard-
ening and enhanced ductility. On the other hand, the extra strain
hardening of GS IF steels was successfully described by a dislocation
density-based continuum plasticity model [21]. The high strain
hardening capability was attributed to the generation of abundant
GNDs in the gradient structure during plastic deformation.
The aforementioned studies suggest that materials having a
grain size gradient structure could possess superior mechanical
properties, in comparison with those having a monotonic grain size
structure. However, most of the previous studies were focused on

https://doi.org/10.1016/j.actamat.2018.04.065
1359-6454/© 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
280 Y. Lin et al. / Acta Materialia 153 (2018) 279e289
only one type of gradient structure due to limitations in the syn-
thesis technology. How to control the grain size distribution (i.e.
degree of grain size gradient) and what is the effect of the grain size
gradient profile on deformation behaviors were rarely studied. Is
there an optimum gradient profile? What is the key parameter of
the gradient structure that controls the mechanical properties?
These remaining issues may hinder the development of a thorough
understanding of deformation mechanisms in GS materials and
thus realization of their full potential in applications.
This work outlins a systematic investigation of the effect of
degree of gradient on the mechanical properties of GS Ni samples.
Direct current (DC) electrodeposition was adopted as a bottom-up
method for preparing GS Ni samples possessing various degrees
of gradient. By regulating processing conditions such as the current
density and additive concentration, Ni plates up to 2 mm in thick-
ness were prepared with the grain size changing continuously from
29 nm to 4 mm. An optimum grain size distribution was found in GS
Ni samples where ductility is peaked. The underlying mechanism
for such an optimization is also discussed in this work.
2. Experimental
2.1. The degree of gradient
Fig. 1a shows a schematic diagram of a number of grain size
variations as a function of position along the deposition direction.
The maximum and minimum grain sizes, dmax and dmin, are kept the
same among different cases, while the distributions of grain size are
quite different. For example, the transition in the grain size of
gradient A is gentler (Fig. 1b), resulting in a larger volume fraction
of fine grains (i.e. hard phases). On the other hand, gradient C has a
steeper change in grain size and a smaller volume fraction of fine
grains (Fig. 1b). Here, we employ a power law equation to charac-
terize the degree of gradient in GS metals with different types of
grain size profile. The relationship between grain size d and
normalized position x can be expressed as follows:
d ¼ dmax  ðdmax  dmin Þð1  xÞn
where n is the power index for the grain size distribution, which
can be considered as the degree of the gradient and the
Fig. 1. (a) Schematic illustration of various grain size gradient profiles as a function of position in gradient materials. (b) Three typical gradient structures with distinct grain size
distributions.
characteristic parameter of gradient materials. Generally, with an
increase in the n value, the volume fraction of coarse grains in-
creases, while the volume fraction of fine grains continuously de-
creases (Fig. 1a). The mechanical properties of GS Ni samples are
expected to have a dependency on the n value.
2.2. Sample preparation
The key to electroplating GS Ni plates having various degrees of
gradient is to establish a relationship between the grain size and
deposition conditions. Based on the previous studies [24,25], a
quantitative relationship between grain size and current density/
additive (sodium saccharin) content had been established, as
shown in Fig. 2a. Different from the previous works [24,25] where
the range of variation of grain size was limited to one order of
magnitude, a much wider range of change in grain size from several
microns to a few of tens nanometers has been attained by simul-
taneously and continuously adjusting the current density
(10e100 mA/cm2) and additive content (1e5 g/L) during deposi-
tion. In addition, their changing rates were modified to control the
degree of gradient. Fig. 2b shows a schematic diagram where the
output current and additive content continuously change with the
deposition time, contributing to a continuous refinement of the
grain size along the deposition direction.
Ni deposits having six different profiles of gradient structure
were designed and synthesized with a thickness up to 2 mm
through a conventional rotating disc electrode set-up. The plating
bath was a modified Watts-type electrolyte containing nickel sul-
fate (300 g/L), nickel chloride (45 g/L), boric acid (40 g/L) and
dodecyl sodium sulfate (0.05 g/L), maintained at pH value of
4.0 ± 0.2 and temperature of 328 ± 1 K. Monolithic CG and nano-
grained (NG) Ni samples were also prepared by electrodeposition
for comparison.
2.3. Elemental analysis and microstructure characterization
(1) The contents of nitrogen, hydrogen, oxygen, carbon and sulfur in
the GS Ni deposits were assessed by gas analysis (TCH-600
Hydrogen/Nitrogen/Oxygen Analyzer) and IR absorption method
(CS844 Carbon & Sulfur Determinator). The content of light
 Y. Lin et al. / Acta Materialia 153 (2018) 279e289 281

