metals

Article
Experimental Continuous Casting of Nitinol
Gorazd Lojen 1 , Aleš Stambolić 2 , Barbara Šetina Batič 2 and Rebeka Rudolf 1, *
1 Faculty of Mechanical Engineering, University of Maribor, Smetanova ulica 17, 2000 Maribor, Slovenia;
gorazd.lojen@um.si
2 Institute of Metals and Technology, Lepi pot 11, 1000 Ljubljana, Slovenia; ales.stambolic@imt.si (A.S.);
barbara.setina@imt.si (B.Š.B.)
* Correspondence: rebeka.rudolf@um.si; Tel.: +386-(2)-220-7865




Received: 10 March 2020; Accepted: 10 April 2020; Published: 14 April 2020


Abstract: Commercially available nitinol is currently manufactured using classic casting methods
that produce blocks, the processing of which is difficult and time consuming. By continuous casting,
wherein molten metal solidifies directly into a semi-finished product, the casting and processing
of ingots can be avoided, which saves time and expense. However, no reports on continuous
casting of nitinol could be found in the literature. In this work, Φ 12 mm nitinol strands were
continuously cast. Using a graphite crucible, smelting of pure Ni and Ti in a medium frequency
induction furnace is difficult, because it is hard to prevent a stormy reaction between Ni and Ti and to
reach a homogeneous melt without a prolonged long holding time. Using a clay-graphite crucible,
the stormy reaction is easily controlled, while effective stirring assures a homogeneous melt within
minutes. Strands of nearly equiatomic chemical compositions were obtained with acceptable surface
quality. The microstructure of strands containing over 50 at. % Ni, consisted of Ti2 Ni and cubic
NiTi, whereas the microstructure of strands containing less than 50 at. % Ni consisted of TiNi3 and
cubic NiTi. This is consonant with the results of some other authors, and indicates that the eutectoid
decomposition NiTi → Ti2 Ni + TiNi3 does not take place.

Keywords: nitinol; shape memory alloy; continuous casting; characterisation; microstructure

1. Introduction
Nitinol describes a group of nearly equiatomic alloys composed of nickel and titanium. The alloy
was developed in the 1970s.
The alloy belongs to a group of materials called shape memory alloys (SMAs).
SMAs exhibit unconventional correlations between strain, stress and temperature, based on
crystallographically-reversible, thermoelastic martensitic transformation. The low-temperature and
the high-temperature phases are, analogously to steel, named martensite and austenite. Austenite
has a cubic (B2) structure [1]; martensite has a monoclinic B19’ structure [1]. High cooling rates are
necessary to prevent the decomposition of austenite into at-equilibrium low-temperature phases and
to inforce martensitic transformation instead. However, since the martensitic transformation of SMAs
is crystallographically reversible, high cooling rates are necessary only the first time. Once martensite
is formed, further martensitic transformations are possible at any temperature-change rate, and upon
cooling and heating.
Depending on temperature, stress state and deformation state, several different phenomena can
occur, the most interesting being pseudoplastic deformation, one-way shape memory effect, two-way
shape memory effect and superelasticity. In the martensitic state, apparently plastic deformation based
on coalescence of martensitic variants, practically without dislocation glide, is possible—pseudoplastic
deformation. Upon heating above the austenite start temperature, a pseudoplastically deformed element

