materials

Article
Dissolution of Ag Precipitates in the Cu–8wt.%Ag
Alloy Deformed by High Pressure Torsion
Anna Korneva 1, *, Boris Straumal 2,3,4 , Askar Kilmametov 2,3 , Robert Chulist 1 ,
Grzegorz Cios 5 , Brigitte Baretzky 3 and Paweł Zi˛eba 1
1 Institute of Metallurgy and Materials Science, Polish Academy of Sciences, 25 Reymonta Street,
30-059 Krakow, Poland; [email protected] (R.C.); [email protected] (P.Z.)
2 Institute of Solid State Physics and Scientific Center of RAS, Russian Academy of Sciences, Ac. OssipyanStr.
2, 142432 Chernogolovka, Russia; [email protected] (B.S.); [email protected] (A.K.)
3 Karlsruhe Institute of Technology (KIT), Institute of Nanotechnology, Hermann-von-Helmholtz-Platz 1,
76344 Eggenstein-Leopoldshafen, Germany; [email protected]
4 National University of Science and Technology «MISIS», Leniskijprosp. 4, 119049 Moscow, Russia
5 AGH University of Science and Technology, Academic Centre for Materials and Nanotechnology,
30 Mickiewicza Av, 30-059 Krakow, Poland; [email protected]
* Correspondence: [email protected]; Tel.: +48-12-295-2867




Received: 10 January 2019; Accepted: 29 January 2019; Published: 1 February 2019


Abstract: The aim of this work was to study the influence of severe plastic deformation (SPD) on the
dissolution of silver particles in Cu–8wt.%Ag alloys. In order to obtain different morphologies of silver
particles, samples were annealed at 400, 500 and 600 ◦ C. Subsequently, the material was subjected to
high pressure torsion (HPT) at room temperature. By means of scanning and transmission electron
microscopy, as well as X-ray diffraction techniques, it was found that during SPD, the dissolution
of second phase was strongly affected by the morphology and volume fraction of the precipitates
in the initial state. Small, heterogeneous precipitates of irregular shape dissolved more easily than
those of large size, round-shaped and uniform composition. It was also found that HPT led to the
increase of solubility limit of silver in the copper matrix as the result of dissolution of the second
phase. This unusual phase transition is discussed with respect to diffusion activation energy and
mixing enthalpy of the alloying elements.

Keywords: Cu–Ag alloy; high-pressure torsion; ultrafine microstructure; phase dissolution;

microhardness

1. Introduction
Over the last decade, Cu–Ag alloys have attracted attention due to their high strength and high
conductivity [1–3]. The mechanical and electrical properties of these alloys with low Ag content
mainly depend on the volume fraction and distribution of Ag precipitates. Small Ag precipitates act
as obstacles against the dislocation movement, increasing both strength and conductivity when Ag
is extracted from the Cu matrix. It was found that applying cold drawing to the Cu–6wt.%Ag alloy
resulted in a significant increase of strengthening effect from Ag precipitates (from 100 to 560 MPa) at
the drawing strain equal to 6 [3]. In this process, fine Ag precipitates are produced which are elongated
and evolve into filamentary structure along the drawing direction. It can be assumed that applying
severe plastic deformation (SPD) with higher strain should further increase the strength of the material
conserving its high conductivity.
It is well known that SPD allows producing bulk ultra-fine-grained materials with extraordinary
mechanical properties, such as exceptionally high strength with considerable ductility at room
temperatures or large super-plasticity at elevated temperatures [4–6]. Recently, it has been shown

Materials 2019, 12, 447; doi:10.3390/ma12030447 www.mdpi.com/journal/materials

Materials 2019, 12, 447 2 of 12

that the presence of the second phase (precipitates) additionally influences the grain refinement when
the material is subjected to SPD [7,8]. This effect depends on morphology of the second phase (size,
volume fraction, distribution). For instance, it has been shown in [8] that an extensive grain refinement
of the Al–5.4%Mg–0.5%Mn–0.1%Zr alloy under equal-channel angular pressing (ECAP) was facilitated
by a dispersion of Al6 Mn particles with an average size of 25 nm. They precipitated during the
homogenization annealing at intermediate temperature. On the contrary, the formation of coarse
recrystallized grains took place in this material after ECAP, when coarse Al6 Mn particles with a
plate-like shape were present in the initial state. On the other hand, the second phase is also affected
by SPD, because SPD frequently induces phase transformations [9–11]. For example, some phases
precipitate or dissolve after SPD at room temperature [12–14], which usually should happen after heat
treatment at higher temperatures. W. Huang [15] reported that the dissolution of the second phase
occurring in SPD is an important phenomenon of phase transition. The dissolution of the second
phase induced by SPD also depends on distribution and morphology of the particles. The influence of
dissolved precipitated phases on the grain refinement and improvement of mechanical properties of
severely deformed materials was reported in [16,17], however there is no systematic research about the
effect of SPD on the behavior of particles, with respect to their morphology and properties. Therefore,
the aim of this work is to study the influence of high-pressure torsion (HPT) on dissolution of the
second phase and microhardness of the Cu–8wt.%Ag alloy characterized by different morphology of
Ag precipitates.

