coatings
Article
Structure and Mechanical Properties of Porous TiNi Alloys with
Ag Nanoparticles
Ekaterina Marchenko
Citation: Marchenko, E.;
Baigonakova, G.; Larikov, V.;
Monogenov, A.; Yasenchuk, Y.
Structure and Mechanical Properties
of Porous TiNi Alloys with Ag
Nanoparticles. Coatings 2023, 13, 24.
https://doi.org/10.3390/
coatings13010024
Academic Editor: Mehmet Yilmaz
Received: 9 November 2022
Revised: 17 December 2022
Accepted: 19 December 2022
Published: 23 December 2022
Copyright: © 2022 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Coatings 2023, 13, 24. https://doi.org/10.3390/coatings13010024
, Gulsharat Baigonakova * , Viktor Larikov, Aleksandr Monogenov and Yuri Yasenchuk
Laboratory of Superelastic Biointerfaces, National Research Tomsk State University, 36 Lenin Ave.,
634045 Tomsk, Russia
* Correspondence: gat27@mail.ru
Abstract: The work studies the influence of the silver dopant (<0.5 at.%) on the structure and
mechanical properties of porous TiNi alloys obtained by self-propagating high-temperature synthesis.
These alloys are of high scientific and practical interest in medicine. The presence of silver in the TiNi
alloy will ensure improved cytocompatibility and antibacterial properties. The TiNi porous alloys
with 0.2 and 0.5 at.% Ag nanoparticles have multiphase composition. Quantitative X-ray diffraction
analysis of the obtained alloys showed that an increase in the silver content is accompanied by
a quantitative decrease in the austenite phase TiNi(B2) and an increase in the martensite phase
TiNi(B19’), as well as in secondary phases Ti2 Ni, Ti4 Ni2 O. Evenly distributed silver nanoparticles
up to 10 nm were found in the surface layer by transmission electron microscopy. The results of
the scanning electron microscopy showed that inclusions containing silver are located mainly in the
zones of Ti2 Ni peritectic crystallization. The mechanical characteristics were studied by means of
compression tests and it was found that with an increase in the silver dopant, the elastic modulus
and elastic limit decrease, but the maximum deformation to fracture increases significantly. It was
found that with an increase in the volume fraction of silver, the plastic properties of the alloy increase.
No dependency of the tensile strength on the amount of silver was found.
Keywords: mechanical characteristics; nanoparticles; porous alloy; silver; structure; TiNi
1. Introduction
Currently, TiNi-based alloys are of high scientific and practical interest [1,2]. The
unique properties of the TiNi alloys such as shape memory effect, superelasticity, strength,
ductility, and corrosion resistance make them highly biocompatible compared to other
alloys, which ensures their wide use in medicine. Various doping additives introduced
into the TiNi composition give it various structure-phase states and effectively influence its
physical and mechanical characteristics [3–5]. In work [3], aluminum was added into the
porous TiNi alloy to improve the physical and mechanical properties and make it possible
to use as an implantation material. In [4], the authors determined the range of silver
content for the production of TiNi-Ag wires. It was found that the optimal balance between
strength, ductility, and shape memory parameters was achieved at a silver concentration of
0.1 at.%. In a study of the silver effect on cell viability in cast TiNiAg alloys, results showed
that silver in small amounts (0.1–0.2 at.%) is favorable for cell adhesion, and increases the
cell viability level by more than 30% [6].
Porous TiNi alloys are well integrated into biological tissues and at the same time
they remain permeable to biological fluids. Therefore, porous TiNi alloys are used as an
effective osteoplastic material [7,8]. Nowadays, the implant industry pays special attention
to materials with antimicrobial activity which prevent infection [9]. Among the metals with
antimicrobial properties, silver has attracted the interest of many researchers due to its
high biocidal activity. Silver has bactericidal activity at concentrations up to 35 parts per
billion [9,10] without any toxic effect on mammalian cells. For the Ag particles in the range
https://www.mdpi.com/journal/coatings
Coatings 2023, 13, 24 2 of 13

of 20–30 nm, optimal characteristics of antibacterial activity, biocompatibility, and corrosion