carried out on an INSTRON-5848 micro-tester system at a strain

rate of 3  104 s1 at room temperature. All GS Ni plates were
annealed at 373 K for 1 h to release the residual stress before cut-
ting and mechanical polishing into dog-bone shaped samples with
a total length of 25 mm, a gauge cross-section of about
0.5  1.2 mm2 and a gauge length of 6 mm. Moreover, these dog-
bone shaped samples were processed with a round of electro-
polishing, to acquire a smooth and residual-stress-free surface. A
laser extensometer was used to measure strain within the sample
gauge upon loading. The surface morphologies around the necking
areas of various GS Ni tensile specimens were examined by SEM
and confocal laser scanning microscope (CLSM) before and after
tension, respectively.

2.5. MD simulations

MD simulations were performed to understand the origin of the

superior ductility of gradient structures. The simulated gradient
sample consists of four regions, each with identical dimensions of
200 (X)  200 (Y)  2 (Z) nm3. To create the gradient grain distri-
bution along the X direction, the average grain size of the four re-
gions were chosen as d ¼ 10, 25, 50 and 100 nm, respectively. The
entire system contains about 26, 000, 000 atoms and 500 randomly
oriented grains in total. For comparison, uniform nanostructured
samples with d ¼ 10 and 100 nm were considered. Periodic
boundary conditions were imposed in Y and Z directions, while free
surfaces were created on the boundaries of the sample in X direc-
tion (i.e., gradient direction). The embedded atom method potential
for Ni [26] was adopted. The integration time-step was fixed at 1 fs.
All simulations were performed at 600 K using a Nose-Hoover
thermostat [27]. The sample was relaxed for 500 ps before strain-
ing. During uniaxial tension, a 20% strain was applied to the sample
at a strain rate of 5  108 s1. To identify plastic deformation, colors
were assigned to the atoms according to their atomic shear strain
[28].
Fig. 2. (a) Grain size as a function of additive content and current density during
deposition. (b) Schematic showing precise control of grain size gradient during
3. Results
electrodeposition.