2. Materials and Methods

The Cu–8wt.%Ag alloy was manufactured by induction melting in vacuum from the high-purity
5N5 Cu and 4N5 Ag. The resulting ingots with the diameter of 10 mm were cut by means of spark
erosion into 0.7 mm thick disks. Three disks of the Cu–8wt.%Ag alloy were sealed separately into
quartz ampoules (HMB Quarzglass, Helmenhorst, Germany) with the residual pressure of 4 × 10−4 Pa
for annealing in a SUOL resistance furnace (Tula-Term, Tula, Russia) at 400 ◦ C (1200 h), 500 ◦ C (710 h)
and 600 ◦ C (86 h). After annealing, the samples were quenched in water (ampoules were broken).
Afterwards, discs were subjected to HPT in a Bridgman anvil chamber (W. Klement GmbH, Lang,
Austria) at a pressure of 5 GPa, five revolutions at the speed of 1 rpm at room temperature. In our
experiment three discs for each state were deformed and then examined with X-ray diffraction (XRD,
Siemens, München, Germany) technique. Since the obtained XRD-curves were identical for each
state, one deformed disc was used for further microstructural investigations using scanning electron
microscopy (SEM, FEI, Hillsboro, OR, USA) and transmission electron microscopy (TEM, TECNAI,
Hillsboro, OR, USA) techniques. The samples for the structure studies were cut at the distance of 3 mm
from the center of the deformed discs. For the metallographic investigations, the samples were ground
with SiC grinding paper, and sequentially polished with 6, 3 and 1 µm diamond pastes. The detailed
microstructure observation and electron backscatter diffraction (EBSD) analysis were carried out on a
FEI Quanta 3D FEGSEM scanning electron microscope (SEM, FEI, Hillsboro, OR, USA) equipped with
a field emission gun (FEG) and an energy-dispersive X-ray spectrometer (EDX) manufactured by EDAX
(Mahwah, NJ, USA). The SEM images were taken using backscattered electron signal (BSE mode) in
order to obtain the composition contrast between different phases. The EBSD maps combined with
element maps were carried out on a sample plane perpendicular to the normal direction. The working
voltage and current were set to 20 KV and 8 nA, respectively. The mappings were carried out in
the beam-scanning mode with a step size of 50 nm. Crystallographic and microstructural features
were analyzed with the TSL OIM software (version Analysis 7 EDAX, Mahwah, NJ, USA). In order to
visualize orientation maps the so-called inverse pole figure (IPF) color coding was used. The details
of the resulting microstructure components, especially in nanoscale, were revealed using a TECNAI
G2 FEG super TWIN (200 kV) transmission electron microscope (TEM, TECNAI, Hillsboro, OR, USA)
equipped with an energy dispersive X-ray (EDS) spectrometer manufactured by EDAX TECNAI
(Mahwah, NJ; USA). Thin foils of the alloy for TEM observation were prepared by a twin-jet polishing
 Materials 2019, 12, 447 3 of 12

Materials 2019, 12, x FOR PEER REVIEW 3 of 12

technique using D2 electrolyte of Struers company (Ballerup, Denmark) with parameters recommended
by the manufacturer.
obtained The X-raygeometry
in the Bragg–Brentano diffractiononpatterns
a Philipswere obtained
X’Pert powder indiffractometer
the Bragg–Brentano with thegeometry
use of
on a Philips
Cu-Kα X’Pert
radiation. powder
Lattice diffractometer
parameters with the use
were evaluated of Cu-Kα
by the radiation.[18]
Fityk software Lattice
usingparameters were
a Rietveld-like
evaluated by the Fityk software [18] using a Rietveld-like whole profile refinement.
whole profile refinement. Relative amounts of Cu- and Ag-rich solid solutions were estimated from Relative amounts
of Cu-
the and Ag-rich
integrated solid solutions
intensities. were estimated
Pure polycrystalline from
copper theused
was integrated intensities.
as reference. Pure polycrystalline
The phases in the alloys
copper
were was used
identified byascomparing
reference. with
The phases in the alloys were identified
the X’PertHighScorePANalytical by comparing
phase database [19]. withThethe
X’PertHighScorePANalytical phase database [19]. The hardness measurements
hardness measurements were performed using an G200 nanoindenter (KLA-Tencor, Milpitas, CA, were performed using
an G200
USA) withnanoindenter
XP head with(KLA-Tencor,
the indentation Milpitas,
load ofCA,1.96USA)
mN at with
theXP head with
distance the indentation
of 3 mm from the centerloadofof
1.96 mN at the distance of 3 mm from the center of the deformed disc. There
the deformed disc. There were 100 microhardness measurements taken on each sample with 10 × 10 were 100 microhardness
measurements
points with the taken on each sample
measurement step of with
3 µ m. × 10 that,
10After pointseach
withmeasurement
the measurement was step of 3 µm.as
categorized After that,
copper
each measurement
matrix wasby
or silver particle categorized
means of SEMas copper matrix orThe
observations. silver particle
indents by on
lying means of SEM observations.
the boundaries between
matrix or particles were discarded. A minimum of ten measurements for both phases were takenofinto
The indents lying on the boundaries between matrix or particles were discarded. A minimum ten
account. Low force was chosen to measure hardness of particles and matrix because the particlesof
measurements for both phases were taken into account. Low force was chosen to measure hardness
particles
were small.and
The matrix
samebecause
force forthe particles
both particleswereandsmall.
matrixThe same
were force
used for both
in order particles and
to compare them. matrix
The
were used in order to compare them. The size of the indenter imprint was
size of the indenter imprint was about 0.5 and 0.26 µ m before and after HPT, respectively. about 0.5 and 0.26 µm before
and after HPT, respectively.
3. Results and Discussion
3. Results and Discussion
The Cu–Ag equilibrium phase diagram is presented in Figure 1a [20]. The vertical line shows
The Cu–Ag
the chemical equilibrium
composition phase
of the diagramalloy,
examined is presented
while thein Figure
dots show1a [20].
theThe verticaltemperatures,
annealing line shows the
chemical
i.e., 400, 500composition
and 600 °C.ofThese
the examined alloy, correspond
temperatures while the dots show
to the (α the
+ β)annealing
state, wheretemperatures,
the α-phasei.e., 400,
is the
500 and 600 ◦ C. These temperatures correspond to the (α + β) state, where the α-phase is the solid
solid solution of Ag in Cu whereas the β-phase is the solid solution of Cu in Ag.
solution of Ag in Cu whereas the β-phase is the solid solution of Cu in Ag.