Metals 2020, 10, 505; doi:10.3390/met10040505 www.mdpi.com/journal/metals

Metals 2020, 10, 505 2 of 14

starts to recover its original shape—one-way shape memory effect. With special thermomechanical
treatments called training, it can be achieved that a part made of SMA changes its shape, not only
upon heating, but also upon cooling—two-way shape memory effect. In the austenitic state, SMAs are
capable of unusually large elastic deformations, which is enabled by stress-triggered transformation:
austenite → martensite—superelastic deformation. Upon unloading, transformation takes the reverse
course and the material recovers its original shape. In different products, components are needed that
are capable of sensing and responding, movement (stroke), mechanical work/force, energy absorption,
vibration damping, etc. Using SMAs, many such components can be built without electronic controllers,
switches, motors, gears, moving parts, bearings, lubrication, mechanical wear, etc. Consequently,
the devices are simpler and use less material, and fewer different kinds of materials are needed to build
certain devices; less or no energy is needed for operation; operation is more reliable; and, after the end
of their life time, recycling is easier and more efficient.
Beside shape memory properties and superelasticity, nitinol exhibits good corrosion resistance,
an unusual combination of high strength and high ductility, a strong tendency toward
self-passivation, paramagnetic properties, high fatigue strength, low Young’s modulus and excellent
biocompatibility [2–4]. Such a unique combination of properties has enabled its use [5], especially for
biomedical purposes, first in orthodontic treatments; and later on in cardiovascular surgery for stents,
guide wires, filters, etc.; in orthopaedic surgery for various staples and rods; and in maxillofacial and
reconstructive surgery [6,7]. Moreover, nitinol is used in aerospace, automotive, marine and chemical
industries, and civil and structural engineering [8–12].
Nitinol manufacturing is a very complex process. Titanium has a high melting point, low fluidity
(high viscosity) and a susceptibility to oxidation at high temperatures. These properties make Ti and
its alloys difficult to cast. As molten nitinol is highly reactive, it is commonly produced by vacuum
induction melting (VIM) or vacuum arc melting (VAR) [7,13] and cast into ingots. Processing of
ingots into semi-finished products involves a number of secondary processing methods and finishing
techniques [7,8,14], among them deformation and recrystallisation, whereby the microstructure is
refined [13,14]. Further operations, such as machining and post-processing (e.g., heat treatments or
surface treatments) are necessary to create finished components of the desired shape and properties,
and to incorporate those components into tools and devices [13,14]. Difficult machining and poor
workability due to its high strength, ductility and high work hardening are limiting its wider use [15].
Machining of nitinol is characterised by severe tool wear, high specific cutting energy and high strain
hardening. Furthermore, functional properties are very sensitive to machining parameters [16].
To reduce the production time and costs, alternative processes can be an advantage. Relatively
old alternatives to the classic route are casting and classic powder metallurgy (compressing powders
into green products and sintering). However, the possibilities of these processes with respect to the
shape of the products are quite limited. Compression of powders into green parts is possible only
for relatively simple shapes, and pore-free products can not always be obtained [17]. Today, the most
versatile alternative is additive manufacturing (AM), including selective laser melting, electron beam
melting and wire-arc additive manufacturing. Additive manufacturing has significant advantages in
the production of very complexly-shaped construction parts and prototypes, and a very small series
of parts. In general, the static mechanical properties of AM metallic materials are comparable to
conventionally fabricated metallic components [18]. Nearly fully dense products can be fabricated
with optimum combinations of process parameters [19]. Even the high standards of the aerospace
industry can be met [20]. Nevertheless, it is still a challenge to produce a flawless product with
the intended characteristics [21], and the building orientation has an impact on the mechanical
properties [22]. Besides, in spite of the high quality of AM parts, post-processing involving hot working,
cold working [17], conventional machining [23], heat treatments and surface treatments, enhances
the shape memory properties [24], corrosion resistance and biocompatibility. By appropriate surface
treatments, corrosion resistance can be improved significantly [25].
Metals 2020, 10, 505 3 of 14

In the production of wires, rods, tubes and thin sheets, the above-described alternative
processes cannot be applied. Such products are still produced by casting, rolling and drawing
(wires). If the production starts with thick ingots, numerous stages of rolling and intermediate
annealing are necessary to obtain the desired semi-finished product, which is time consuming and
expensive. In such a case, continuous casting can be the preferable alternative to ingot casting.
By continuous casting, wherein molten metal solidifies directly into a semi-finished product of
a relatively small cross-section, casting of ingots and several following processing steps can be
avoided, which saves time and expense [8,26,27]. Solidification is much faster, and takes place under
stationary conditions, which refines the microstructure and improves the homogeneity of the castings
significantly. Continuously cast products usually have simply-shaped cross-sections. However,
by using adequately shaped moulds, quite complex-shaped cross-sections can also be realised [28].
Nevertheless, the majority of nitinol wires, thin sheets and similar products are still produced by
the conventional route, starting with the casting of ingots. Suzuki et al. [29] studied ductility and
other properties of nitinol and some other Ti-based alloys at high temperatures, and suggested that
titanium alloys could be produced successfully by continuous casting. However, only twin roll casting
of wide bands was realised [30], while successful continuous casting of nitinol into strands has not yet
been reported.
Our objective was to research the feasibility of continuous casting of a 50Ni-50Ti strand,
which would have properties similar to products that are already on the market. A combination of
vacuum induction melting (VIM) and vertical continuous casting (VCC) was used for this purpose.
A number of experiments were performed, and the microstructures of the obtained strands have been
studied by different characterisation techniques.

