Journal of Alloys and Compounds 854 (2021) 157174

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Synergistic effect of Nb and Zr additions on the structure-property

relationships of nanocrystalline Cu processed by mechanical alloying
and hot pressing
D. Roy a, *, S. Chakraborty b, A.K. Gupta a, A. BasuMallick c, R.O. Scattergood d,
Carl C. Koch d
a
Department of Materials and Metallurgical Engineering, NIFFT, Ranchi, 834003, India
b
School of Materials Science and Engineering, IIEST, Shibpur, Howrah, 711103, India
c
Department of Metallurgy and Materials Engineering, IIEST, Shibpur, Howrah, 711103, India
d
Department of Materials Science and Engineering, NCSU, Raleigh, NC, 27606, USA

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

Article history: In the present study, bulk nanocrystallineCu99.5Zr0.5, Cu99Nb1.0, and Cu98.5Zr0.5Nb1.0alloys have been
Received 5 July 2020 synthesized by using mechanical alloying followed by hot pressing (HP) at 550
C. Further, these as-
Received in revised form fabricated alloys were annealed at 800
C and 900
C for 1 h to investigate the structure-property cor-
26 August 2020
relation. Grain size and phase identification has been carried out using X-ray diffraction (XRD) and
Accepted 11 September 2020
transmission electron microscopy (TEM). While mechanical properties were investigated using Vickers
hardness and shear punch test (SPT). The grain size of the as-processed alloys was found to remain
Keywords:
nanosized 41 ± 2.2 nm in Cu99.5Zr0.5(CZ), 50 ± 1.5 nm in Cu99Nb1.0(CN) and 26 ± 1.2 nm in Cu98.5Zr0.5Nb1.0
X-ray diffraction (XRD)
Transmission electron microscopy (TEM)
(CNZ) even after annealing at 900
C. This is attributed to the stabilization of the nanosize grains by
Shear punch test (SPT) segregation of solute atoms (Nb and Zr) along grain boundaries and/or Zenner pinning by intermetallic
precipitates like Cu5Zr in CZ and CNZ alloys.
© 2020 Elsevier B.V. All rights reserved.

1. Introduction commercial applications. Therefore, the thermal stability of NC-Cu

Nanocrystalline (NC) materials possess improved strength, 2 to
10 times over the coarse-grain counterpart [1,2]. Mechanical
alloying (MA) is an efficient and well-established way to produce
NC alloys, and when milling is performed at cryogenic tempera-
tures (~77 K), the processing time is lowered substantially [3].
Mechanical alloying of powder blend/or alloy powder involves
energization of powder blend, which eases the formation of non-
equilibrium phases [4]. However, these powder NC-materials
tend to exhibit grain growth at the high working temperatures in
most of the consolidation processes [5]. Experimental results have
revealed that many elemental nano-sized powders such as Mg, Cu,
Sn, Pb show significant coarsening even at room temperature [6,7].
The superior mechanical, electrical, and wear resistance properties
are thus lost when these NC-grains revert to coarser grain size. This
tendency for grain growth becomes a substantial hindrance to
alloys is of prime concern in preserving the excellent mechanical
and physical properties [8,9].
To advance the commercial viability of stabilization of these NC-
materials, understanding their microstructural stabilization at
elevated temperatures is highly desirable. Existing work suggests
two methods through which these NC-materials could be stabi-
lized, viz., thermodynamic and kinetic stabilization. The thermo-
dynamic stabilization involves lowering the grain boundary
energies and therefore the driving force for grain growth [10,11],
while kinetic stabilization restricts grain boundary mobility by a
particle (Zener) pinning or solute drag [12e14]. Thermodynamic
stabilization is reported in Fe-Zr [15], and CueNb [16], etc. while
kinetic stabilization is observed in CueW [17,18], Cu-Zr [19] sys-
tems. Thermodynamic stabilization is reportedly achieved by the
addition of oversize solute atom, which lowers the grain boundary
energy upon segregation [20,21]. It may be also possible that these

* Corresponding author.
E-mail address: droy2k6@gmail.com (D. Roy).