Figure 1. (a) phase diagram of Cu–Ag system [20] with vertical line showing chemical composition of
the examined
Figure alloys,
1. (a) phase while dots
diagram showsystem
of Cu–Ag annealing
[20]temperatures
with vertical of examined
line showingsamples;
chemical(b) SEM imageofof
composition
theexamined
the as-cast Cu–8wt.%Ag alloy.
alloys, while dots show annealing temperatures of examined samples; (b) SEM image
of the as-cast Cu–8wt.%Ag alloy.
The SEM microstructure observations show that the as-cast Cu–8wt.%Ag alloy contains the
precipitates
The SEM of (α + β) eutectic with
microstructure irregular shape
observations show andthat small rounded
the as-cast particles of the
Cu–8wt.%Ag β-phase
alloy of about
contains the
1 µm size) uniformly
precipitates of (α + β) distributed
eutectic with in the α-phase
irregular (Cu-matrix),
shape and smallFigure 1b. The
rounded eutectic
particles andβ-phase
of the β particles
of
were enriched with silver (from 11 to 55 wt.%). The chemical composition of as-cast
about 1 µ m size) uniformly distributed in the α-phase (Cu-matrix), Figure 1b. The eutectic and β Cu-matrix was
inhomogeneous:
particles the Agwith
were enriched content changed
silver (from from 55±wt.%).
11 to3.6 6.7 ±chemical
0.5 to The 0.3 wt.%.composition
Annealing the of as-cast alloy
Cu-
◦
at 400 was
C resulted in the preservation of (α + changed
β) eutectic and3.6 particles with theAnnealing
average size
matrix inhomogeneous: the Ag content from β-phase
± 0.5 to 6.7 ± 0.3 wt.%. theof
about 1.1 µm. The β-phase particles were observed within the grains and at the grain
as-cast alloy at 400 °C resulted in the preservation of (α + β) eutectic and β-phase particles with the boundaries of
the Cu-matrix (Figure ◦
average size of about 1.12a).
µ m. Annealing at 400
The β-phase C resulted
particles also in thewithin
were observed discontinuous
the grainsprecipitation (DP)
and at the grain
of a duplex of
boundaries structure containing
the Cu-matrix a new2a).
(Figure fineAnnealing
β-phase and at the
400 solute depleted
°C resulted initial
also in theα-phase (see SEM
discontinuous
precipitation (DP) of a duplex structure containing a new fine β-phase and the solute depleted initial
α-phase (see SEM image in Figure 2a and TEM images in Figure 3a,b). The DP phenomenon was
frequently observed in Cu-based alloys [21,22] including Cu–Ag alloys with low Ag content [3]. A
Materials 2019, 12, 447 4 of 12

image in Figure 2a and TEM images in Figure 3a,b). The DP phenomenon was frequently observed in
Materials 2019, 12, x FOR PEER REVIEW 4 of 12
Cu-based alloys
Materials 2019, 12, x[21,22]
FOR PEERincluding
REVIEW Cu–Ag alloys with low Ag content [3]. A similar microstructure 4 of 12 of
DPsimilar
was observed in the of
as-cast Cu–6wt.%Ag ◦ C for 32 h [3]. The DP process
microstructure DP was observed inalloy after ageing
the as-cast at 450 alloy
Cu–6wt.%Ag after ageing at 450 °C for
wassimilar microstructure
controlled by the of DP
diffusion was
at observed
the moving in the as-cast
reaction Cu–6wt.%Ag
front between alloy
the after ageing Cu-matrix
supersaturated at 450 °C forand
32 h [3]. The DP process was controlled by the diffusion at the moving reaction front between the
32
formingh [3]. The DP process
(α + β) lamellae. was
The controlled by the diffusion at the moving reaction front between the
supersaturated Cu-matrix andmoving
formingreaction front corresponded
(α + β) lamellae. The movingtoreaction
the high-angle grain boundary.
front corresponded to
supersaturated Cu-matrix and forming (α + β) lamellae. The moving reaction front corresponded to
The selected
the areagrain
high-angle electron diffraction
boundary. The(SAED)
selectedpattern (Figurediffraction
area electron 3c) of the(SAED)
bright field image
pattern presented
(Figure 3c) of in
the high-angle grain boundary. The selected area electron diffraction (SAED) pattern (Figure 3c) of
Figure 3b confirms
the bright that the
field image observed
presented in duplex structure
Figure 3b is related
confirms that thetoobserved
fine β precipitates with the
duplex structure thickness
is related
the bright field image presented in Figure 3b confirms that the observed duplex structure is related
to fine β precipitates with the thickness of about 50 nm in the depleted
of about 50 nm in the depleted initial Cu-matrix. The measurement of chemical composition by meansinitial Cu-matrix. The
to fine β precipitates with the thickness of about 50 nm in the depleted initial Cu-matrix. The
of measurement
EDS in TEM showed of chemicalthatcomposition by means
the silver content in of
theEDS in TEM
primary β showed
particlesthat the silver
remained content
after in the
casting, (see
measurement of chemical composition by means of EDS in TEM showed that the silver content in the
primary
Figure 3a) β particles
was about remained
87 wt.%Ag, after
in casting,
the fine β (see Figure 3a)
precipitates was 30
around about 87 wt.%Ag,
wt.%Ag, while inthe
in theCu-matrix
fine β
primary β particles remained after casting, (see Figure 3a) was about 87 wt.%Ag, in the fine β
precipitates
it was around 30 wt.%Ag, while in the Cu-matrix it was 0.9 wt.%Ag.
0.9 wt.%Ag.
precipitates around 30 wt.%Ag, while in the Cu-matrix it was 0.9 wt.%Ag.