2. Materials and Methods

2.1. The Nitinol Preparation

The nitinol was prepared by vacuum induction melting of pure Ni and Ti immediately before
casting. For economic reasons, the metals used in the first two trials were of lower purity, while high
purity metals were used in the third and fourth trials; see Table 1. The target composition was equiatomic,
50 at. % Ni and 50 at. % Ti, which corresponds to 55.08 wt. % Ni and 44.92 wt. % Ti. According to the
most common Ni–Ti phase diagram proposed by Murray [31], at this composition, the alloy solidifies
congruently into a cubic intermetallic compound NiTi at 1310 ◦ C. The eutectoid decomposition of NiTi
into Ti2 Ni and TiNi3 at 630 ◦ C was proposed in older literature [32,33]. Later, Murray [31] considered
the eutectoid reaction as uncertain, while in the newer literature, it was found to be unrealistic [34,35],
or even nonexistent [1]. Anyway, rapid cooling, i.e., quenching, results in martensitic transformation
of the undercooled NiTi. At the equiatomic chemical composition, the martensite start temperature
should be at approximately 47–48 ◦ C [22]. As the difference between the martensite-start and finish
temperature of nitinol alloys does not exceed 20–25 ◦ C [36,37], at room temperature the quenched alloy
should be martensitic and capable of shape memory effect. Usually, nickel contents below 50 at. % are
selected if the goal is to exploit the shape memory effect. Less nickel results in higher transformation
temperatures. If superelasticity should be exploited, the martensite-start temperature must be below
the service temperature range, and usually nickel contents above 50.5 at. % are selected. However,
in the case of continuous casting, it was expected that the cooling rate would be too low for the
martensitic transformation.

2.2. The Continuous Casting Device

Experimental casting was performed with a laboratory scale vertical continuous casting (VCC)
device, Technica Guss, which was connected to the 60 kW medium-frequency (4 kHz) vacuum
induction melting (VIM) furnace Leybold Hereaus. The withdrawal-parameters are programmable,
so an almost arbitrary time-velocity curve can be realised (the limits being set by the performance of
Metals 2020, 10, 505 4 of 14

the motor and inertia of the moving parts). For more details, please see the supplementary file S1
“Continuous_casting_device”.
According to the literature, a graphite crucible is the best choice with respect to contamination of
the melt [38–40], although both Ni and Ti are carbide-forming elements. Namely, a protective layer
of TiC forms quickly on the crucible wall [41], which decelerates further chemical reactions strongly,
and prevents excessive contamination of the melt with carbon. Therefore, a graphite crucible was
selected for the first trial. For the second, third and fourth trials, a clay-graphite crucible was used.
At first sight, it seems logical to combine a graphite crucible with a graphite mould. However,
the conditions in the mould are different than in the crucible. While in the crucible no abrasive wear
takes place, in the mould during each stroke, movement of solidified metal destroys the TiC protective
layer mechanically, and exposes fresh graphite to the melt. In this way, the wear in the upper part of the
mould is much faster than in the lower part, which is not in contact with the melt. The mould becomes
conical and the strand eventually jams. According to our experience with Ni-based superalloys, this can
happen within minutes after the start. In addition, the wear of the mould contributes to contamination
of the strands with carbides. Therefore, a water-cooled copper mould was chosen for the experiments.
Bearing in mind that one of the most important reasons for continuous casting of nitinol is to minimise
time and effort for processing the strands into wires and similar semi-finished products, a mould was
applied with a relatively small diameter d = 12 mm. A yttria-stabilised zirconia nozzle was used in the
first three trials, and an Si3 N4 nozzle in the fourth trial.