resistance were achieved [11,12]. In addition, the bacteria showed a low propensity to
develop resistance to silver. But the results of studies on the antimicrobial efficacy of silver
alloys are often inconclusive and conflicting.
Regarding the studies on TiNiAg alloys, there are mainly works on cast titanium
nickelide alloys. TiNi alloys with the Ag concentration from 0.5 to 9 at.% are of particular
interest in medicine. The presence of silver in the alloy ensures the improved cytocompat-
ibility and antibacterial properties of TiNi [13–17] as well as increases the yield strength
and tensile strength [18,19]. The shape memory effect of TiNi alloys was studied at the Ag
concentration of 1.4 at.% [14]. Martensitic transformations, as well as microhardness, were
mainly considered in the range of 0.6–1.9 at.% Ag [20–23]. The effect low silver content
(<0.5 at.%) has on the structure, mechanical characteristics, and deformability of porous
TiNiAg alloys has not been fully studied. No study was found on Ag addition during the
production of porous TiNi alloys by self-propagating high-temperature synthesis. There
are few studies on adding Ag during the sintering of porous TiNi alloys, as well as on
modifying the surface of porous TiNi alloys using Ag. Ag addition reduces the Young’s
modulus of the porous TiNi alloy, which results in a greater similarity to the Young’s
modulus of the human bone, as well as an increase in the maximum deformation of the
alloy [24].
The aim of this work is to study the effect silver dopant has on the structure and
physical and mechanical properties of porous TiNi alloys obtained by self-propagating
high-temperature synthesis (SHS).
The authors believe that the silver addition in the nanopowder form will provide
antibacterial properties while maintaining the high functional characteristics of the porous-
permeable NiTi. This will create a new material with a suitable microenvironment for
osteogenesis and an antibacterial, anti-inflammatory effect in order to counteract the
development of infection at the interface of the implant-biological tissue.

2. Materials and Methods

Two powder mixtures were prepared for the study, each containing the main part of
nickel PNK OT-4, titanium PTOM-2, titanium nickelide PN45T55OM, and silver nanopow-
der dopant with an average particle size of 8 nm and the concentration of 0.2 at.% Ag and
0.5 at.% Ag. To distribute the dopant more evenly, silver nanopowder was mixed with
nickel powder in equal amounts, then the main part of the nickel and titanium powders
was added to the resulting mixture in small portions and mixed. The TiNiAg alloy samples
were obtained by the SHS method in a flow reactor in the flowing argon atmosphere to
prevent the mixture oxidation during heating and the oxidation of the synthesized alloy
during cooling. The synthesis was initiated by an electric arc, after preheating the reactor
to a stable temperature of 520 ◦ C. After the synthesis reaction was passed, the reactor with
the obtained porous alloys was cooled by immersion in water at room temperature.
The phase composition and structure of the alloys were studied with a Shimadzu
XRD-6000 diffractometer in CuKα radiation. X-ray diffraction patterns were indexed
with the PowderCell 2.4 full-profile analysis program and compared with the PDF 4+
database. The volume fractions of the phases were estimated by full-profile analysis
based on calculations in relation to the intensities ratio of diffraction reflections using the
POWDER CELL 2.4 program and the PDF-4+ database. The lattice parameters and micro-
stresses were calculated with precision using the POWDER CELL 2.4 software. SEM images
of porous TiNiAg samples were obtained with a scanning electron microscope (TESCAN
ORSAY HOLDING, Brno, Czech Republic) with a Tescan MIRA 3 LMU Schottky cathode
equipped with an Oxford Instruments Ultim Max 40 energy dispersive X-ray spectrometer
(Oxford Instruments, High Wycombe, UK).
The structure of the samples in cross-section geometry was studied using transmission
electron microscopy at an accelerating voltage of 200 kV using the JEOL JEM-2100 (JEOL
Ltd., Tokyo, Japan) electron microscope at the Center for Collective Use Nanotech, Institute
 Coatings 2022, 12, x FOR PEER REVIEW 3 of 13

The structure of the samples in cross-section geometry was studied using transmis-
Coatings 2023, 13, 24 3 of 13
sion electron microscopy at an accelerating voltage of 200 kV using the JEOL JEM-2100
(JEOL Ltd., Tokyo, Japan) electron microscope at the Center for Collective Use Nanotech,
Institute of Physics and Mathematics, Siberian Branch of the Russian Academy of Sci-
of Physics
ences. Theand
studyMathematics, Siberian
of mechanical Branch
properties wasofperformed
the RussianonAcademy
an Instronof5969
Sciences. Thea
(Instron,
study of mechanical properties was performed on an Instron 5969 (Instron, a division
division of Illinois Tool Works Inc., Norwood, IL, USA) setup using a compression load- of
Illinois Tool Works Inc., Norwood, IL, USA) setup using a compression loading
ing scheme. Samples for compression with geometric dimensions 6 mm × 3 mm × 3 mm scheme.
Samples for compression with geometric dimensions 6 mm × 3 mm × 3 mm were cut
were cut from the workpiece with an electric spark machine. Uniaxial compression load-
from the workpiece with an electric spark machine. Uniaxial compression loading was
ing was carried out at a room temperature of 24 °C. When studying the mechanical prop-
carried out at a room temperature of 24 ◦ C. When studying the mechanical properties of
erties of each composition, at least 5 samples were tested.
each composition, at least 5 samples were tested.