https://doi.org/10.1016/j.jallcom.2020.157174
0925-8388/© 2020 Elsevier B.V. All rights reserved.
D. Roy, S. Chakraborty, A.K. Gupta et al.
solute atoms form precipitates at a higher temperature and offer
additional stabilization via Zenner pinning. In this context, Sikdar
et al. [22] reported the formation of nano-precipitates of Cu5Zr in
CueZr system.
Similarly, Chen et al. [23] demonstrated that the thermal sta-
bility of the NC-Fe-Zr alloy arises due to the contribution from both
kinetic and thermodynamic stabilization. In the past, hybrid ther-
mal stabilities (combined effect of both mechanisms) were also
investigated in CueY [24] and CueTa systems [25] and in our
previous study [26], we demonstrated the contribution of a syn-
ergistic effect of Nb and Zr responsible for providing superior
thermal stability in (CueNbeZr) alloy system. The alloy
Cu98.5Zr0.5Nb1.0 (CNZ) indeed exhibits high resistance to grain
coarsening at elevated temperatures. In the present work, an
experimental investigation on the mechanical performance of the
thermally stabilized CueNbeZr is performed. The artifact-free bulk
NC-alloys of Cu99.5Zr0.5(CZ), Cu99Nb1.0(CN), and Cu98.5Zr0.5Nb1.0
(CNZ) were prepared via MA followed by hot pressing (HP) and
were further annealed at 800
C and 900
C. The effect of the
thermal stability of the bulk NC-alloys was investigated through
XRD and TEM, while overall mechanical performance was evalu-
ated through Vickers hardness and shear punch tests.
2. Experimental procedure
The elemental powders blended in appropriate quantities for
Fig. 1. (a, b, and c) shows XRD pattern, while (d) shows grain size variation for Cu99.5Zr0.5, Cu99Nb1.0 and Cu98.5Zr0.5Nb1.0 after hot pressing and annealed at different temperature.
2
Journal of Alloys and Compounds 854 (2021) 157174
desired alloy compositions were subjected to ball milling under
cryogenic condition (196
C) in a modified Spex 8000 mixer. In
the present study, the cryo-milled powder with the composition of
Cu-0.5 at% Zr, Cu-1.0 at% Nb and Cu- 0.5 at% Zr-1.0 at% Nb were
compacted in a cylinder (10 mm dia) tool steel die under a uniaxial
loading of 2 GPa in a hot press (Fritsch Postfech-500428, Germany)
at 550
C. The load on the sample was applied for 45 min until the
desired temperature was attained and then allowed to cool to room
temperature. Finally, the samples were stripped from the die for
further annealing treatment at different temperatures for 1 h and
characterization.
The phases present in the compacted samples were examined
by recording the XRD patterns in a Rigaku DMax diffractometer
with a Cu Ka (l ¼ 0.15405 nm) source. Scans were performed with a
scanning angle (2q) from 20
to 100
. Background correction and
removal of Cu Ka2 was optimized by Xpowder software (http://
www.xpowder.com).
Transmission electron microscopy (TEM) was carried out in JEOL
JEM 2000FX, beam energy of 200 keV. The TEM samples were
prepared via a conventional thinning process followed by electro-
polishing (Tenupol 2) in a composition mixture of 30 vol % nitric
acid and methanol at 20
C.
The mechanical properties of the hot-pressed compact and after
the annealing treatments were investigated by using Vickers
micro-hardness and shear punch tests (SPT). Micro-hardness
measurements were carried out using Buehler MicrometII
D. Roy, S. Chakraborty, A.K. Gupta et al.
hardness tester, at 25 g load, and dwell time of 12 s on polished
alloy samples of 3 mm thickness. At least 15 indentations were
recorded for each condition and then averaged to get the average
hardness value. The corresponding standard deviation was also
calculated for the comparison. A detailed description of the SPT
procedure is described elsewhere [27]. A punch
(dpunch ¼ 0.99568 mm) and die (ddie ¼ 1.016 mm) were used for the
shear punch test. The clearance between the punch and die was
10.16 mm for shear loading, and the punch speed was maintained at
0.24 mm/s. SPT samples were ~100 mm thick, and the surface was
ground with 3000 grit polishing paper followed by cloth polishing
with 0.1micron alumina slurry. In the study, stress (MPa) vs.
displacement was recorded. To investigate the morphological
deformation via SPT, scanning electron microscopic (JEOL JEM
6010LA) investigation was performed using 20 keV beam energy.
3. Results and discussion
The XRD pattern for the bulk NC-alloys, namely: CZ, CN, and
CNZ, respectively, processed via hot pressing (HP) and further
annealing at 800
C and 900
C is shown in Fig. 1. Fig. 1(a, b, and c)