Figure 2. SEM images of the Cu–8wt.%Ag alloy after annealing at (a) 400 °C; (b) 500 °C;
◦ C;(b) (c) 600 °C◦and
◦ C;
Figure
Figure 2. 2.SEM
SEMimages
imagesofofthe
theCu–8wt.%Ag
Cu–8wt.%Ag alloy annealing at
alloy after annealing at(a)
(a)400
400°C; (b)500
500°C; (c)(c)
600600 C and
°C and
after HPT deformation: (d) 400◦°C + HPT; (e) 500 °C ◦
+ HPT; (f)600 °C ◦
+ HPT.
after
after HPTHPT deformation:(d)
deformation: (d)400
400 °C
C ++ HPT; (e)
(e) 500
500 °CC++HPT;
HPT;(f)600 °C +CHPT.
(f) 600 + HPT.

Figure (a,b)
3. 3. Bright field TEM images of the Cu–8wt.%Ag alloy after annealing at 400 ◦ C and (c) SAED
Figure (a,b) Bright field TEM images of the Cu–8wt.%Ag alloy after annealing at 400 °C and (c)
Figuretaken
pattern 3. (a,b)
fromBright
imagefield TEM images of the Cu–8wt.%Ag alloy after annealing at 400 °C and (c)
SAED pattern taken from(b).
image (b).
SAED pattern taken from image (b).
The microstructure ◦ C (Figure 2b) also contained
The microstructureofofthetheCu–8wt.%Ag
Cu–8wt.%Ag alloy alloy after annealingatat500
after annealing 500°C (Figure 2b) also contained
thethe The microstructure
eutectic, primary β-phaseof the Cu–8wt.%Ag
particles and finealloy after annealing
β-phase lamellae at 500the
from °C discontinuous
(Figure 2b) alsoprecipitation,
contained
eutectic, primary β-phase particles and fine β-phase lamellae from the discontinuous
the
however eutectic,
the DP primary
volume β-phase particles and fine β-phase lamellae from the discontinuous ◦
precipitation, however thefraction
DP volume is fraction
much lower is much than
lowerthat inthat
than theinsample
the sampleannealed
annealedat at400
400 C.
Theprecipitation, however the DP volume fraction is much lower than that in◦ the sample annealed at 400
°C.microstructure of the
The microstructure of Cu–8wt.%Ag
the Cu–8wt.%Ag alloy after
alloy annealing
after annealingat at 600
600 °C C differs
differssignificantly
significantlyfromfrom
°C.
that The microstructure
described of the Cu–8wt.%Ag alloy after annealing at 600 °C differs significantly from
that describedabove; onlyone
above; only onetype
typeof of homogeneous
homogeneous β-phase
β-phase particles
particles with the with the average
average sizes of
sizes of about
that described above; only one type of homogeneous β-phase particles with the average sizes of about
about
1.4 µ1.4 µm were
m were observed
observed (Figure (Figure
2c). It 2c). It isknown
is well well known that discontinuous
that discontinuous precipitation
precipitation basically
basically occurs
1.4 µ m were observed (Figure 2c). It is well known that discontinuous precipitation basically occurs
occurs
at lowat temperatures
low temperatureswhenwhengrain grain boundary
boundary diffusion
diffusion dominates
dominates overdiffusion.
over bulk bulk diffusion. Generally,
Generally, the
at low temperatures when grain boundary diffusion dominates over bulk diffusion. Generally, the
theincrease
increase ofof
temperature
temperature causes thethe
causes increase
increaseof the
of bulk diffusion
the bulk coefficient
diffusion in comparison
coefficient with the
in comparison with
increase of temperature causes the increase of the bulk diffusion coefficient in comparison with the
thegrain
grainboundary
boundary one. ThisThis
one. is because the activation
is because enthalpy
the activation of bulkofdiffusion
enthalpy is nearlyistwo
bulk diffusion times
nearly two
grain boundary one. This is because the activation enthalpy of bulk diffusion is nearly two times
higher than that of grain boundary diffusion. Therefore, the increase of annealing temperature
higher than that of grain boundary diffusion. Therefore, the increase of annealing temperature
resulted in the reduction of discontinuous precipitation at 500 °C and its complete disappearance at
resulted in the reduction of discontinuous precipitation at 500 °C and its complete disappearance at
Materials 2019, 12, 447 5 of 12

times higher than that of grain boundary diffusion. Therefore, the increase of annealing temperature
resulted in the reduction of discontinuous precipitation at 500 ◦ C and its complete disappearance at
600 ◦ C. The increase of bulk diffusion taking place through the volume of crystal grains at 600 ◦ C
explains also the transformation of (α + β) eutectic precipitates into the homogeneous β-phase particles.
The measurement of volume fraction of the β-phase on the basis of X-ray diffraction (XRD) patterns
showed that with increasing annealing temperature, the volume fraction of the β-phase decreases
from about 8.6 to 6.3% (Table 1). This trend correlates with the lever rule for the calculation of the
relative number of phases in a two-phase mixture in a binary alloy system. It should be noted that the
amount of the β-phase measured in XRD patterns includes all β precipitates in the material; namely,
primary ones, those from the eutectic and from the discontinuous precipitation. It should be also noted
that according to the equilibrium Cu–Ag phase diagram, the higher the temperature of annealing,
the higher the solubility of Ag in the Cu-matrix. The measurement of chemical composition by means
of EDS/SEM confirmed that with increasing annealing temperature, the silver concentration in the
Cu-matrix (α-phase) and in the coarse β-phase particles grew (Table 2).

Table 1. The volume fraction (%) of β-phase precipitates in the Cu–8wt.%Ag alloy after annealing at
different temperatures T (◦ C) measured on the bases of XRD data.

Volume Fraction %
T ◦C
Before HPT After HPT Increment ∆
400 8.6 2.6 6.0
500 6.6 3.5 3.1
600 6.3 3.9 2.4

Table 2. Distribution of silver (wt.%) in the Cu–8wt.%Ag alloy before and after HPT process measured
by EDS/SEM.