3.3.Results
Resultsand
andDiscussion
Discussion
3.1.Results
3.1. Results
3.1.1.XRD
3.1.1. XRDof ofCross
CrossSections
SectionsTiNiAg
TiNiAgSpecimens
Specimens
Figure
Figure11shows
showsX-ray
X-raydiffraction
diffractionpatterns
patternsof
ofTiNi
TiNisamples
samplescontaining
containingAg.
Ag.The
Thephase
phase
composition
composition of
of the
the studied
studiedalloys
alloysconsists
consistsofofTiTi
4 Ni
4Ni22O,
O, Ti
Ti22Ni,
Ni, TiNi(B19’),
TiNi(B19’), and
and TiNi(B2)
TiNi(B2)
phases.
phases.Due
Duetotothe
thesmall
smallamount
amountof ofsilver,
silver,no
noAg-based
Ag-basedphasesphaseswere
werefound.
found.

Figure1.1.X-ray
Figure X-raydiffractograms
diffractogramsof
ofSHS–TiNi
SHS–TiNiporous
porousalloys
alloysspecimens:
specimens: (a)
(a)TiNi;
TiNi;(b)
(b)TiNi
TiNi++0.2%
0.2%Ag;
Ag;
(c) TiNi + 0.5% Ag.
(c) TiNi + 0.5% Ag.

Quantitative X-ray diffraction analysis of TiNiAg alloys shows an increase in the

volume fraction of the TiNi martensitic phase with the B19’ structure, Ti2 Ni, Ti4 Ni2 O
secondary phases, and a decrease in the fraction of the TiNi austenite phase with the B2
structure with increasing silver content (Table 1 and Figure 2a).
Coatings 2023, 13, 24 4 of 13

Table 1. X-ray analysis of TiNiAg alloys.

Lattice Parameters
Volume Fraction, CSR Dimensions, Microdistortions,
Sample Detected Phases Å, and Unit Cell
vol.% nm ∆d/d, 10−3
Volume, Å3
a = 11.3414
Ti2 Ni + Ti4 Ni2 O 46 28 2.4
V = 1458.8143
TiNi
B19’ 16 - 22 2.0
a = 2.9969
B2 38 38 1.5
V = 26.9164
a = 11.1026
Ti2 Ni + Ti4 Ni2 O 51 26 2.1
V = 1368.5923
TiNi + 0.2% Ag
B19’ 18 - 22 1.1

Coatings 2022, 12, x FOR PEER REVIEW a = 3.0058 4 of 13

B2 31 34 2.1
V = 27.1569
a = 11.3065
Ti2 Ni + Ti4 Ni2 O 64 35 3.5
V = 1445.3884
TiNi + 0.5% Ag Quantitative X-ray diffraction analysis of TiNiAg alloys shows an increase in the vol-
B19’
ume fraction of the 22
TiNi martensitic phase- 18
with the B19’ structure, Ti2Ni, Ti4Ni1.2
2O second-

ary phases, and a decrease in the a = 3.0039

fraction of the TiNi austenite phase with the B2
B2 14 20 4.3structure
V = 27.1054
with increasing silver content (Table 1 and Figure 2a).

Figure
Figure 2.
2. Concentration
Concentrationdependence
dependenceaccording
according to
tothe
theresults
resultsof
ofX-ray
X-raydiffraction
diffractionanalysis
analysisof
ofTiNiAg:
TiNiAg:
(a)
(a) volume
volume fraction
fraction of
of the
the phases;
phases; (b)
(b) CSR
CSR values;
values; (c)
(c) microdistortions.
microdistortions.

TableQuantitative
1. X-ray analysis of TiNiAg
X-ray alloys.analysis showed microdistortions of all the phases in
diffraction
the TiNiAg alloy system. It can be assumed, and it follows from
Volume Lattice Parameters CSR
Table 1, that silver is
Microdistortions,
Sample Detected Phases Fraction, Å, and Unit Cell Dimensions,
Δd/d, 10−3
vol.% Volume, Å3 nm
a = 11.3414
Ti2Ni + Ti4Ni2O 46 28 2.4
V = 1458.8143
Coatings 2022, 12, x FOR PEER REVIEW 5 of 13
Coatings 2022, 12, x FOR PEER REVIEW 5 of 13

Coatings 2023, 13, 24 Quantitative X-ray diffraction analysis showed microdistortions of all the phases 5 ofin
13
Quantitative X-ray diffraction analysis showed microdistortions of all the phases in
the TiNiAg alloy system. It can be assumed, and it follows from Table 1, that silver is
the TiNiAg alloy system. It can be assumed, and it follows from Table 1, that silver is
probably incorporated into the crystal lattice of both the B2 and Ti2Ni phases, since the
probably incorporated into the crystal lattice of both the B2 and Ti2Ni phases, since the
greatest microdistortion of these lattices is observed, especially in the B2 phase (Figure
greatest microdistortion
probably of the
incorporated into these lattices
crystal is observed,
lattice especially
of both the B2 and inTi2the B2 phase
Ni phases, (Figure
since the
2c).
2c).
greatest microdistortion of these lattices is observed, especially in the B2 phase (Figure 2c).
3.1.2.
3.1.2.SEM Study of Polished TiNiAg Samples
3.1.2. SEM
SEM Study
Study of
of Polished
Polished TiNiAg
TiNiAgSamples
Samples
With
Withan increase in the silver content, the porosity of the samples did not change and
With an increase in the silver content,the
an increase in the silver content, theporosity
porosityof
ofthe
thesamples
samplesdid
did not
not change
change and
and
accounted for 62% ± 2% (Figure 3).
accounted
accounted for 62%±
for 62% ± 2% (Figure 3).