shows only Cu-fcc peaks, while no reflections from the bcc struc-
ture of Nb and hcp structure of Zr was observed. It is to be noted
that under equilibrium conditions, both Nb and Zr are immiscible in
Cu [28,29]. However, the absence of reflections from the Nb and Zr
indicates that both elements possibly have formed a solid solution
in Cu under the prevailing non-equilibrium processing condition.
Furthermore, in Fig. 1(a, b and c), a shift in of (111) peak towards
higher Bragg angle is seen with the increase in annealing temper-
ature. The peak shift towards higher angle with the increase in
annealing temperature indicates a reduction of lattice parameters,
which probably arise due to the rejection of solute atoms from the
metastable solid solution of Cu. The corrected breadth of XRD peaks
was used to determine the grain size of the NC- alloys using the
Williamson- Hall method [30]. The variation of grain size is shown
in Fig. 1d. The grain size in the CZ, CN, and CNZ alloys was still found
to remain nano-dimensional, measuring 41 ± 2.2 nm, 50 ± 1.5 nm,
and 26 ± 1.2 nm, respectively, even after annealing at 900
C. It
shows that the grain size of the NC-alloys remains stable compared
to the grain size of NC-pure Cu [19].
It is known that though the XRD pattern exhibit signature peaks
as evidence for the presence of second phase/intermetallic phase
or/phase transformation, but becomes ineffective when these
phases/aggregates present in low volume fraction, beyond the
Fig. 2. (a and b) are TEM images for Cu99.5Zr0.5(CZ) before and after annealing, respectively.
3
Journal of Alloys and Compounds 854 (2021) 157174
detection limit of XRD [19,31]. Thus for more in-depth investiga-
tion, TEM is used for examining microstructures of NC-alloys.
Fig. 2 depicts the TEM analysis of the CZ alloy. Fig. 2 (a) shows
the grain morphology after HP, while Fig. 2 (b) shows the grain
morphology after annealing at 900
C. The inset of Fig. 2 (a) and 2
(b) depicts the selected area diffraction (SAD) pattern for the cor-
responding conditions. The TEM microstructure and the corre-
sponding ring patterns of the SAD, confirms that grain sizes in CZ
alloys are in the nanometric length scale. The average grain size was
ascertained by using ImageJ software analysis over the dark field
TEM images. The grain size after annealing was estimated as
~42 nm and the frequency distribution is shown in the inset of
Fig. 2b. The average grain size is in close approximation, as calcu-
lated from XRD analysis. In the XRD analysis (refer Fig. 1a), although
there is no evidence of precipitation of the intermetallic phase, but
in TEM analysis, fine precipitation of Cu5Zr is evidenced in the SAD
pattern shown in Fig. 2b, which has been also been reported else-
where [22,26].
Fig. 3 shows the TEM images of the alloy CN. Fig. 3 (a) and 3 (b)
show the respective microstructure of the samples after HP and
after annealing at 900
C. The inset of Fig. 3a and b depicts the
corresponding SAD pattern for the same. The SAD pattern shows
the presence of ring patterns of the nanocrystalline grains. The
average grain size measured from the microstructure of the
annealed sample with the aid of imageJ software is ~48 nm. The
inset of Fig. 3b shows the frequency distribution of the grain size,
which is close to the value estimated from the XRD pattern. The
SAD pattern (shown in Fig. 3a) indicates the formation of a super-
saturated solid solution of Nb in the Cu matrix in Cu during cryo-
genic attrition, as the Nb ring pattern is missing. This result is
consistent with the results obtained by Botcharova et al. [9,32],
where the formation of a 10% supersaturated solid solution by
mechanical milling is reported. Examination of the SAD pattern
shown in Fig. 3b, as opposed to the SAD pattern shown in Fig. 3a,
the ring pattern of Nb (110) is distinctively visible; the appearance
of Nb (110) ring arises due to the segregation of Nb during
annealing of CN alloy. For further confirmation, we performed
scanning transmission electron microscopy (STEM) imaging for the
same alloy. The segregation of Nb could be explicitly seen in Fig. 3
(c), which is nearly 15e18 nm in size. The segregation of large size
solute atoms such as Nb requires high thermal energy [33], which
seems to be favored by 1 h of annealing treatment at 900
C.
Similarly, Fig. 4 (a) shows the TEM images of the CNZ alloy after
HP, while Fig. 4 (b) shows the microstructure after 1 h annealing at
D. Roy, S. Chakraborty, A.K. Gupta et al. Journal of Alloys and Compounds 854 (2021) 157174