2.3. Casting Parameters

The charge was approximately 15 kg. The induction power was 10 kW for the first 10 min;
for the next 10 min 20 kW; and in the final 5 min, 30 kW. Heating was interrupted during the
exothermic reaction between Ni and Ti. During casting, 25–30 kW was necessary to maintain the
casting temperature. Melting was carried out in a vacuum. Just before the start of casting, the chamber
was filled with argon (purity 5.0).
Based on previous experience with Ni-based alloys [42], a withdrawal sequence “pull-pause” and
melt overheating of about 100–150 ◦ C were estimated as appropriate. With respect to the melting point
of equiatomic intermetallic phase NiTi [17], this means a casting temperature in the range 1410–1460 ◦ C.
To minimise the risk of sticking and fracture of the strand in the mould, relatively low casting rates were
selected, and the pulling sequence was programmed with the lowest possible acceleration. The applied
parameter sets are summarised in Table 1.

2.4. Examination of Strands

A visual macroscopic examination was carried out of the surfaces. To estimate the actual chemical
composition, X-ray fluorescence (XRF) chemical analysis of the strands followed, using a Thermo
Scientific Niton XL3t GOLDD+ apparatus (Thermo Fisher Scientific, Waltham, MA, USA). Samples
for microscopy and X-ray diffraction (XRD) were machined from the strands having a chemical
composition near the target. For the optical microscopy, a Nikon Epiphot 300 optical microscope
(Nikon, Tokio, Japan) was used, equipped with an Olympus DP-12 digital camera (Olympus, Boston,
MA, USA). Scanning electron microscopy (SEM) was performed with a JEOL JSM 6500-F microscope
(JEOL, Tokyo, Japan), equipped with an energy dispersive spectrometer (EDS) Oxford INCA X-SIGHT
(Oxford Instruments, Abingdon, UK) and an electron backscattered diffraction (EBSD) detector Nordlys
II (Oxford Instruments, Abingdon, UK). Data processing and analysis were performed with the Oxford
INCA software (Oxford Instruments, Abingdon, UK) suite for EDS measurements and the Channel 5
suite for EBSD measurements. To verify the results of EDS and EBSD analysis, X-ray diffraction was
performed with a PANalytical X’Pert XRD system with a Cu-cathode.
Metals 2020, 10, 505 5 of 14

Table 1. Materials and casting parameters.

Trial (Strand) 1 Trial (Strand) 2 Trial (Strand) 3 Trial (Strand) 4

Base metals purity/wt. Ni 99.8 99.8 99.99 99.99
% Ti Scrap, 99.8 Scrap, 99.8 99.99 99.99
Target composition/wt. Ni 55.08 55.08 55.08 55.08
Metals 2020, 10,%x FOR PEER REVIEW
Ti 44.92 44.92 44.92 44.92 5 of 14
Ni 63.2 56.5 54.6 54.6
2.4.Strands–analysed/wt.
Examination of Strands
Ti 34.4 43.3 45.4 45.4
%
Fe 1.53 0.2 -
A visual macroscopic examination was carried out of the surfaces. To estimate the - actual
chemical composition,
Crucible X-ray fluorescence (XRF) chemical
Electrographite analysis of
Clay-graphite the strands followed,
Clay-graphite using a
Clay-graphite
Thermo Scientific Niton XL3t GOLDD+
Nozzle ZrOapparatus
2
(Thermo
ZrO2 Fisher Scientific,
ZrO2 Waltham, Si MA,
3 N4
USA).
SamplesNozzle
for microscopy
diameter/mm
and X-ray diffraction (XRD) were machined
11.1
from the strands having a
chemical composition near the target. For the optical microscopy, a Nikon Epiphot 300 optical
Mould Copper, water-cooled
microscope (Nikon, Tokio, Japan) was used, equipped with an Olympus DP-12 digital camera
Mould
(Olympus, diameter/mm
Boston, MA, USA). Scanning electron microscopy (SEM) 12.0 mm
was performed with a JEOL JSM
Starter bar tip Steel Steel
6500-F microscope (JEOL, Tokyo, Japan), equipped with an energy dispersive Ti, grade 2 spectrometer
Ti, grade (EDS)
2
Oxford Melt
INCA X-SIGHTC (Oxford Instruments,
temperature/ ◦ 1420 Abingdon,
1420 UK) and 1420 an electron backscattered
1420
diffraction (EBSD) detector
Casting sequence Nordlys II (Oxford Instruments, Abingdon,
Pull-pause UK). Data processing and
analysis were performed with the Oxford INCA software (Oxford Instruments, Abingdon, UK) suite
Stroke/mm 8
for EDS measurements and the Channel 5 suite for EBSD measurements. To verify the results of EDS
Pause/s 0.3 0.3
and EBSD analysis, X-ray diffraction was performed with a PANalytical0.5 X'Pert XRD system0.5
with a
Productivity/mm·min −1 630 630 422 422
Cu-cathode.