Figure 3. The cross-sectional SEM image of SHS–TiNi porous alloys specimens.

Figure3.3. The
Figure The cross-sectional
cross-sectionalSEM
SEMimage
imageof
ofSHS–TiNi
SHS–TiNiporous
porousalloys
alloysspecimens.
specimens.
Apart from titanium
Apart titaniumand andnickel powders,
nickel powders,the the
mixture includes
mixture TiNi powder
includes PN55T
TiNi powder
Apart from titanium and nickel powders, the mixture includes TiNi powder
45OM. It is not
PN55T45OM. possible
It is to distinguish
not possible the TiNi
to distinguish thepowder whichwhich
TiNi powder does not
doesparticipate in the
not participate
PN55T45OM. It is not possible to distinguish the TiNi powder which does not participate
synthesis
in reaction
the synthesis from the
reaction fromTiNithephase
TiNiafter
phase SHS bySHS
after X-raybydiffraction. At the same
X-ray diffraction. time,
At the the
same
in the synthesis reaction from the TiNi phase after SHS by X-ray diffraction. At the same
SEM the
time, study of the
SEM phase
study of and elemental
the phase andcomposition of porous alloys
elemental composition made italloys
of porous possible
madeto do
it
time,Phase
this. the SEM
1 study of
enriched thenickel
with phaseforms
and elemental
a residual composition
skeleton of of inert
the porous alloysparticles
powder made it
possible to do this. Phase 1 enriched with nickel forms a residual skeleton of the inert
possible
which to do this. Phase
partially 1 enriched with nickel forms a residual skeleton of the inert
powder particlesdissolve in the
which partially reaction
dissolvemelt (Figure
in the 4, Table
reaction melt2).
(Figure 4, Table 2).
powder particles which partially dissolve in the reaction melt (Figure 4, Table 2).

(a) (b)
(a) (b)
Figure 4. SEM image (a) and EDS elemental mapping (b) of initial porous TiNi alloy..
Figure4.4. SEM
Figure SEM image
image(a)
(a)and
andEDS
EDSelemental
elementalmapping
mapping(b)
(b)of
ofinitial
initialporous
porousTiNi
TiNialloy.
alloy..

Table 2. Elemental composition of phases in TiNi SHS alloys.

Table2.2.Elemental
Table Elementalcomposition
compositionof
ofphases
phasesininTiNi
TiNiSHS
SHSalloys.
alloys.
Identification
Identification Ti,Ti,
at.%
at.% Ni,Ni,
at.%
at.% O,
O,at.%
at.%
Identification Ti, at.% Ni, at.% O, at.%
TiNi (inert) 40.57 59.43 0
TiNi matrix 49.36 50.64 0
Ti2 Ni 56.2 36.87 6.93
 Coatings 2022, 12, x FOR PEER REVIEW 6 of 13
Coatings 2022, 12, x FOR PEER REVIEW 6 of 13

Coatings 2023, 13, 24 TiNi (inert) 40.57 59.43 6 of0 13

TiNi (inert) 40.57 59.43 0
TiNi matrix 49.36 50.64 0
TiNi matrix 49.36 50.64 0
Ti2Ni 56.2 36.87 6.93
Ti2Ni 56.2 36.87 6.93
The presence of silver in the form of light inclusions up to 0.1 µm was detected on the
The presence of silver in the form of light inclusions up to 0.1 µm was detected on
SEM–EDS maps
The presence of of element
silver in thedistribution
form of lightin porous SHS
inclusions up toalloys
0.1 µmTiNi
was+detected
0.2% Ag, onTiNi + 0.5%
the SEM–EDS maps of element distribution in porous SHS alloys TiNi + 0.2% Ag, TiNi +
theAg
SEM–EDS
(Figuresmaps
5 andof element
6, Tables distribution
3 and 4). in porous
The SHS alloys
localization of TiNiparticles
silver + 0.2% Ag,is TiNi +
predominantly on
0.5% Ag (Figures 5 and 6, Tables 3 and 4). The localization of silver particles is predomi-
0.5%
theAg (Figuresof5 the
particles and Ti6,2Tables
Ni or 3 and
Ti 4 Ni2
4).
O The localization
phases. of silver particles is predomi-
nantly on the particles of the Ti2Ni or Ti4Ni2O phases.
nantly on the particles of the Ti2Ni or Ti4Ni2O phases.