Fig. 3. (a and b) are TEM images for Cu99Nb1.0(CN) before and after annealing, respectively; (c) segregation of Nb.

Fig. 4. (a and b) are TEM images for Cu98.5Zr0.5Nb1.0 (CNZ) after hot pressing and annealed at a different temperature, respectively; (c) shows precipitation of Cu5Zr.

900
C. The inset of Fig. 4a and b depict the SAD pattern for the synergistic stabilization of NC-grains occurs, via a combined effect
same. Analysis of SAD patterns (Fig. 4a) indicates that the cryogenic of grain boundary pinning and consequent lowering of grain
attrition process is quite effective and successful in producing a boundary mobility. This effect attributes for superior thermal sta-
supersaturated solid solution of Zr and Nb, as their characteristic bilization of the NC- grains in CNZ alloy even after a long annealing
reflections are absent. However, in Fig. 4 (b), the SAD pattern clearly period.
shows the characteristic ring pattern, which corresponds to the Fig. 6 (a and b) shows the variation of shear stress versus
(110) plane of Nb. Distinct diffraction spots of intermetallic Cu5Zr is displacement for HP samples and after 1 h annealing at 900
C, for
also visible. Thus, we conclude that the ring pattern of Nb arises due the CZ, CN, and CNZ alloy. The shear punch tests in the samples
to the occurrence of nanoscale precipitation of Nb from the su- were performed till their failure. A more detailed description of the
persaturated solid solution, and the diffraction spots of Cu5Zr arise shear punch test is provided by Guduru et al. [27, 34, 35]. In Fig. 6, a
due to their existence as single crystals in the Cu matrix. Further- sharp decrease in shear stress after a critical point is observed in the
more, Fig. 4 (c) reveals the presence of Cu5Zr precipitates in the size
range of ~3e5 nm.
Mechanical properties of the as processed NC-alloys were
studied through Vickers hardness measurement and shear punch
test. Fig. 5a shows the variation of hardness after HP and after 1 h
annealing at 800
C and 900
C. The inset of Fig. 5b shows the
variation of hardness with the annealing temperature of pure
milled nanocrystalline copper [19]. The hardness of the HP alloys is
assigned to the cumulative effect of solid solution and Hall-Petch
strengthening due to smaller grain sizes. It can be also seen that
as the percentage of solute atoms is increased, the hardness also
increases, which is due to the solid solution strengthening effect.
Annealing tends to coarsen the grains, resulting in the decrease of
hardness. However, a gradual reduction in hardness is seen in all
the samples after annealing at 800
C, but a sharp fall in hardness is
observed after the samples were annealed at 900
C. In CN alloy, the
decrease in the hardness value is conspicuously higher compared to
the CZ and CNZ alloys. This has happened because the NC-grains of
the CN alloys are stabilized by the solute drag and Zenner pinning
effect of the precipitated Nb particles, while in CZ, the NC-grains are
thermally stabilized by fine intermetallic phase (Cu5Zr) particu-
lates, leading to Zenner stabilization. Thus it is inferred that nano-
precipitate stabilization (as in case of CZ alloy) is superior to the Fig. 5. (a) variation of hardness with hot pressing and annealing temperature for
segregation and precipitation of Nb particles. In the alloy, CNZ, a Cu99.5Zr0.5, Cu99Nb1.0, and Cu98.5Zr0.5Nb1.0 and inset (b) shows the variation of hardness
with an annealing temperature of pure milled Nanocrystalline copper.

4
D. Roy, S. Chakraborty, A.K. Gupta et al. Journal of Alloys and Compounds 854 (2021) 157174

Fig. 6. (a, b) Variation of Shear stress (MPa) vs. displacement variation for CZ, CN, and CNZ at HP and annealing at 900
C, respectively.

hot pressed samples, which has arisen due to the formation and
rapid propagation of cracks. In contrast, the annealed samples show
that the shear stresses remain nearly constant prior to their failure,
which can be attributed to the improved plastic deformability
achieved by annealing, which possibly lead to blunting the crack
tips and eventually arrest propagation of cracks in the sample.
The stress vs. displacement plot for HP condition (Fig. 6 a) shows
lower plasticity as compared to the annealed samples (as shown in
Fig. 6b), the maximum strength in the hot-pressed samples is found
in the CNZ alloy followed by CN and CZ alloy respectively. The
reason for this behavior is attributed to the solid solution
strengthening, as because the HPed samples, irrespective of the
alloy composition, possess nearly similar grain size distribution.
Thus the result could be explicitly expressed.