Before HPT After HPT

T ◦C Coarse Ag Coarse Ag
Cu-Matrix Cu-Matrix
Precipitates Precipitates
400 4.0 ± 0.4 32.5 ± 0.6 5.6 ± 0.2 14.1 ± 0.7
500 4.7 ± 0.5 44.1 ± 0.9 5.4 ± 0.2 33.8 ± 0.7
600 5.0 ± 0.4 52.3 ± 1.0 5.1 ± 0.2 39.2 ± 0.8

The observation of microstructure of the Cu–8wt.%Ag alloy after HPT by means of TEM technique
showed that HPT resulted in a strong grain refinement of Cu-matrix (down to about 400 nm) with
high density of dislocations within the grains (see bright and dark field TEM images in Figure 4).
The selected area electron diffraction (SAED) patterns (Figure 4c,f,i) also showed a strong grain
refinement; a large number of spots formed almost continuous diffraction rings which indicates the
occurrence of large quantity of small grains with different crystallographic orientation. The maximum
number of spots in the diffraction rings were observed in the deformed sample after prior annealing at
600 ◦ C. It seems that the higher temperature of preliminary annealing, the stronger grain refinement of
Cu-matrix. However, the EBSD measurements and XRD diffraction analysis with much better statistics
showed the reverse dependencies of grain refinement on temperature of preliminary annealing (see
this in the subsequent part of manuscript). A close examination of diffraction rings (Figure 4c,f,i)
also showed the presence of small Ag particles in all deformed samples. Most likely, they are
related to the fragmentation and refinement of β-phase precipitates (enriched by Ag) due to the
HPT deformation. The analysis of their behavior under HPT was additionally carried out using SEM.
The SEM observations of deformed samples of the Cu–8wt.%Ag alloy showed blurring of the (α + β)
eutectic and β-phase precipitates along slip lines formed during the HPT deformation (Figure 2d–f).
Materials 2019, 12, 447 6 of 12

The lower the temperature of preliminary annealing, the more blurry precipitate boundaries could be
observed. Heterogeneity of chemical composition and irregular shape of eutectic and the presence of
fine discontinuous precipitation may be the reason that the β-phase observed in the initial samples
annealed ◦ C dissolved easier and had more blurry boundaries after the HPT. Moreover,
Materialsat 40012,and
2019, 500
x FOR PEER REVIEW 6 of 12
the primary precipitates and eutectics in the samples annealed at 400 and 500 ◦ C showed slightly lower
slightly
hardness lower3)hardness
(Table (Table 3) that
than precipitates thanappeared
precipitates that
after appearedatafter
annealing ◦ C, which at
600 annealing 600 °C, which
contained more Ag
contained
content (Tablemore2) andAgwere
content (Table 2) and
characterized by awere characterized
rounded shape andbyuniform
a rounded shape and uniform
composition.
composition.

4. 4.TEM ◦ + HPT;
Figure
Figure TEMimages
images ofof the
theCu–8wt.%Ag
Cu–8wt.%Ag alloy
alloy after
after annealing
annealing and (a–c)
and HPT: HPT:400 (a–c)
°C +400
HPT;C(d–f)
(d–f) 500 ◦ ◦
500 °C C + HPT;
+ HPT; (g–i)
(g–i) 600600
°C +CHPT;
+ HPT; (a,d,g)
(a,d,g) bright
bright field
field images;
images; (b,e,h)
(b,e,h) dark
dark field
field images;
images; (c,f,i)
(c,f,i) SAEDSAED
patterns taken from (b,e,h).
patterns taken from (b,e,h).

Figure
Figure5 presents
5 presents XRD
XRDpatterns
patternsofof the
the Cu–8wt.%Ag
Cu–8wt.%Ag alloy alloyafter
afterannealing
annealing andand after
after thethe
HPTHPT
deformation. The Ag and Cu peaks were observed in all the samples after annealing.
deformation. The Ag and Cu peaks were observed in all the samples after annealing. The Cu peaks The Cu peaks
(α-phase) observed
(α-phase) observedat at
higher
higherdiffraction
diffractionangles
angles(137 144◦ )were
(137 and 144°) weresplit,
split, which
which indicated
indicated lowlow internal
internal
stresses and
stresses andlarger
largergrain
grainsizes in the
sizes in theannealed
annealed samples.
samples. TheThe significant
significant broadening
broadening of Cuwas
of Cu peaks peaks
wasobserved
observed after HPT
after HPT suggesting
suggesting a strong
a stronggrain refinement
grain and significant
refinement micro-distortion
and significant of the of
micro-distortion
the crystal
crystallattice. A slight
lattice. shiftshift
A slight of Cuofpeaks to lower
Cu peaks to diffraction angles after
lower diffraction HPTafter
angles was observed
HPT wasasobserved
well.
This corresponds to the increase of Cu lattice parameters due to migration of
as well. This corresponds to the increase of Cu lattice parameters due to migration of Ag atoms Ag atoms from the β-
fromphase
the (Ag particles)
β-phase (Ag into the Cu-matrix.
particles) into theAtCu-matrix.
the same timeAtthe
the(111)
same reflection
time the of (111)
the β-phase became
reflection of the
β-phase became smaller and more broadened (in the samples annealed at 500 and 600 Cwhile
smaller and more broadened (in the samples annealed at 500 and 600 °C prior to deformation), ◦ prior to
the remaining β-phase peaks disappeared or became blurred and undetectable. The disappearance
deformation), while the remaining β-phase peaks disappeared or became blurred and undetectable.
of most β-phase reflections after HPT indicates the partial dissolution of this phase.
The disappearance of most β-phase reflections after HPT indicates the partial dissolution of this phase.
Materials 2019, 12, 447 7 of 12
Materials 2019, 12, x FOR PEER REVIEW 7 of 12
Materials 2019, 12, x FOR PEER REVIEW 7 of 12

Figure
Figure5.
Figure X-ray
5.5.X-ray diffraction
X-raydiffraction patterns
diffractionpatterns
patterns of
ofof the
thethe Cu–8wt.%Ag
Cu–8wt.%Ag alloy
alloy
Cu–8wt.%Ag after
alloy after annealing
annealing
after at at different
at different
annealing temperatures
temperatures
different temperatures
before
before and
and after
after HPT.
HPT.
before and after HPT.

