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Mechanical Properties and Optimal Grain Size Distribution Profile of Gradient Grained Nickel
Mechanical Properties and Optimal Grain Size Distribution Profile of Gradient Grained Nickel
Acta Materialia
journal homepage: www.elsevier.com/locate/actamat
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.
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- characteristic parameter of gradient materials. Generally, with an
thesis technology. How to control the grain size distribution (i.e. increase in the n value, the volume fraction of coarse grains in-
degree of grain size gradient) and what is the effect of the grain size creases, while the volume fraction of fine grains continuously de-
gradient profile on deformation behaviors were rarely studied. Is creases (Fig. 1a). The mechanical properties of GS Ni samples are
there an optimum gradient profile? What is the key parameter of expected to have a dependency on the n value.
the gradient structure that controls the mechanical properties?
These remaining issues may hinder the development of a thorough
2.2. Sample preparation
understanding of deformation mechanisms in GS materials and
thus realization of their full potential in applications.
The key to electroplating GS Ni plates having various degrees of
This work outlins a systematic investigation of the effect of
gradient is to establish a relationship between the grain size and
degree of gradient on the mechanical properties of GS Ni samples.
deposition conditions. Based on the previous studies [24,25], a
Direct current (DC) electrodeposition was adopted as a bottom-up
quantitative relationship between grain size and current density/
method for preparing GS Ni samples possessing various degrees
additive (sodium saccharin) content had been established, as
of gradient. By regulating processing conditions such as the current
shown in Fig. 2a. Different from the previous works [24,25] where
density and additive concentration, Ni plates up to 2 mm in thick-
the range of variation of grain size was limited to one order of
ness were prepared with the grain size changing continuously from
magnitude, a much wider range of change in grain size from several
29 nm to 4 mm. An optimum grain size distribution was found in GS
microns to a few of tens nanometers has been attained by simul-
Ni samples where ductility is peaked. The underlying mechanism
taneously and continuously adjusting the current density
for such an optimization is also discussed in this work.
(10e100 mA/cm2) and additive content (1e5 g/L) during deposi-
tion. In addition, their changing rates were modified to control the
2. Experimental degree of gradient. Fig. 2b shows a schematic diagram where the
output current and additive content continuously change with the
2.1. The degree of gradient deposition time, contributing to a continuous refinement of the
grain size along the deposition direction.
Fig. 1a shows a schematic diagram of a number of grain size Ni deposits having six different profiles of gradient structure
variations as a function of position along the deposition direction. were designed and synthesized with a thickness up to 2 mm
The maximum and minimum grain sizes, dmax and dmin, are kept the through a conventional rotating disc electrode set-up. The plating
same among different cases, while the distributions of grain size are bath was a modified Watts-type electrolyte containing nickel sul-
quite different. For example, the transition in the grain size of fate (300 g/L), nickel chloride (45 g/L), boric acid (40 g/L) and
gradient A is gentler (Fig. 1b), resulting in a larger volume fraction dodecyl sodium sulfate (0.05 g/L), maintained at pH value of
of fine grains (i.e. hard phases). On the other hand, gradient C has a 4.0 ± 0.2 and temperature of 328 ± 1 K. Monolithic CG and nano-
steeper change in grain size and a smaller volume fraction of fine grained (NG) Ni samples were also prepared by electrodeposition
grains (Fig. 1b). Here, we employ a power law equation to charac- for comparison.
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: 2.3. Elemental analysis and microstructure characterization
d ¼ dmax ðdmax dmin Þð1 xÞn (1) The contents of nitrogen, hydrogen, oxygen, carbon and sulfur in
the GS Ni deposits were assessed by gas analysis (TCH-600
where n is the power index for the grain size distribution, which Hydrogen/Nitrogen/Oxygen Analyzer) and IR absorption method
can be considered as the degree of the gradient and the (CS844 Carbon & Sulfur Determinator). The content of light
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.
Y. Lin et al. / Acta Materialia 153 (2018) 279e289 281
2.5. MD simulations
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 consistent with those obtained from monolithic NG and CG Ni
to 5 in sample VI (Table 1). samples. Similar to the grain size gradient, hardness also exhibits
Grain sizes below 1 mm along the deposition direction in sample distinct gradient profiles for various GS samples. The change in
II were further confirmed by TEM. With an increase in the hardness is much slower in samples II and III than in samples V and
normalized distance from 0.05 to 0.76, the average grain size VI.
gradually increases from about 35 to 224 nm (Fig. 5a). Equiaxed Fig. 7a displays engineering stress-strain curves of the GS Ni
nano-grains were found at normalized distances of 0.05 and 0.58 samples under uniaxial tension at room temperature. For com-
(Fig. 5b and c), while elongated columnar grains appeared at parison, the data obtained from CG (4 mm) and NG (29 nm) Ni
normalized distance of 0.76 (Fig. 5d). The average grain sizes ob- samples are also included. The yield strength (0.2% offset, sy),
tained by TEM are consistent with those calculated by XRD. uniform elongation (εue) and ultimate tensile strength (sUTS) of each
specimen are listed in Table 1. As expected, both strength and
3.2. Mechanical properties of GS Ni samples ductility are strongly dependent on the degree of gradient. From
samples I to VI, sy decreases monotonously from 880 to 409 MPa
Fig. 6 presents the microhardness profiles of various GS Ni with n increasing from 0.01 to 5. More interestingly, εue first in-
samples. The microhardness continuously decreases from a creases from 4.5% in sample I to 8.9% in sample V, and then de-
maximum value of ~5.4 GPa to the minimum value of ~2.5 GPa as creases to 8.0% in sample VI. A maximum uniform elongation is
the normalized distance shifts from 0 to 1. These values are 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
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.
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).
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 shown in Fig. 11b, where plastic deformation is governed by dis-
deformation is governed by grain boundary associated activities, locations emitted from triple junctions and free surfaces. Large
including grain boundary sliding, grain rotation and grain coales- values of atomic shear strain occur mainly in a few inclined slip
cence. Fig. 11a shows that plastic deformation is localized along a bands, indicating highly localized plastic deformation in the
few planes forming inclination angles of roughly 45 with respect sample.
to the loading axis, which can be attributed to the fact that the In contrast, the deformation patterns of the gradient nano-
driving force for grain boundary sliding, which is the resolved shear structured Ni sample (Fig. 11c) displays several distinct features
stress on the grain boundaries, reaches its maximum value on these compared with those shown in Fig. 11a and b: (1) Shear localization
planes. The result for the sample with d ¼ 100 nm at strain 20% is 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.
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 material in nacre and bone e perspectives on de novo biomimetic materials,
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