Fig. 7. Fracture Surface of CZ, CN, and CNZ after shear punch test (SPT) after HP-550
C.

5
D. Roy, S. Chakraborty, A.K. Gupta et al.
Fig. 8. Fracture Surface of CZ, CN, and CNZ after shear punch test (SPT) after HP-550
C and annealing at 900
C.
However, the results of the annealed samples are governed by
the kinetic and thermal stabilization of grain boundaries. All alloys
in the annealed condition, show higher plasticity. In the CZ alloy,
since nano-sized Cu5Zr precipitates are homogeneously distributed
in the matrix, it confers higher strength property in the alloy.
Similarly, in CN alloy, fine precipitation of Nb contributes signifi-
cantly in terms of increasing strength as compared to the segre-
gation of solute atoms. Hence, a similar trend has been noticed in
both CZ and CN alloy after annealing. Further, in CNZ alloy, as the
synergistic effect of precipitation of Cu5Zr and segregation of Nb
particles is active, it leads to the superior strength of CNZ alloy, and
also causes stabilization of NC-grain boundaries. Herein, it would
be worth mentioning that the radius of Zr atom is larger than Nb
and Cu atoms. Therefore, when Zr atoms are incorporated in the Cu
lattice forming solid solution under the nonequilibrium condition,
the magnitude of lattice strain in Cu is much higher than lattice
strain in the solid solution of Nb in Cu. However, in the case of CNZ
alloy, since the atom percent of Nb is twice than that of Zr, it is quite
probable that Nb atoms would preferentially occupy more number
of lattice sites in Cu than Zr, rendering them to be less brittle than
the CZ alloy. Thus, we infer that the CZ alloy is more brittle
compared to CN and CNZ alloys.
Furthermore, it is to be noted that the shear punch test for all the
samples were performed under identical conditions, however, in
6
Journal of Alloys and Compounds 854 (2021) 157174
the hot pressed CZ alloys, the non-uniform nature of elastic loading
observed (Fig. 6a) is associated with its tendency to fracture at
comparatively low shear load leading to free slip movements of the
punch head in the early stages affecting the total displacement. The
corresponding fractographic image of the surface presented later
(Fig. 7a), clearly show that the crack length and the size of the
fragments are larger and there are lesser deviations in the crack
propagation path compared to other alloys. These features confirm
that cracks form and propagate rapidly leading to fracture in the
early stages of shear loading.
Fig. 7 (a-f) shows SEM micrograph for the CZ, CN, and CNZ alloys,
respectively, after performing the shear punch test on the HPed
samples. Fig. 7 (b, d, and e) shows the shear morphology for the
corresponding alloys. As we have mentioned above, the alloys show
low plasticity; numerous cracks are formed in the alloys, as
revealed in Fig. 7 (a, c, and e). Further, if we compare the cracks
among the alloys, CNZ exhibits maximum resistance for crack
propagation, as fewer cracks are formed (Fig. 7 e).
Similarly, Fig. 8 shows SEM morphology for the CZ, CN, and CNZ
alloys after annealing at 900
C. Fig. 8 (b, d, and e) shows shear
morphology for the corresponding alloys. The alloys show signifi-
cant resistance to crack formation and propagation due to ap-
pearances of a lesser number of cracks. Furthermore, among the
alloys, CNZ shows superior morphology of the punched out disk.
D. Roy, S. Chakraborty, A.K. Gupta et al.
The magnified view of the crack morphology is shown in Fig. 8 (b, d,