5. SEM Figure
image and5. SEMelemental
EDS image andmapping
EDS elemental
ofSHSmapping
porous ofTiNi
porous SHS TiNi + 0.2% Ag.
Figure
Figure 5. SEM image and EDS elemental mapping of porous TiNi SHS
+ 0.2% Ag.+ 0.2% Ag.

Coatings 2022, 12, x FOR PEER REVIEW 7 of 13

Figure 6. SEM image and EDS elemental mapping

Figure 6. mapping of
of porous
porous SHS
SHS alloy
alloy TiNi
TiNi++ 0.5%
0.5% Ag.
Ag.

Table 3. Elemental composition of phases in SHS alloys TiNi + 0.2% Ag.

Identification Ti, at.% Ni, at.% O, at.% Ag, at.% Ca, at.%
TiNi matrix 51.18 48.82 - - -
 Figure 6. SEM image and EDS elemental mapping of porous SHS alloy TiNi + 0.5% Ag.
Coatings 2023, 13, 24 7 of 13
Table 3. Elemental composition of phases in SHS alloys TiNi + 0.2% Ag.

Identification Table 3. Elemental

Ti, at.% composition
Ni, at.% O, at.% Ag, at.%
of phases in SHS alloys TiNi + 0.2% Ag.
Ca, at.%
TiNi matrix 51.18 48.82 - - -
Ti2Ni Identification
59.55 Ti, at.%
29.84 Ni, at.%
10.09 O, at.%
0.52 Ag, at.%- Ca, at.%

Ag TiNi matrix
0.41 51.18 0.29 48.824.23 - 89.06 - 6.01 -
Ti2 Ni 59.55 29.84 10.09 0.52 -
Ag 0.41 0.29 4.23 89.06 6.01
Table 4. Elemental composition of phases in SHS alloys TiNi + 0.5% Ag.

Identification Table 4. Elemental

Ti, at.% composition
Ni, at.%
of phases inO, at.%
SHS Ag,+at.%
alloys TiNi 0.5% Ag. Ca, at.%
TiNi matrix 28.75
Identification
71.19
Ti, at.%
-
Ni, at.%
0.05
O, at.%
-
Ag, at.% Ca, at.%
Ti2Ni 51.2 48.73 - 0.1 -
TiNi matrix 28.75 71.19 - 0.05 -
Ag 0.41
Ti2 Ni
0.2951.2 4.23
48.73 89.06
- 6.01
0.1 -
AgxCay Ag
- - 0.41 0.29
- 4.23
x 89.06
y 6.01
Agx Cay - - - x y
Ag (Ag9Ca2, Ag7Ca2) Ag (Ag Ca- , Ag Ca ) - - -- 96.03
-
3.97
96.03 3.97
9 2 7 2

Silver was found not only in the form of subnanocrystalline particles but also in the
Silver was found not only in the form of subnanocrystalline particles but also in
composition of larger, up to 7 µm, intermetallic inclusions of the Ca–Ag system (Figures
the composition of larger, up to 7 µm, intermetallic inclusions of the Ca–Ag system
7 and 8). Calcium is (Figures
a residual technological
7 and 8). Calcium isimpurity,
a residual which is usedimpurity,
technological in the production
which is usedofin the produc-
titanium powder bytion calcium hydride reduction. Elemental EDS mapping showed the
of titanium powder by calcium hydride reduction. Elemental EDS mapping showed
presence of Ca and Ag in the form
the presence ofand
of Ca inclusions
Ag in theofform
5–10ofµm. Most of 5–10
inclusions the inclusions
µm. Most ofare
theininclusions are
in thecompound
the form of the chemical form of the chemical compound Ag
AgxCay containing Agx Ca y containing
less than 1 µm.Ag less than 1 µm.

EER REVIEW 8 of 13

Figure 7. SEM image of the microstructure and EDS mapping of the element composition of the pure
Figure 7. SEM image of the microstructure and EDS mapping of the element composition of the
silver phase in the porous TiNi + 0.5% Ag alloy.
pure silver phase in the porous TiNi + 0.5% Ag alloy.
Ag and Ca form a number of chemical compounds [25] which contain some of the
detected Ag in a dissolved state. Some amount of the unreacted Ag was found in a free
state or in the compound with the predominant content of silver, Ag9 Ca2 , Ag7 Ca2 .
Coatings 2023, 13, 24 8 of 13

The results of the EDS mapping of TiNiAg (0.2–0.5) samples showed that inclusions
containing silver are located mainly in the zones of Ti2 Ni peritectic crystallization. The
temperature of Ti2 Ni peritectic crystallization is about 950 ◦ C, while the crystallization of
Figure 7. SEM
all Ag–Ca image
system of theoccurs
compounds microstructure
in the rangeand EDS mapping
of 750–910 ◦ C. With anof the element
increase in the comp
pure silver phaseininthe
Ag concentration the porous
alloy from TiNi + 0.5%,
0.2% to 0.5% the
Agsize
alloy.
of agglomerates from inclusions
containing Ag increases from 0.2 to 6 µm (Table 5 and Figure 8).