3.
3. Results
Results

Casting, Chemical
3.1. Casting, Chemical Composition,
Composition, Surface Quality and Optical Microscopy of Strands
of all,
First of all,both
botha avisual
visualexamination
examination and
and chemical
chemical analysis
analysis of the
of the strands
strands werewere carried
carried out.
out. The
The photographs
photographs of theofstrands
the strands are presented
are presented in Figure
in Figure 1. 1.

Figure 1.
Figure Macro photographs
1. Macro photographs of
of the
the strands.
strands. (a)
(a) Strand
Strand 1;
1; (b)
(b) strand
strand 2;
2; (c)
(c) strand
strand 3,
3, (d)
(d) strand
strand 4.
4.

The actual chemical compositions are summarised in Table 1. Because at the bottom of the crucible
The actual chemical compositions are summarised in Table 1. Because at the bottom of the
the melt dissolves the tip of the starter bar and the mixing in this area is the weakest, the strongest
crucible the melt dissolves the tip of the starter bar and the mixing in this area is the weakest, the
strongest deviation from the target composition was expected in this area. Therefore, all samples for
chemical analysis were taken from the start-end of the strands.
In trial 1, intensive sputtering during melting could not be prevented. The primary witness
marks (regular circumferential grooves on the strands) were very shallow and narrow, and the
surface between them was very smooth. Taking into account that witness marks are unavoidable in
this casting process, the surface of the strand 1, Figure 1a, is excellent. Very shallow and narrow
Metals 2020, 10, 505 6 of 14