and e), which reveal shear band formation and plastically deformed
morphology in all the alloys signifying ductile failure. Thus, the
SEM micrographs also indicate the achievement of higher plasticity
after annealing, which is in agreement with the results obtained
from the shear stress versus displacement plots.
4. Conclusions
In Summary, bulk nanocrystalline Cu99.5Zr0.5(CZ), Cu99Nb1.0(CN),
and Cu98.5Zr0.5Nb1.0 (CNZ) alloys were synthesized by performing
8 h cryo-milling elemental Cu, Zr and Nb powder blends of
appropriate quantity. The milled alloy powders were consolidated
by hot pressing at 550
C. The stability of Cu99.5Zr0.5(CZ),
Cu99Nb1.0(CN), and Cu98.5Zr0.5Nb1.0 (CNZ) is confirmed by the TEM
investigations. Addition of 0.5 at.% Zr and 1.0 at. % Nb in Cu restricts
grain growth and stabilizes the NC grain boundaries to 26 ± 1.2 nm
even after annealing at 900
C. The superior thermal stabilization in
Cu98.5Zr0.5Nb1.0 alloy was attributed to the synergistic effect of
thermal stabilization by solute segregation and Zenner pinning. The
mechanical properties evaluated through the hardness test and
novel shear punch test show that annealing the specimens, leads to
enhancement of ductility due to the removal of stresses, which
have accumulated during the ball milling. The interplay of the
synergistic effect of solute segregation and Zenner pinning confer
superior mechanical property in these novel NC- materials.
CRediT authorship contribution statement
D. Roy: Experiments, Writing - original draft. S. Chakraborty:
Experiments, Writing - review & editing. A.K. Gupta: Character-
ization of samples. A. BasuMallick: Resources, Supervision. R.O.
Scattergood: Writing - review & editing. Carl C. Koch: Supervision,
Writing - review & editing.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
References
[1] C.C. Koch, K.M. Youssef, R.O. Scattergood, K.L. Murty, Breakthroughs in opti-
mizationof mechanical properties of nanostructured metals and alloys, Adv.
Eng. Mater. 7 (2005) 787e794.
[2] K.M. Youssef, R.O. Scattergood, K.L. Murty, J.A. Horton, C.C. Koch, Appl. Phys.
Lett. 87 (2005) 1.
[3] D.B. Witkin, E.J. Lavernia, Synthesis and mechanical behavior of nano-
structured materials via cryomilling, Prog. Mater. Sci. 51 (2006) 1e60.
[4] C. Suryanarayana, Mechanical alloying and milling, Prog. Mater. Sci. 46 (2001)
1e184.
[5] SomrajChakravarty, et al., “Stabilization of nanocrystalline Cu by Al addition”,
materials characterization”, June 128 (2017) 189e194.
[6] J. Weissmuller, J. Loffler, M. Kleber, Nanostruct. Mater 6 (1995) 105e114.
[7] B. Gunther, A. Kumpmann, H.D. Kunze, Scripta Metall. Mater. 27 (1992)
833e842.
[8] N. Takata, S.H. Lee, N. Tsuji, Ultrafine grained copper alloy sheets having both
Journal of Alloys and Compounds 854 (2021) 157174
high strength and high electric conductivity, Mater. Lett. 63 (2009)
1757e1760.
[9] E. Botcharova, J. Freudenberger, L. Schultz, Mechanical and electrical proper-
ties of mechanically alloyed nanocrystalline CueNb alloys, Acta Mater. 54
(2006) 3333e3341.
[10] J. Weissmuller, W. Krauss, T. Haubold, R. Birringer, H. Gleiter, Nanostruct.
Mater. 1 (1992) 439e447.
[11] E.D. Hondros, M.P. Seah, in: third ed., in: R.W. Cahn, P. Haasen (Eds.), Physical
Metallurgy, Elsevier, Amsterdam, 1983, pp. 856e931.
[12] H.J. Hofler, R.S. Averback, Scripta Metall. Mater. 24 (1990) 2401e2406.
[13] R.J. Perez, B. Huang, A.A. Sharif, E.J. Lavernia, in: D.L. Bourell (Ed.), Synthesi-
sand Processing of Nanocrystalline Powder, TMS, Warren Dale, PA, 1996,
pp. 273e280.