Figure 8. The dependence of the particle size containing silver on the Ag dopant concentration.
Figure 8. The dependence of the particle size containing silver on the Ag dopant conc
Table 5. The size of agglomerates of inclusions with silver.
AgSample
and Ca form a number Min, µm
of chemical compounds Average,
Max, µm
[25] which
µm
contain
detected Ag in a dissolved0.19state. Some amount
TiNi + 0.2% Ag 1.619
of the unreacted0.81
Ag was fou
state TiNi
or in theAg
+ 0.5% compound 0.542 with the predominant 5.962 content of silver,1.79 Ag9Ca2, Ag
The results of the EDS mapping of TiNiAg (0.2–0.5) samples showed th
3.1.3. TEM Image and EDS Elemental Mapping of Cross-Section of TiNiAg Alloy
containing silver are located mainly in the zones of Ti2Ni peritectic crystall
According to the results of transmission electron microscopy of TiNiAg(0.2–0.5) sam-
temperature of Ti2Ni peritectic crystallization is about 950 °C, while the cryst
ples in the cross-section geometry, silver was found in the form of nanoparticles up to
all10Ag–Ca
nm in thesystem compounds
surface layer of Ti4 Ni2 Ooccurs in Moreover,
(Figure 9). the rangethey of were
750–910
found°C.not With
in ag- an in
Agglomerates, but in thein
concentration form
theofalloy
isolated particles
from 0.2% evenly distributed
to 0.5%, over the
the size entire surface
of agglomerates from
layer. Importantly, silver was found in the matrix in large inclusions up to 2 µm. Other
containing Ag increases from 0.2 to 6 µm (Table 5 and Figure 8).
authors have found Ag in the form of dispersed particles on the surface of ternary TiNiAg
alloys [13,14], and also [4,26] showed the solubility limit of silver in a TiNi solid solution
Table
up to 5. The
0.26 size of agglomerates of inclusions with silver.
wt.%.
The mechanical properties of porous alloys were studied under a compression loading
scheme. TheSample
stress–strain dependence of theMin, µmsystem alloysMax,
TiNiAg µm
is characterized by Aver
the absence of a martensitic plateau, and the porous alloy deforms elastoplastically. With
TiNi + 0.2% Ag 0.19 1.619
an increase in the silver content, the strength properties do not change and the ultimate
0
strengthTiNi
is 70 +±0.5%
4 MPaAg(Figure 10 and Table 0.542 5.962 from 26 to
6). The elastic limit decreases 1
11.5 MPa, the elastic modulus decreases from 1700 to 950 MPa. The maximum strain to
fracture in compression of porous TiNiAg alloys increased from 7% to 27% with increasing
3.1.3.
silverTEM Image and
concentration. SEMEDS
imagesElemental
of fracture Mapping of after
surfaces taken Cross-Section
compression of TiNiAg A
testing
showed that the alloy
According to with
the the silver of
results content 0.2 at.% and 0.5
transmission at.% is partially
electron in a martensitic
microscopy of TiNiAg(0
state, which can be proved by the presence of the areas of quasi-cleavage and plastic
ples in the cross-section geometry, silver was found in the form of nanoparti
shear traces.
nm in the surface layer of Ti4Ni2O (Figure 9). Moreover, they were found no
erates, but in the form of isolated particles evenly distributed over the entire s
Importantly, silver was found in the matrix in large inclusions up to 2 µm. O
have found Ag in the form of dispersed particles on the surface of ternary Ti
 Coatings 2022, 12, x FOR PEER REVIEW
Coatings 2023, 13, 24 9 of 13

(a)

(b)
Figure 9.Figure 9. TEM
TEM image image of
of TiNiAg TiNiAg
sample sample
in the in the geometry
cross-section cross-section geometry
(a); TEM–EDS (a); TEM–EDS
elemental
mappingping of TiNiAg
of TiNiAg matrix (b).
matrix (b).

3.2. Discussion
The mechanical properties of porous alloys were studied under a com
Silver dissolves in the TiNi(B2) phase of the porous alloy to a limited extent, up to
0.1 at.%,ing scheme.
although otherThe stress–strain
authors dependence
found that the solubility of of theinTiNiAg
silver system
the cast alloy doesalloys
not is ch
the at.%
exceed 0.26 absence ofSilver
[13,14]. a martensitic
crystallizesplateau,
in its pureand
form.the porous
Silver alloy
particles deforms
were found inelastopl
the matrix in the zones of peritectic crystallization
an increase in the silver content, the strength of the Ti 2 Ni phase in the form
properties do not of large
change an
particles. In the surface Ti4 Ni2 O layer, silver particles crystallized in the nanocrystalline
strength is 70 ± 4 MPa (Figure 10 and Table 6). The elastic limit decreases f
state evenly over the entire surface layer.
MPa, the elastic modulus decreases from 1700 to 950 MPa. The maximum str
in compression of porous TiNiAg alloys increased from 7% to 27% with in
concentration. SEM images of fracture surfaces taken after compression te
that the alloy with the silver content 0.2 at.% and 0.5 at.% is partially in a ma
which can be proved by the presence of the areas of quasi-cleavage and
traces.
Coatings 2023,
2022, 13,
12, 24
x FOR PEER REVIEW 1010of
of 13