3.1. Microstructure of GS Ni samples

element impurities was less than 200 ppm (wt.) in all deposits.
Based on Archimedes' principle, the density was measured to be
Fig. 3aed shows the cross-sectional SEM images of four GS Ni
larger than 99% in all deposits, implying that the deposits are dense.
samples, i.e. samples II, III, IV and V, respectively. A microstructural
Cross-sectional morphologies of various GS Ni were character-
evolution from coarse grains to fine grains along the deposition
ized by scanning electronic microscope (SEM FEI Nova NanoSEM
direction without a sharp interface is observed in these specimens,
430). Before cutting and polishing, the GS specimens were coated
indicating a typical gradient structure. In all GS specimens, the
with a protective Ni layer. Microstructure of the NG side was
grain size starts from ~4 mm at the end of columnar coarse grains
investigated by transmission electron microscope (TEM FEI Tecnai
(Fig. 3e), and gradually decreases to 29 nm near the end of fine
G2 F20) operated at 200 kV.
grains (Fig. 3f and g). The range of change in grain size almost spans
To measure the profile of grain size distribution, the GS Ni sheets
three orders of magnitude, comparable to those reported in the
were mechanically polished layer by layer along the deposition
literature [7,9]. Moreover, the change in grain size of the finer grains
direction, then directly tested by X-ray diffraction (XRD, Bruker D2
is much gentler in sample II than that in sample IV, leading to a
phaser) with Cu Ka radiation. Before the XRD measurement, all
higher fraction of nano-grains. This indicates a clear difference in
samples were annealed at 373 K for 1 h to release possible residual
the degree of grain size gradient in samples II and IV.
stresses generated during electrodeposition. Grain size was calcu-
The XRD patterns of sample II display a gradual change in the
lated based on the corresponding full width at half maximum
intensity and FWHM of diffraction peaks at various positions along
(FWHM) using Scherrer formula after correcting the instrumental
the deposition direction, as shown in Fig. 4a. From the substrate to
line broadening. The grain sizes of columnar coarse grains and
the surface, the diffraction intensity of (200) decreases and (111)
nano-grains were measured by SEM and TEM, respectively.
becomes the predominant crystal orientation. The obvious broad-
ening in the diffraction peaks denotes a decrease in the grain size.
2.4. Mechanical testing In addition, the diffraction peaks slightly shift to a higher angle
(~0.2 ) from surface to substrate, which could be attributed to a
The hardness profiles of GS Ni samples along the deposition compressive residual stress induced by the process of mechanical
direction were determined using Qness Q10 A þ microhardness polishing just before the XRD measurement. Detailed grain size
tester with Vickers indenter. The load for measurement was 5 g, profiles of various GS samples as a function of the normalized
with a dwell time of 10 s. Quasi-static uniaxial tensile tests were distance are plotted in Fig. 4b. Based on Eq. (1), the degree of
282
Fig. 3. Gradient structures of as-deposited Ni plates. (aed) Cross-sectional SEM images of samples II, III, IV and V, respectively; (e) Representative SEM image of coarse grains on the
CG side. (f) Dark-field TEM image and (g) the corresponding grain size distribution of the topmost surface layer on the NG side.
gradient, estimated by the value of n, ranges from 0.01 in sample I
to 5 in sample VI (Table 1).
Grain sizes below 1 mm along the deposition direction in sample
II were further confirmed by TEM. With an increase in the
normalized distance from 0.05 to 0.76, the average grain size
gradually increases from about 35 to 224 nm (Fig. 5a). Equiaxed
nano-grains were found at normalized distances of 0.05 and 0.58
(Fig. 5b and c), while elongated columnar grains appeared at
normalized distance of 0.76 (Fig. 5d). The average grain sizes ob-
tained by TEM are consistent with those calculated by XRD.
3.2. Mechanical properties of GS Ni samples
Fig. 6 presents the microhardness profiles of various GS Ni
samples. The microhardness continuously decreases from a
maximum value of ~5.4 GPa to the minimum value of ~2.5 GPa as
the normalized distance shifts from 0 to 1. These values are
Y. Lin et al. / Acta Materialia 153 (2018) 279e289
consistent with those obtained from monolithic NG and CG Ni
samples. Similar to the grain size gradient, hardness also exhibits
distinct gradient profiles for various GS samples. The change in
hardness is much slower in samples II and III than in samples V and
VI.
Fig. 7a displays engineering stress-strain curves of the GS Ni
samples under uniaxial tension at room temperature. For com-
parison, the data obtained from CG (4 mm) and NG (29 nm) Ni
samples are also included. The yield strength (0.2% offset, sy),
uniform elongation (εue) and ultimate tensile strength (sUTS) of each
specimen are listed in Table 1. As expected, both strength and
ductility are strongly dependent on the degree of gradient. From
samples I to VI, sy decreases monotonously from 880 to 409 MPa
with n increasing from 0.01 to 5. More interestingly, εue first in-
creases from 4.5% in sample I to 8.9% in sample V, and then de-
creases to 8.0% in sample VI. A maximum uniform elongation is
observed in sample V, which is 1.2 times higher than that of the CG
 Y. Lin et al. / Acta Materialia 153 (2018) 279e289 283