[14] P. Knauth, A. Charai, P. Gas, Scr. Metall. Mater 5 (1995) 327e336.
[15] A. Kris, Darling, N. Ryan, Chan, Z. Patrick, Wong, Jonathan E. Semones, Ronald
O. Scattergood, Carl C. Koch, Grain-size stabilization in nanocrystallineFeZr
alloys, Scripta Mater. 59 (2008) 530e533.
[16] H. Bahmanpour MulaSuhrit, S. Mal, P.C. Kang, M. Atwater, W. Jian,
R.O. Scattergood, Carl C. Koch, Thermodynamic feasibility of solid solubility
extension of Nb in Cu and their thermal stability, Mater. Sci. Eng. A 539 (2012)
330e336.
[17] Mark A. Atwater, Debdas Roy, Kristopher A. Darling, Brady G. Butler,
RonaldO. Scattergood, Carl C. Koch, The thermal stability of nanocrystalline
copper cryogenically milled with tungsten, Mater. Sci. Eng., A 558 (2012)
226e233.
[18] S. Chakraborty, A.K. Gupta, D. Roy, A. Basumallick, Studies on nano-metal
dispersed Cu-Cr matrix composite, Materials Letters 257 (2019) 126739.
[19] A. Mark, Atwater, Ronald O. Scattergood, Carl C. Koch, The stabilization
ofnanocrystalline copper by zirconium, Mater. Sci. Eng., A 559 (2013)
250e256.
[20] G.L. Hankin, M.B. Toloczko, M.L. Hamilton, F.A. Garner, R.G. Faulkner, J. Nucl.
Mater. (1998) 258e263, 1657e1663.
[21] M.B. Toloczko, M.L. Hamilton, G.E. Lucas, J. Nucl. Mater. 283e287 (2000)
987e991.
[22] K. Sikdar, et al., Hybrid thermal stabilization of Zr doped nanocrystalline Cu,
Mater. Des. 164 (2019) 107564, https://doi.org/10.1016/j.matdes.2018.107564.
[23] Y.Z. Chen, K. Wang, G.B. Shan, A.V. Ceguerra, L.K. Huang, H. Dong, L.F. Cao,
S.P. Ringer, F. Liu, Grain size stabilization of mechanically alloyed nano-
crystalline Fe-Zralloys by forming highly dispersed coherent Fe -Zr-O nano-
clusters, Acta Mater. 158 (2018) 340e353.
[24] Suhrit Mula, Daria Setman, Khaled Youssef, R.O. Scattergood, Carl C. Koch,
Structural evolution of Cu(1  X)YX alloys prepared by mechanical alloying:
their thermal stability and mechanical properties, J. Alloys Compd 627 (2015)
108e116.
[25] K.A. Darling, A.J. Roberts, Y. Mishin, S.N. Mathaudhu, L.J. Kecskes, Grain size
stabilization of nanocrystalline copper at high temperatures by alloying with
tantalum, J. Alloys Compd. 573 (2013) 142e150.
[26] D. Roy, S. Chakraborty, A.K. Gupta, A. BasuMallick, Carl C. Koch, Synergistic
effect of Nb and Zr addition in thermal stabilization of nanocrystalline Cu
synthesized by ball milling, Mater. Lett. 271 (2020) 127780.
[27] R.K. Guduru, K.A. Darling, R. Kishore, R.O. Scattergood, C.C. Koch, K.L. Murty,
Mater. Sci. Eng. A 395 (2005) 307e314.
[28] M. Ames, J. Markmann, R. Karos, A. Michels, A. Tscho € pe, R. Birringer, Acta
Mater. 56 (2008) 4255e4266.
[29] K.M. Youssefa, M.A. Abazaa, R.O. Scattergood, C.C. Koch, Mater. Sci. Eng., A 711
(2018) 350e355.
[30] N. Khobragade, K. Sikdar, B. Kumar, S. Bera, D. Roy, J. Alloys Compd. 776
(2019) 123e132.
[31] D. Roy, M.A. Atwater, K. Youssef, J.C. Ledford, R.O. Scattergood, C.C. Koch,
J. Alloys Compd. 558 (2013) 44e49.
[32] E. Botcharova, M. Heilmaier, A. Freudenberger, G. Drew, D. Kudashow,
U. Martin, L. Schultz, J. Alloys Compd. 351 (2003) 119e125.
[33] Mohamed A. Abaza, Leena Al-Sulaiti, Ronald O. Scattergood, Khaled
M. Youssef, Influence of 1%Nb solute addition on the thermal stability of in
situ consolidated nanocrystalline Cu, Adv. Eng. Mater. vol. 1 (2019) 6,
1800859.
[34] R.K. Guduru, K.L. Murty, K.M. Youssef, R.O. Scattergood, C.C. Koch, Mater. Sci.
Eng. A 463 (2007) 14e21.
[35] R.K. Guduru, A.V. Nagasekhar, R.O. Scattergood, C.C. Koch, K.L. Murty, Metall.
Mater. Trans. 37A (2006) 1477e1483.