deviation from the target composition was expected in this area. Therefore, all samples for chemical
analysis were taken from the start-end of the strands.
In trial 1, intensive sputtering during melting could not be prevented. The primary witness
marks (regular circumferential grooves on the strands) were very shallow and narrow, and the surface
between them was very smooth. Taking into account that witness marks are unavoidable in this casting
process, the surface of the strand 1, Figure 1a, is excellent. Very shallow and narrow witness marks
(regular circumferential grooves on the strands) mean that the temperature was high enough to prevent
solidification deep into the nozzle. The secondary witness marks (less regular circumferential grooves,
located between the primary witness marks) are hardly visible, which means that almost complete
remelting of the edges of the static and dynamic skin was possible. A comprehensive explanation of the
causes and mechanisms of witness mark formation can be found in the literature; e.g., [42]. However,
the analysed chemical composition was far from the target composition; see Table 1. Therefore, strand
1 was not subjected to any further examination.
The sputtering and the inadequate chemical composition in trial 1 can both be attributed to the
crucible material. When producing nitinol by smelting of pure metals, the self-propagating exothermic
reaction between components must be taken into account. In the case of powders, the reaction starts
already in the solid state below 900 ◦ C [43]. When smelting pellets or larger pieces of materials,
the reaction starts approximately at the melting point of nickel. Depending on the furnace and the
crucible material, at the latest at this point, the power should be reduced or cut-off until the reaction is
completed. Otherwise, the reaction will be too stormy, which leads to overheating of the melt and
intensive sputtering all over the furnace. However, in the case of a graphite crucible and a medium
frequency furnace, it is very difficult to find the right moment. Namely, as also reported by other
authors [44], at frequencies around 5 kHz, the magnetic field in the graphite crucible wall is substantially
stronger than inside the crucible. The crucible absorbs most of the power, and heats much faster
than the metallic batch in the crucible. Consequently, power must be cut-off before the reaction starts.
Once it starts it is already too late, because the batch continues to absorb heat from the hot crucible.
The other disadvantage of a weak magnetic field inside the crucible is poor stirring of the melt.
Due to the higher density and lower melting point of nickel compared to titanium, nickel melts first
and flows to the bottom, while solid titanium remains on the top—regardless of how the crucible is
charged. Even after the reaction between Ni and Ti and melting is completed, due to poor stirring,
the Ti-concentration remains much higher on the top for a long time. Prolongation of holding time
in order to improve homogeneity of the melt is not a good option, because the contamination of the
melt with carbon also increases with time [41]. Therefore, the first part of strand 1 contained far too
much Ni, while the Ti-concentration was too high, closer to the surface of the melt in the crucible.
Other possible reasons for inadequate composition, which, however, cannot cause such significant
deviations, are: evaporation of liquid metals in the vacuum; burn-off due to residual oxygen in the
protective atmosphere; errors in weighing of the batch; and the use of scrap in the first two trials,
which means that the weighed mass included not only pure metals, but also some impurities, mostly
oxides, the majority of which formed the slag. The extremely high Fe-concentration in the start-end
of strand 1 can also be explained only with a highly inhomogeneous melt due to insufficient mixing.
Namely, so much iron could not originate either from the Ti-scrap or from nickel, although Fe is
a common impurity in both of them. The other source of iron was the starter bar tip. Some material
from the starter bar tip always dissolves in the melt. In the case of strand 1, approximately 3 mm of
an M8-threaded pin dissolved, which corresponds to approximately 1 g of steel and a concentration of
0.007 wt. % Fe in 15 kg of homogeneous melt. However, to reach a concentration of over 1.5 wt. % Fe,
almost 230 g Fe would be necessary. Consequently, the only possible explanation is that stirring was
too weak, and that practically all the dissolved iron remained at the bottom of the crucible.
For trial 2, a clay-graphite crucible was selected, in order to avoid problems with temperature
control during smelting and insufficient stirring. Due to the poor electric conductivity of the
clay-graphite, the induction power is absorbed predominantly by the metallic batch, while the crucible
Metals 2020, 10, 505 7 of 14

receives the major part of heat from the hot metallic batch. Thus, reduction of power resulted instantly
in reduction of the heat-input into the batch, and too stormy of an exothermic reaction and sputtering
of melt could have been prevented easily. The start of casting in trial 2 was smooth. The surface quality
of the strand was even and quite smooth; see Figure 1b. However, soon after the start, the strand broke.
The rupture occurred on a primary witness mark, approximately 25 mm below the nozzle. Examination
of the strand revealed that, in the moment of rupture, the solid shell was not extremely thin (Figure 2)
yet not strong enough to withstand the pulling force. This indicates that the pulling force probably
increased because the strand was sticking to the mould surface due to excessive reduction of the oxide
layer by the titanium-rich melt. The increasing pulling force in combination with the notch effect due
to witness
Metals marks
2020, 10, x FORfinally led to rupture.
PEER REVIEW 7 of 14

Figure 2. The fracture of strand 2.