expense of reduced ductility, known as the strength and ductility

Fig. 4. (a) XRD patterns of sample II at various positions along deposition direction; (b)
Average grain size as a function of the normalized distance in samples II, IV and V,
respectively.
trade-off in conventional metals. It is thus surprising to observe the
simultaneous enhancement in strength and ductility in our GS Ni
samples (Fig. 8a). The true strain at which necking occurs reaches a
peak value of 8.5% at n ¼ 3, which is even larger than that of CG Ni
sample. Our results show that superior uniform elongation is
achievable by optimizing the gradient profile.
To further recognize the influence of degree of gradient on the
mechanical properties, various gradients from previous studies
[7,29,30] are summarized. The gradient structure synthesized by
surface plastic deformation (e.g. SMGT and SMAT) contains a GS
layer with a thickness up to 200 mm, regardless of the sample size.
The degree of gradient (the volume fraction of GS layer) is
controlled by the diameter or thickness of samples. In contrast, the
electrodeposition method developed in the present work for the
synthesis of GS samples imposes no restriction on the sample size
and degree of gradient, and allows for a similar range of variation in
the grain size compared to that by surface plastic deformation. To
eliminate any size effect and offer an intuitive comparison among
various GS materials, both grain size and distance of various GS
materials are normalized in Fig. 8b. The degree of gradient of
sample V is almost the same as that of GNG Cu, i.e. n ¼ 4 [7] (Fig. 8b
and Table 2), despite their distinct profiles in grain size. GS IF-steel
[29] showing favorable strength-ductility synergy has a similar
grain size profile to those of GNG Cu and sample V (Fig. 8b and
Table 2). In addition, there is an optimum range of volume fractions
of GS layer that produces the largest enhancement in strengthening
and extra strain hardening in pure Cu treated by SMAT [30].
Based on the above summary, an optimal grain size gradient
profile with a n value around 3 (such as sample V and GNG Cu [7])
can be reasonably deduced to exist where mechanical properties
can be optimized. The optimization of mechanical properties are
possibly ascribed to the effective constraint between coarse grains
and nano-grains in the gradient structure.

Table 1 4.2. Countering strain localization via reduced surface roughening

Lists of yield stresse sy, uniform elongation εue, ultimate tensile strength sUTS of CG,
NG, and GS Ni under uniaxial tension at a strain rate of 3  104 s1.
For the purpose of acquiring a large uniform ductility, the main
NG I II III IV V VI CG challenge is to delay strain localization and instability during
n 0.01 0.016 0.4 0.75 3 5 plastic deformation. Surface roughening is an important factor
sy (MPa) 1130 880 790 573 488 460 409 380 associated with strain localization in polycrystalline metals. If
εue (%) 2.96 4.56 5.2 6.72 7.04 8.9 8 7.5 plastic strain can no longer be fully accommodated by slip, the
sUTS (MPa) 1437 1200 1093 851 766 698 627 592 incompatibility between neighboring grains causes grains to move
normal to the surface, leading to roughening on the surface [31].
The unstable growth in surface roughening is considered as the
Ni sample, implying that ductility can be optimized by tuning the onset of critical strain localization, which is a direct precursor to
grain size distribution profile in the GS Ni samples. failure such as formations of cracks or necking [32e34]. Previous
Fig. 7b shows the relationship between strain hardening rate studies have shown that a reduction in strain hardening ability
(Q ¼ ds=dε) and true strain (εT ) for CG, NG, and two typical GS Ni caused by strain localization is accompanied by increased surface
samples. The strain hardening rate of NG Ni sample drops quickly roughness [31]. On the other hand, the inhibition of strain locali-
with straining, resulting in early plastic instability and premature zation is a key to improving the tensile ductility of metals [35].
failure. The strain hardening rates of GS Ni samples depend on the Consequently, it is important to establish a solid causality between
degree of gradient, i.e., the value of n in Eq. (1). Similar to NG Ni ductility and surface roughness in our GS Ni samples.
sample, Q in sample II drops quickly due to the small value of Surface roughness decreases with a decrease in grain size
n ¼ 0.016, leading to a reduced uniform elongation. Sample V has an [36e38]. In GS Ni samples, fine grains are expected to ease surface
appropriate value of n ¼ 3, and thus exhibits an enhanced strain roughening and inhibit strain localization. For gradient structures
hardening rate at the initial stage of straining as well as a slower with relatively high n values (such as sample VI), the gradient is too
decay in Q compared with CG Ni sample. steep and the nano-grains are less effective in reducing surface
roughening. The nano-grains fluctuate with inhomogeneous
deformation of the coarse grains after the onset of plastic insta-
4. Discussion bility. In other words, this kind of gradient structure cannot most
efficiently ease surface roughening and acquire optimal tensile
4.1. Optimal gradient property either, because of the lack of adequate constraint on
plastic instability in the coarse grains.
In general, increase in strength is usually achieved at the For gradient structures with relatively low n values (such as
284 Y. Lin et al. / Acta Materialia 153 (2018) 279e289