Figure 10. The

Figure 10. The fracture
fracture surface
surface of
of the alloy sample
the alloy sample for TiNi +
for TiNi + 0.2%
0.2% Ag
Ag (a); TiNi +
(a); TiNi + 0.5%
0.5% Ag
Ag (b); σ-ε
(b); σ-ε
dependence for the alloys of the TiNiAg system (c).
dependence for the alloys of the TiNiAg system (c).

Table 6. Mechanical properties of porous TiNiAg alloys.

Table 6. Mechanical properties of porous TiNiAg alloys.
Alloys E, MPa σу, MPa σb, MPa εb, % P, %
Alloys E, MPa σy , MPa σb , MPa εb , % P, %
TiNi 1733 26 71.5 6.8 62
TiNi +TiNi
0.2% Ag 1733
1000 15 26 70 71.5 16 6.8 62
63
TiNi + 0.2% Ag 1000 15 70 16 63
TiNi
TiNi +0.5%
+ 0.5% Ag
Ag 958.3
958.3 11.511.5 74 74 27 27 62
62
WhereE—modulus
Where E—modulus of elasticity;
of elasticity; σy—elastic
σy —elastic limit; σlimit; σb—compressive
b —compressive strength; strength; εb—maximum
εb —maximum deformation defor-
during
compression
mation up to
during fracture; P—porosity.
compression up to fracture; P—porosity.

Out of the three alloying elements, Ag is known to have a significantly different

3.2. Discussion
electronic
Silverstructure
dissolvescompared to Ni and
in the TiNi(B2) phaseTi.of
Moreover,
the porousAgalloy
atoms
to significantly differ
a limited extent, upintosize
0.1
in comparison with Ni atoms. Thus, different electron shell structures of the
at.%, although other authors found that the solubility of silver in the cast alloy does Ag, Ni, andnot
Ti
atoms cause the difference in the structure of the binary state diagrams of the Ag-Ni,
exceed 0.26 at.% [13,14]. Silver crystallizes in its pure form. Silver particles were found in Ag-Ti,
andmatrix
the Ni-Ti systems. Theofbehavior
in the zones peritecticofcrystallization
the electronicofsubsystem correlates
the Ti2Ni phase in thewith
formtheofphase
large
diagrams of the binary Ti-Ag alloy state, in which Ti and Ag in the Ti-Ag system
particles. In the surface Ti4Ni2O layer, silver particles crystallized in the nanocrystalline can form
solid evenly
state solutions
overbased on the
the entire initiallayer.
surface components (Ag), (αTi), (βTi) and two intermetallic
compounds AgTi and AgTi2 at 1020 ± 5 and 940 ◦ C. In the Ni-Ag system with a simple
Out of the three alloying elements, Ag is known to have a significantly different elec-
monotectic system, Ni and Ag are practically insoluble in each other on the state diagram.
tronic structure compared to Ni and Ti. Moreover, Ag atoms significantly differ in size in
The maximum solubility of Ni in Ag is 0.102 at.%, and the maximum solubility of Ag in Ni
comparison with Ni atoms. Thus, different electron shell structures of the Ag, Ni, and Ti
is about 1 at.% and decreases with decreasing temperature [4,6,27–29].
atoms cause the difference in the structure of the binary state diagrams of the Ag-Ni, Ag-
In the Ag-Ti system, there are solid solutions based on alloy-forming elements (Ag),
Ti, and Ni-Ti systems. The behavior of the electronic subsystem correlates with the phase
(αTi), and (βTi) with wide areas of homogeneity (Figure 1) [27,28]. Moreover, the solubility
diagrams of the binary Ti-Ag alloy state, in which Ti and Ag in the Ti-Ag system can form
of Ag in (βTi) reaches 15 at.% at 1020 ◦ C. The solubility of Ti in (Ag) is much lower
solid solutions based on the initial components (Ag), (αTi), (βTi) and two intermetallic
and corresponds to 5 at.%. In the area of stoichiometric compositions Ag2 Ti and AgTi,
compounds AgTi and AgTi2 at 1020 ± 5 and 940 °C. In the Ni-Ag system with a simple
Coatings 2023, 13, 24 11 of 13