Figure
Figure 6a
Figure 6a6ashows
shows an
shows an enlarged
anenlarged part
enlargedpart
partofofof
thethe
the X-ray
X-ray
X-ray diffraction
diffraction patterns
patterns
diffraction of theofdeformed
patterns of thethedeformed
deformed
samplessamples
samples
preliminarily annealed
preliminarily annealed atat400
400 and
and600
600°C.◦ C.
It is
It easy
is to note
easy to thatthat
note maximum
maximumbroadening and maximum
broadening and maximum
preliminarily annealed at 400 and 600 °C. It is easy to note that maximum broadening and maximum
shiftof
shift of (111) Cu
Cu peak isisobserved in the sample annealed at 400 ◦
°C. Additionally the (111) Ag peak
shift of(111)
(111) Cupeak
peak is observed
observed inin the sample
the sample annealed
annealed atat400
400°C.C.Additionally
Additionally thethe (111)
(111) AgAg peak
peak
disappeared
disappeared after HPT in the sample. It confirms that the maximum grain refinement and maximum
disappearedafterafterHPT
HPTin in the
the sample.
sample. ItIt confirms
confirmsthat thatthe
themaximum
maximumgrain grain refinement
refinement andand maximum
maximum
dissolution of β-phase takes place there.
dissolution of β-phase takes place
dissolution of β-phase takes place there.there.

Figure 6. (a) Enlarged part of X-ray diffraction patterns of samples of the Cu–8wt.%Ag alloy after
Figure 6. (a) Enlarged part of X-ray diffraction patterns of samples of the Cu–8wt.%Ag alloy after
HPT and preliminary annealed at 400 and 600 ◦ C. Vertical dotted line shows the (111) peak position of
HPT
Figureand6.preliminary
(a) Enlargedannealed
part of at 400
X-ray and 600 °C.
diffraction Vertical
patterns dotted
of line shows
samples of theCu–8wt.%Ag
(111) peak position
pure copper; (b) Changes of lattice parameter of Cu-matrix induced by the
HPT alloy after
in samples preliminarily
of
HPT pure
andcopper; (b)
preliminary Changes◦
annealed ofat lattice
400 andparameter
600 °C. of Cu-matrix
Vertical dotted induced
line showsby HPT
the in peak
(111) samples
position
annealed at 400, 500 and 600 C.
preliminarily annealed at 400, 500 and 600 °C.
of pure copper; (b) Changes of lattice parameter of Cu-matrix induced by HPT in samples
The changes annealed
preliminarily of latticeatparameter
400, 500 andof 600Cu-matrix
°C. before and after HPT are graphically presented
The changes of lattice parameter of Cu-matrix before and after HPT are graphically presented in
inFigure
Figure 6b. Generally, doping copper with silver leads to an increase in the lattice parameter of
6b. Generally, doping copper with silver leads to an increase in the lattice parameter of copper
copper The changes of lattice parameter of Cu-matrix beforewith
and afterincrease
HPT are of graphically presented in
[23,24]. One can see from Figure 6b that along with the increase ofthe
[23,24]. One can see from Figure 6b that along annealing
annealing temperature, thetemperature,
lattice
Figure
the 6b.parameter
lattice Generally,increases,
doping copper withthe
because silver leads toofan
solubility Agincrease in the lattice
in Cu increases parameter
alongside theofsolvus
copperline
on the phase Cu–Ag diagram. HPT resulted in the increase of the lattice parameters values, lattice
[23,24]. One can see from Figure 6b that along with the increase of annealing temperature, the wherein
Materials 2019, 12, 447 8 of 12