Fig. 5. (a) Grain size measured by XRD and TEM as a function of the normalized distance in sample II. Bright-field TEM images at normalized distances of (b) 0.05, (c) 0.58 and (d)
0.76 in sample II, where the corresponding average grain sizes are 35, 85, 224 nm, respectively.

suppressed by the coarse grains, leading to a rapid fracture after

yielding.
In the gradient structure with an optimum n value (i.e. appro-
priate grain size gradient profile), such as sample V with n ¼ 3,
surface roughening is mitigated by the mutual constraint of coarse
grains and nano-grains. The strain localization of nano-grains and
coarse grains can be efficiently suppressed simultaneously,
contributing to the smoothest surface and best accommodated
plastic deformation in the gradient structure.
In order to validate the above hypothesis, the surface roughness
of all samples was investigated. Fig. 9 presents the surface mor-
phologies and height variations of the GS Ni samples after tension.
Fig. 9b shows the morphology of surface valleys [31] observed in
the necking region on the CG side. Strain localization of the coarse
grains is verified by the largest height variation in Fig. 9j.
In contrast, a smoother surface morphology without obvious
cracks is observed on the NG side in sample VI (Fig. 9f and i).
However, the relatively large height variation (Fig. 9j) indicates that
the coarse grains are not effectively constrained. In addition,
intense strain localization in samples I and II leads to a rough sur-
Fig. 6. Hardness distributions of GS Ni having different degrees of grain size gradient.
face in the necking area (Fig. 9c, d and j) and micro-cracks (Fig. 9g)
on the NG side, indicating a rapid rupture of the whole structure.
Sample V has the smoothest surface on the NG side (Fig. 9e and
samples I and II), plastic deformation of GS Ni is dominated by the
j) and no obvious cracks (Fig. 9h) were observed, indicating that the
mechanical behavior of nano-grains, where limited dislocation
coarse grains are effectively constrained and strain localization of
activity [39e41] results in poor strain hardening capacity in the GS
nano-grains is also inhibited. This suppresses tensile instability and
specimens, thus a rougher surface is facilitated by early necking and
results in a superior elongation in sample V (Fig. 7a).
cracking. The strain localization of nano-grains cannot be
 Y. Lin et al. / Acta Materialia 153 (2018) 279e289 285

Fig. 7. (a) Engineering stress-strain curves of CG, NG and GS Ni with different degrees
Fig. 8. (a) Yield strength (experimental) versus necking strain for electrodeposited CG,
of gradient obtained at room temperature and a strain rate 3  104s1. (b) Strain
NG, and various GS Ni. (b) Summary of the grain size distribution in grain size gradient
hardening rate (Q ¼ ds/dε) vs. true strain (εT) curves of CG Ni, NG Ni, sample II and V,
materials, including GNG Cu [7], IF steel [35] and the present GS Ni. Normalized grain
respectively.
size is defined as: 1-(dmax-d)/(dmax-dmin).