The
The chemical
chemicalanalysis
analysisrevealed
revealedthat thethe
that NiNiandand
Ti-contents in trial
Ti-contents 2 were
in trial muchmuch
2 were closercloser
to the totarget
the
than
targetinthan
the previous trial, which
in the previous trial,means
whichthat mixing
means thatofmixing
the meltof in the
the clay-graphite
melt crucible was
in the clay-graphite much
crucible
more efficient
was much than
more in the graphite
efficient than in the crucible.
graphiteFe-content
crucible.was much lower
Fe-content wasthan
much in lower
strandthan
1, butinstill much
strand 1,
too
but high. As intoo
still much trialhigh.
1, in As
trialin2,trial
the iron
1, in content wasiron
trial 2, the too high to be
content caused
was solely
too high to by
be the dissolution
caused solely byof
the
the starter bar tip.
dissolution This
of the indicated
starter thatThis
bar tip. the iron content
indicated thatinthe
at least
iron one of the
content in base metals
at least one was
of thehigher
base
than declared by the supplier. However, since the ratio Ni:Ti was not far from
metals was higher than declared by the supplier. However, since the ratio Ni:Ti was not far from the target, strand 2 was
the
used
target,for further
strand examination.
2 was used for further examination.
The longitudinal
longitudinalsection
section of of
strand 2 was
strand typical
2 was for continuous
typical cast strands
for continuous with a small
cast strands withdiameter;
a small
see Figuresee
diameter; 3. Figure 3.
For trial 3, as shown in Table 1, three changes were made: To improve the chemical composition,
high purity primary-production metals were used, and a grade 2-titanium starter bar tip was mounted
instead of a steel tip. The casting speed was reduced to decrease the temperature in the mould, an,
therewith, the probability of the reaction with the melt. The start was smooth. The strand surface was
a bit rougher than in the previous trials. The appearance of the longitudinal section was practically
identical to the longitudinal section of strand 2—as expected, as the only difference compared to trial 2
was a longer stop between the strokes (Table 1). However, the secondary witness marks were more
distinguished (Figure 1c). Such a surface is not desirable, but it may still be acceptable, as the surface
layer of continuously cast strands is often removed (peeled off) prior to further processing in order to
obtain a flawless surface without defects. The cause for distinguished secondary witness marks was
incomplete remelting of the edges of the static and dynamic skin due to the lower average temperature
in the upper part of the mould. But despite the temperature being lower, it was still too high to prevent
the strand sticking to the mould completely. Figure 4 shows a copper particle sticking to the strand
just below the primary witness mark. The location of the copper-particle indicates that it was torn
off the mould-wall in the uppermost part of the mould, just below the ceramic nozzle, where the
mould-material is exposed to the highest temperatures.

Figure 3. Longitudinal section of strand 2.

For trial 3, as shown in Table 1, three changes were made: To improve the chemical composition,
high purity primary-production metals were used, and a grade 2-titanium starter bar tip was
but still much too high. As in trial 1, in trial 2, the iron content was too high to be caused solely by
the dissolution of the starter bar tip. This indicated that the iron content in at least one of the base
metals was higher than declared by the supplier. However, since the ratio Ni:Ti was not far from the
target, strand 2 was used for further examination.
MetalsThe 10, 505
2020, longitudinal section of strand 2 was typical for continuous cast strands with a small 8 of 14
diameter; see Figure 3.

Metals 2020, 10, x FOR PEER REVIEW 8 of 14

secondary witness marks was incomplete remelting of the edges of the static and dynamic skin due
to the lower average temperature in the upper part of the mould. But despite the temperature being
lower, it was still too high to prevent the strand sticking to the mould completely. Figure 4 shows a
copper particle sticking to the strand just below the primary witness mark. The location of the copper-
particle indicates that it was torn off the mould-wall in the uppermost part of the mould, just below
the ceramic nozzle, where the mould-material
Figure 3.
Figure is exposed
3. Longitudinal
Longitudinal sectionto
section ofthe
of highest
strand
strand 2. temperatures.
2.