peritectic reactions form compounds with tetragonal syngonies with space symmetry
groups I4/mmm and P4/ptt, respectively. In the Ag-Ti system, the eutectoid transformation
(βTi)↔(αTi) + AgTi2 takes place on the Ti side. On the Ag side, a eutectic transformation is
observed.
The phase diagram of Ag-Ni is characterized by the presence of monotectic and eutectic
equilibria [29] (Figure 1). The eutectic point is located at a composition of 99.679 at.% Ag
at 960 ◦ C. Ni in Ag dissolves very slightly (on the order of 0.1 at.%). The maximum
solubility of Ag in Ni is not high and amounts to ~1 at.%, and it decreases with decreasing
temperature.
The state diagram of the Ti-Ni binary system is characterized by the formation of
three intermetallic compounds Ti2 Ni, TiNi, and TiNi3 . Three compounds are formed in the
system: Ti2 Ni, TiNi, and TiNi3 . The Ti2 Ni compound is formed by a peritectic reaction. The
TiNi and TiNi3 compounds crystallize from the melt with an open maximum. The TiNi
compound has a homogeneity area which has a width range from 49.5 to 57 at.% Ni at
1118 ◦ C and with decreasing temperature the area width narrows. There are three eutectic,
one peritectic, and one eutectoid transformations in the Ni-Ti system. The solubility of Ni
in Ti depends on the crystal structure and reaches 8 at.% in (βTi). Whereas in (αTi) the
solubility of Ni is not high and is equal to 0.2 at.%. The (Ni) based solid solution region
is quite wide and reaches a maximum value of 13.9 at.% at a temperature of 1304 ◦ C and
narrows with decreasing temperature.
According to the results of mechanical testing of porous TiNiAg alloys, a similar effect
on mechanical characteristics was found in the study of the effect silver has on TiNiAg
wires [4]. The study revealed an improvement in the mechanical characteristics of alloys in
TiNiAg wires with an increase in the silver content [21]. In the studied case, an increase in
plasticity can be associated with the change in the ratio of titanium and nickel in the B2
phase. The change in the matrix composition results in martensite formation, which causes
plastic strain when the alloy is deformed at room temperature. The increase in plasticity is
apparently caused by the appearance of a secondary Ag phase in the alloy matrix, which is
softer and more plastic.
Studies of the structure and mechanical properties of porous NiTi alloys doped with
silver have shown positive prerequisites for further research. Moreover, in the future,
studies of physical properties, superelastisity effect, biocompatibility, and antibacterial
effect of porous TiNiAg alloys will be carried out, which are important characteristics for
the use of the alloy for medical purposes.

4. Conclusions
Quantitative X-ray diffraction analysis of the obtained alloys showed that an increase
in the silver content is accompanied by a quantitative decrease in the austenite phase
TiNi(B2) and an increase in the martensite phase TiNi(B19’), as well as in secondary phases
Ti2 Ni, Ti4 Ni2 O. Microdistortions of all the phases in the TiNiAg alloy system indicate that
silver is incorporated into the crystal lattice of both the B2 and Ti2 Ni phases. EDS analysis
showed that silver dissolves in the TiNi(B2) phase of the porous alloy to a limited extent,
up to 0.1 at.%.
The results of the EDS mapping of TiNiAg samples with 0.2 and 0.5 at.% Ag showed
that inclusions containing silver are located mainly in the zones of Ti2 Ni peritectic crystal-
lization. With an increase in the Ag concentration in the alloy from 0.2% to 0.5%, the size of
agglomerates from inclusions containing Ag increases from 0.2 to 6 µm. In the surface layer
of the Ti4 Ni2 O phase, evenly distributed silver nanoparticles up to 10 nm were found.
It was found that with an increase in the volume fraction of silver, the plastic properties
of the alloy increase, while the compressive strength does not change and accounts for
70 ± 4 MPa. Obviously, the increase in the plasticity of the porous TiNi alloy from 7% to
27% is caused by the formation of soft and plastic inclusions with silver in the matrix of the
TiNi alloy.
Coatings 2023, 13, 24 12 of 13

Author Contributions: Conceptualization, V.L. and Y.Y.; methodology, V.L. and A.M.; validation,
E.M. and G.B.; formal analysis, V.L., A.M. and Y.Y.; investigation, V.L., G.B. and A.M.; resources, E.M.;
writing—original draft preparation, V.L., A.M. and Y.Y.; writing—review and editing, E.M. and G.B.;
visualization, G.B.; project administration, E.M. All authors have read and agreed to the published
version of the manuscript.
Funding: This study was supported by the Tomsk State University Development Programme
(Priority-2030).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: The structure research was carried out with the equipment of Tomsk Regional
Core Shared Research Facilities Center of National Research Tomsk State University (Grant of the
Ministry of Science and Higher Education of the Russian Federation No. 075-15-2021-693 (No.
13.RFC.21.0012)).
Conflicts of Interest: The authors declare no conflict of interest.

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