The dependence of surface roughness and necking strain on n Table 2

values in GS Ni samples is further demonstrated in Fig. 10. The Summary of mechanical properties (yield stress, uniform elongation and ultimate
variation of surface roughness exhibits an opposite trend to that of strength) in gradient materials with various degrees of gradient.
the necking strain. Sample V with n ¼ 3 has the minimum surface n sy (MPa) sUTS (Mpa) εue (%) Authors
roughness and the maximum uniform elongation among the six
4 129 250 31 Fang et al.
samples (Fig. 10).
In spite of numerous previous studies on enhanced strength and 0.01 880 1200 4.5 This work
0.016 790 1093 5.2
ductility in NG and gradient metals [7,9,10,42e44], few reported
0.4 573 851 6.7
superior elongation larger than that of their CG counterpart 0.75 488 766 7.0
(Table 3). Our present work indicates that once the surface 3 460 698 8.9
roughening in a CG metal is effectively reduced by marrying to an 5 409 627 8.0
NG partner, the overall gradient structure could acquire higher 290 310 17 Wu et al.
hardening capacity and larger elongation than those in the case of a 240 280 19
free standing CG metal [42]. On the other hand, in case that the 210 275 26
170 265 30
plastic instability (strain localization) in a NG metal is suppressed
through pairing with a CG partner, the brittle NG metals can also
undergo large tensile deformation [45e48]. This synergy between
nano-grains and coarse grains stabilizes plastic instability by investigations in the future.
introducing gradient structure.
As noted, there is a strong (200) texture existing in the coarse 4.3. MD simulations of shear localization for GS Ni
grains inside the GS Ni specimen. However, the volume fraction of
the coarse grains monotonously changes with the degree of MD simulations were performed to further understand the ef-
gradient, thus the texture should not be the reason for the optimal fect of gradient grain distribution on the underlying plastic defor-
mechanical properties in our GS Ni. This issue deserves further mation mechanism in Ni samples. Deformation patterns of two
uniform nanostructured Ni samples with different grain sizes are
286 Y. Lin et al. / Acta Materialia 153 (2018) 279e289

Fig. 9. 3D surface images of GS Ni, including (a) polished sample before tension, (b) CG side of sample V, and (cef) NG sides of sample I, II, V and VI after tension. (gei) SEM images
of lateral surface at NG side of sample II, V and VI, respectively. (j) Height variation profiles of NG side in various GS Ni after tension, as well as the CG side surface and the polished
surface before tension. All profiles are taken from the regions near the fracture surface.

shown in Fig. 11a and b. In the sample with d ¼ 10 nm, plastic
deformation is governed by grain boundary associated activities,
including grain boundary sliding, grain rotation and grain coales-
cence. Fig. 11a shows that plastic deformation is localized along a
few planes forming inclination angles of roughly 45 with respect
to the loading axis, which can be attributed to the fact that the
driving force for grain boundary sliding, which is the resolved shear
stress on the grain boundaries, reaches its maximum value on these
planes. The result for the sample with d ¼ 100 nm at strain 20% is
shown in Fig. 11b, where plastic deformation is governed by dis-
locations emitted from triple junctions and free surfaces. Large
values of atomic shear strain occur mainly in a few inclined slip
bands, indicating highly localized plastic deformation in the
sample.
In contrast, the deformation patterns of the gradient nano-
structured Ni sample (Fig. 11c) displays several distinct features
compared with those shown in Fig. 11a and b: (1) Shear localization
on both sides of the gradient sample has been effectively
 Y. Lin et al. / Acta Materialia 153 (2018) 279e289 287

that the values of atomic shear strain, both at grain boundaries and
in the grain interior, are smaller than those observed in uniform
samples; (3) The size of the surface steps is also reduced due to
suppressed shear localization.
According to the previous works [49e53], NG metals show a
high strain hardening rate but low Q-sustained rate, resulting in
early strain localization. The inhibition of strain localization could
be accomplished by introducing an extra strain hardening mecha-
nism [9,42,44,54] in materials possessing an inhomogeneous
microstructure. The MD simulation results provide atomic scale
evidence in support of the hypothesis that introducing gradient in
grain size could effectively suppress shear localization and help to
achieve enhanced ductility compared with uniform samples.