their maximum increase is observed in the sample preliminary annealed at 400 ◦ C. These results show
a good correlation with the data presented in Table 1, i.e., the largest amount of dissolved β-phase
under action of HPT process is observed in the sample pre-annealed at 400 ◦ C, while the smallest
one in the sample pre-annealed at 600 ◦ C. Therefore, it can be concluded that the lower the annealing
temperature, the greater the enrichment of matrix in Ag after HPT. It is a result of partial dissolution
of the primary β-phase, (α + β) eutectic and probably the effect of complete dissolution of the fine
discontinuous precipitates. It should be also noted, that the lattice parameter of Cu-matrix obtained
after HPT in the samples pre-annealed at 400, 500 and 600 ◦ C reached 0.36433, 0.36356 and 0.36359
± 0.00001 nm, respectively. According to the [24] database, a slightly smaller lattice parameter of
0.36421 nm in the sample pre-annealed at 400 ◦ C, corresponds to the Cu–5.82 at.%Ag alloy obtained
after homogenizing at 760 ◦ C for 48 days and 780 ◦ C for 70 days. The composition of 5.82 at.%Ag
corresponds to 9.5 wt.%Ag, while 8 wt.%Ag is the maximum amount of Ag which can be dissolved
in Cu at eutectic temperature 780 ◦ C. In other words, HPT led to a greater dissolution of Ag than the
possible maximum solubility of Ag in the Cu–8wt.%Ag alloy obtained after prolonged annealing at
780 ◦ C. This effect of increasing solubility limit of Ag induced by HPT was not observed in the other
deformed samples (pre-annealed at 500 and 600 ◦ C) of the examined alloy.
The phenomenon of anomalous phase transitions, i.e., dissolution of the second phase under
the influence of SPD, was observed in many works [9,25] and systematically studied in Fe-based
alloys [26,27]. For example, it was shown that the C, N and Niwas transferred from the second phase
particles into the iron solid solution as a result of SPD, wherein the concentration of these elements
could exceed the equilibrium saturation concentrations [26]. The authors presented the following
scheme of such a dissolution. At the first stage of the SPD the particles were refined, at a more
developed stage of deformation the contribution of “non-crystallographic” deformation mechanisms
increased, accompanied by an intense generation of vacancies. Then the separation and drift of atoms
from particles in the field of edge dislocations became more efficient. Such phase transitions are
also characterized by anomalous rapid diffusion, which can be explained by the generation of excess
vacancies and grain boundary diffusion in ultra-fine-grained materials with a large fraction of high
angle grain boundaries, and it happened despite the fact that the applied pressure additionally slowed
down the diffusion [28,29]. It should be noted that the HPT-induced mass transfer led not only to the
increase of the solubility limit, but also to obtaining nanocomposites from mixtures of micro-powders
even for immiscible systems [30].
Figure 7 shows SEM/EBSD orientation maps (a–c) and corresponding chemical composition maps
(e–g) of the deformed alloy. The character of silver distribution in the form of elongated coarse β-phase
particles well correlates with the microstructure observed in Figure 2d–f. The average grain sizes of
deformed Cu-matrix (measured on the basis of orientation topography maps) reached 0.35 ± 0.12,
0.44 ± 0.16 and 0.48 ± 0.17 µm, respectively for the samples preliminary annealed at 400, 500 and
600 ◦ C. It seems that the presence of the discontinuous precipitates (with the maximum fraction in
the sample annealed at 400 ◦ C) in the form of fine duplex structure additionally leads to the grain
refinement of the microstructure during HPT. The statement that the presence of fine dispersed particles
promotes the microstructure refinement during SPD has been confirmed in works [7,8]. For example,
the nanosize Al3 (Sc,Zr) precipitates play an important role in the grain refinement of the Al–0.2Sc–0.1Zr
alloy subjected to the process of accumulative continuous extrusion forming [8]. The grain size of
the alloy dramatically refined from 100 µm to 800 nm through continuous dynamic recrystallization
(CDRX). The nanosize particles promoted grain refinement through three mechanisms: the precipitates
(i) facilitated retention of high dislocation density in the alloy by enabling the generation of dislocation
and pinning dislocation slip, which increased the driving force for CDRX; (ii) promoted the formation
of deformation bands, providing sites for activation of CDRX, and (iii) activated CDRX near the grain
boundary. The texture of HPT processed samples of the Cu–8wt.%Ag alloy did not show significant
differences in intensity and component position. All samples yielded a typical shear texture with A,
Materials 2019, 12, 447 9 of 12
Materials 2019, 12, x FOR PEER REVIEW 9 of 12

B, Cyielded
components ofshear
a typical fcc metals.
textureItwith
strongly suggested
A, B, C thatofthe
components fcc discussed particlessuggested
metals. It strongly did not change
that the the
deformation
discussed mechanism
particles did during the the
not change HPT process. mechanism during the HPT process.
deformation

Figure 7. (a–c)
Figure SEM/EBSD
7. (a–c) SEM/EBSD orientation mapsand
orientation maps and(e–g)
(e–g) corresponding
corresponding Ag distribution
Ag distribution (green(green
color) color)
in
in Cu-matrix (black color) of the Cu–8wt.%Ag alloy after HPT, preliminary annealed at (a,e) 400 ◦ C,
Cu-matrix (black color) of the Cu–8wt.%Ag alloy after HPT, preliminary annealed at (a,e) 400 °C, (b,f)
500°C◦ C
(b,f)500 and
and(c,g)
(c,g) °C ◦together
600600 withwith
C together (d) standard unit unit
(d) standard triangle for fccfor
triangle α-phase. The inserts
fcc α-phase. inside (a–
The inserts inside
(a–c) display enlarged areas of the EBSD maps with high angle grain boundaries (HAGBs)than
c) display enlarged areas of the EBSD maps with high angle grain boundaries (HAGBs) larger larger
than10°.
10◦ .

TheThe results
results of of microhardnessmeasurements
microhardness measurements are
are presented
presentedininTable
Table3. 3.TheThe
Cu Cu
andand
Ag-Ag-solid
solid
solutions
solutions have
have thesame
the samefcc
fcc lattice
lattice and
andthe
thehardness
hardnessvalues of Cu-matrix
values and Ag
of Cu-matrix andprecipitates are also are
Ag precipitates
similar reaching about 134 H v before HPT. After HPT only, the microhardness of the sample pre-
also similar reaching about 134 Hv before HPT. After HPT only, the microhardness of the sample
annealed atat
pre-annealed 600 °C ◦was
600 measured,
C was in which
measured, the Cu-matrix
in which did not include
the Cu-matrix did notfine Ag particles
include resulting
fine Ag particles
from discontinuous precipitation. HPT led to the increase of microhardness of both phases to the
resulting from discontinuous precipitation. HPT led to the increase of microhardness of both phases
value of about 310 Hv. The increase of microhardness was associated with an increase in the crystal
to the value of about 310 Hv . The increase of microhardness was associated with an increase in the
structure defect density and with the increase of high-angle grain boundary fraction as a result of
crystal structure defect density and with the increase of high-angle grain boundary fraction as a result
grain refinement induced by HPT.
of grain refinement induced by HPT.
Table 3. Microhardness of Cu-matrix and coarse Ag precipitates in the Cu–8wt.%Ag alloy before and
Table Microhardness
3. HPT
after process. of Cu-matrix and coarse Ag precipitates in the Cu–8wt.%Ag alloy before and
after HPT process.
Microhardness Hv
Treatment Microhardness H
Treatment Cu-Matrix Ag Precipitates v
Cu-Matrix Ag Precipitates
400 °C 132 ± 8 134 ± 6
◦
400 C 132 ± 8 134 ± 6
500 °C 131 ± 5 128 ± 10
◦
500 C 131 ± 5 128 ± 10
600 °C 136 ± 8 142 ± 8
◦
600 C 136 ± 8 142 ± 8
600 °C + HPT 311 ± 20 310 ± 32
600 ◦ C + HPT 311 ± 20 310 ± 32
Based on results obtained in Ref. [25], the effect of SPD on phase transformations was established
toBased
depend
onstrongly on diffusion
results obtained activation
in Ref. energy
[25], the effectand
of mixing
SPD onenthalpy of the alloying elements.
phase transformations The
was established
higher the
to depend activation
strongly enthalpy of
on diffusion diffusion,energy
activation the lowerandthe diffusion
mixing relaxation
enthalpy of crystallographic
of the alloying elements.
defects formed by SPD. This, in turn, promoted grain refinement and phase transitions
The higher the activation enthalpy of diffusion, the lower the diffusion relaxation of crystallographic(such as
dissolution of the second phase or the decomposition of supersaturated solid solution). For example,
defects formed by SPD. This, in turn, promoted grain refinement and phase transitions (such as
it was shown that the higher the activation enthalpy of diffusion of the second component (like Ag,
dissolution of the second phase or the decomposition of supersaturated solid solution). For example,
it was shown that the higher the activation enthalpy of diffusion of the second component (like
Materials 2019, 12, 447 10 of 12