4.4. Accommodation of mechanical incompatibility in gradient

structure

The mechanical incompatibility is prominent during the plastic

deformation of a heterogeneous structure, whose contributions to
the enhancement of mechanical properties would vary with
microstructural heterogeneity. As a typical heterogeneous struc-
ture, the influence and accommodation of mechanical in-
compatibility are determined by the type of materials and degree of
gradient.
For GS IF steel [9] or GS Cu [30], in order to accommodate a large
degree of non-uniform plastic deformation caused by the me-
chanical incompatibility, an increasing density of GNDs has to be
stored. The GNDs are the origin of back stress [21,55], which pro-
duces remarkable extra strain hardening and extra strengthening
with greater degree of mechanical incompatibility in GS IF steel [9]
and GS Cu [30]. One consequence of this extra strengthening is the
fact that the yield strength of GS IF steel and GS Cu is above the
Fig. 10. (a) Surface roughness (Ra) and (b) necking strain as a function of n. The region
value calculated using rule of mixture (ROM) [29], while the extra
near the fracture surface on the NG side is selected for measurement.
strain hardening should have contributed to the high ductility [9].
In this sense, the GNDs generated for the accommodation of me-
Table 3 chanical incompatibility induced back stress, which can play an
Summary of uniform elongation for heterogeneous structure and CG counterpart. essential role in the improvement of the strength and ductility for
Materials εue (%) Authors GS IF steel and GS Cu.
On the other hand, the extraordinary plasticity in GNG Cu [7,56]
CG Heterogeneous structure
was accommodated by grain coarsening. In contrast to the
Cu 32 31 Fang et al. strengthening/strain hardening caused by back stress in the case of
Ni 7.5 8.9 This work GS IF steel [9] and GS Cu [30], grain coarsening leads to strain
8.0 softening. Previous studies have shown that grain coarsening oc-
IF steel 38 17 Wu et al. curs in nano-grained Ni under plastic deformation [57,58]. We
19 speculate that the superior plasticity observed in our GS Ni samples
26 is induced by grain coarsening, rather than back stress induced
30
strain hardening. The strength of GS Ni samples follows the ROM
TWIP steel 49 70 Wei et al. and no strain hardening up-turn is observed (Fig. 7b), suggesting
58
that the contribution of back stress might not be significant. This
55
57
issue remains to be fully clarified in the future.
Although several deformation mechanisms on enhancing
Ti 8.0 8.2 Wu et al.
ductility in GS metals have been proposed, such as dissociation of
8.5
9.0 dislocations interacting with twin boundaries [10], GNDs intro-
10.0 duced extra work hardening [9,21], grain coarsening [7,56] and
10.5 back stress hardening [42,55], our current observation provides an
Cu 49 30 Wang et al. additional explanation. Furthermore, it should be pointed out that
Cu 40 3 Yang et al.
the present work is only a starting point. The present gradient
14 structure is asymmetric which may be detrimental to the plastic
25 deformation. If the gradient structure or grain size distribution can
29 be further optimized, a better combination of strength and ductility
can be expected.

suppressed at strain of 20%. Though plastic deformation still tends 5. Conclusions

to localize near the free surfaces, it is uniformly dispersed in the
interior of the sample; (2) From the color of the contour, we can tell In conclusion, we have developed a method to synthesize bulk
288
Fig. 11. Deformation patterns of (a) 10 nm Ni, (b) 100 nm Ni, and (c) gradient Ni with grain size ranging from 10 to 100 nm at a strain of 20%. Colors are assigned based on local shear
strain. (For interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)
and dense GS Ni plates possessing various degrees of grain size
gradient (i.e., grain size distribution profiles). Microstructural
characterization shows a continuous change in grain sizes spanning
up to three orders of magnitude from 4 mm to 29 nm and the degree
of gradient can be accurately controlled. The effect of the degree of
gradient on mechanical properties of GS Ni specimens has been
systematically investigated. The yield stress monotonically de-
creases with an increase in the n value, while the uniform elon-
gation reaches a maximum value of 8.9% at n ¼ 3, signifying an
optimal grain size gradient for enhanced ductility which is even
better than that of the CG counterpart. As revealed by our experi-
mental observations and MD simulations, the surface roughening
of coarse grains and strain localization of nano-grains can be
effectively suppressed due to the mutual constraint between nano-
grains and coarse grains. As a result, the GS Ni sample possessing
the optimal grain size gradient profile undergoes larger plastic
deformation than the homogeneous CG structure, resulting in su-
perior plasticity. This work provides a novel strategy for synthe-
sizing GS materials possessing various degrees of gradient and an
additional insight into the excellent ductility in GS materials.
Acknowledgements
This work was financially supported by National Natural Science
Foundation of China under Grant Nos. 51471165 and 51401220. H.Z.
and H.G. acknowledges support by the US National Science Foun-
dation through grant DMR-1709318. The simulations reported were
performed on resources provided by the Extreme Science and En-
gineering Discovery Environment (XSEDE) through grant
MS090046.
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