Ag, Co, Hf, Cr in the Cu-based alloys), the higher the as-called effective temperature (Teff ), which
corresponded to a new position of the deformed alloy in the equilibrium phase diagram [25]. In other
words, the phases forming during SPD at ambient temperature can also appear after long annealing at
a certain elevated temperature Teff with subsequent quenching. However, if the real annealing at the
elevated temperature led to grain growth, the SPD resulted in the grain refinement of microstructure.
The effect of SPD on phase transformation of compounds with a positive or negative enthalpy
of mixing was different. Due to strong interatomic bonds such as compounds with a negative
enthalpy of mixing (such as Cu–Sn, Cu–In), the process of dissolution of second phase practically
did not occur [31,32] compared with compounds of positive mixing enthalpy (Cu–Ag, Cu–Ni,
Cu–Co). For example, in as-cast Cu–36wt.%Sn alloy which was subjected to HPT at room
temperature [31], the microstructure of the alloy before HPT, contained alternating coarse-grained or
even single-crystalline plates of the hard intermetallic ζ (Cu10 Sn3 ) and ε (Cu3 Sn) phases. After HPT,
neither dissolution of phases, nor phase transformations were observed. Only slight grain refinement
took place inside the ζ and ε plates, however, the shape of alternating plates remained unchanged.

4. Conclusions
The microstructure of the Cu–8wt.%Ag alloy after annealing at 400 and 500 ◦ C contained coarse
(α + β) eutectic, coarse β-phase precipitates and fine (α + β) duplex structure formed due to the
discontinuous precipitation. The volume fraction of discontinuous precipitates after annealing at
500 ◦ C was smaller than that after annealing at 400 ◦ C. Annealing of the alloy at 600 ◦ C resulted in
the transformation of eutectic precipitates into coarse homogeneous β-phase particles. The higher the
temperature of annealing, the lower volume fraction of β-phase precipitates and the higher content of
Ag in the Cu-matrix (α-phase).
Applying HPT to the Cu–8wt.%Ag alloy resulted in: (1) strong grain refinement of the Cu-matrix
(down to about 400 nm); (2) partial dissolution of coarse (α + β) eutectic and coarse β-phase particles,
their fragmentation and refinement; (3) dissolution of fine discontinuous precipitates; and (4) an
increase of solubility limit of Ag in the Cu-matrix in the sample pre-annealed at 400 ◦ C.
The maximum HPT effect on grain refinement of the Cu-matrix and the dissolution of β-phase was
observed in the sample preliminary annealed at 400 ◦ C due to the fact that the initial state of this sample
was characterized by: (1) the largest volume fraction of dispersed duplex structure; (2) the presence of
a slightly softer (α + β) eutectic in comparison with coarse and homogeneous Ag particles; and (3) the
lowest solubility of Ag in Cu-matrix. Specifically, small, heterogeneous precipitates of the irregular
shape dissolved more easily than those of large sizes, rounded shape and uniform composition.

Author Contributions: Conceptualization, A.K. (Anna Korneva) and B.S.; Data Curation, A.K. (Anna Korneva)
and A.K. (Askar Kilmametov); Formal Analysis, A.K. (Anna Korneva) and A.K. (Askar Kilmametov); Investigation,
A.K. (Anna Korneva), A.K. (Askar Kilmametov), R.C. and G.C.; Methodology, A.K. (Anna Korneva); Supervision,
A.K. (Anna Korneva); Writing—Original Draft Preparation, A.K. (Anna Korneva); Writing—Review and Editing,
A.K. (Anna Korneva), P.Z., B.S. and R.C.; Funding Acquisition, P.Z., B.S. and B.B.
Funding: This research was funded by the National Science Centre of Poland (grant OPUS number
2014/13/B/ST8/04247) and Deutsche Forschungsgemeinsgaft (AB 1768). All the research was performed
within the Accredited Testing Laboratories possessing the certificate No. AB 120 issued by the Polish Centre
of Accreditation. This means that all the research is performed according to European standard PN-ISO/IEC
17025:2005 as well as the EA-2/15. B.S. acknowledges the support of Ministry of Education and Science of the
Russian Federation in the framework of the Program to Increase the Competitiveness of NUST “MISiS”.
Conflicts of Interest: The authors declare no conflict of interest. The founding sponsors had no role in the design
of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, and in the
decision to publish the results.

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