For trial 3, as shown in Table 1, three changes were made: To improve the chemical composition,
high purity primary-production metals were used, and a grade 2-titanium starter bar tip was
mounted instead of a steel tip. The casting speed was reduced to decrease the temperature in the
mould, an, therewith, the probability of the reaction with the melt. The start was smooth. The strand
surface was a bit rougher than in the previous trials. The appearance of the longitudinal section was
practically identical to the longitudinal section of strand 2—as expected, as the only difference
compared to trial 2 was a longer stop between the strokes (Table 1). However, the secondary witness
marks were more distinguished (Figure 1c). Such a surface is not desirable, but it may still be
acceptable, as the surface layer of continuously cast strands is often removed (peeled off) prior to
further processing in order to obtain a flawless surface without defects. The cause for distinguished

Figure 4.
Figure 4. Copper
Copper particle
particle below
below aa primary
primary witness
witness mark
mark on
on strand
strand 3.
3.

The temperature
temperature of the the upper
upper part
part of
of the
the mould
mould should
should be be reduced
reduced further
further for
for trial
trial 4.
4. This
This can
can
be achieved
achieved most effectively by decreasing either the casting speed or the temperature of the melt. melt.
However,
However,in inindustrial
industrialproduction,
production,high highproductivity
productivity is desired,
is desired, while
whilethethe
melt temperature
melt temperature was,was,
in the
in
previous trials,trials,
only only
110 C◦ above the melting point. point.
Hence,Hence,the melt-temperature and other casting
the previous 110 °C above the melting the melt-temperature and other
parameters remained
casting parameters the same
remained assame
the in trial
as 3,
inbut,
trialinstead of zirconia,
3, but, instead the nozzle
of zirconia, the was
nozzlemadewasofmadesilicon
of
nitride. The thermal
silicon nitride. conductivity
The thermal of silicon
conductivity nitridenitride
of silicon is, at high
is, attemperatures, more than
high temperatures, morethree
than times
three
higher than that
times higher thanofthat
zirconia [45]. This
of zirconia [45].means that, in
This means trialin4,trial
that, more heat was
4, more heatdissipated from from
was dissipated the meltthe
into the cooler through the nozzle, and, consequently, the temperature of the
melt into the cooler through the nozzle, and, consequently, the temperature of the melt entering themelt entering the mould
was
mouldlower.
wasThe surface
lower. Theofsurface
strand 4ofwas rough4and
strand wasuneven
rough (Figure
and uneven1d). The microscopic
(Figure 1d). Theinvestigation
microscopic of
the longitudinal
investigation of sections revealed that,
the longitudinal during
sections the resting
revealed that, period,
during the the solidification
resting period,front
theintruded more
solidification
than
front1intruded
mm deep into than
more the nozzle
1 mm (Figure
deep into 5a).
theUpon
nozzlethe(Figure
next stroke, the solid
5a). Upon skinstroke,
the next movedthe downwards,
solid skin
from
moved thedownwards,
nozzle into the frommould, which,into
the nozzle as usual, had a slightly
the mould, which, as larger diameter
usual, than thelarger
had a slightly nozzle,diameter
and the
than the nozzle, and the melt started to flow into the gap between the mould and the solid skin which
formed in the nozzle. However, it solidified before the gap was filled completely. Consequently, the
primary witness marks are deep, wide and of irregular shape. In addition, as can be observed in
Figure 5a, the melt in the gap could not remelt the skin which formed in the nozzle. Additionally, at
the secondary witness marks, the edges of the static and dynamic skin were not remelted, and formed
Metals 2020, 10, 505 9 of 14

melt started to flow into the gap between the mould and the solid skin which formed in the nozzle.
However, it solidified before the gap was filled completely. Consequently, the primary witness marks
are deep, wide and of irregular shape. In addition, as can be observed in Figure 5a, the melt in the
gap could not remelt the skin which formed in the nozzle. Additionally, at the secondary witness
marks, the edges of the static and dynamic skin were not remelted, and formed a bond strong enough
to withstand the first stroke after their formation. Therefore, cracks formed at a large number of
secondary witness marks (Figure 5b). Due to the cracks at the witness marks, the strand soon broke
and the trial was interrupted.
Metals 2020, 10, x FOR PEER REVIEW 9 of 14

Figure 5.
Figure 5. Strand
Strand4:4:(a)(a)Primary
Primary witness mark;
witness thethe
mark; distance L marks
distance the approximate
L marks the approximatelength of theofsolid
length the
skin formed
solid whenwhen
skin formed the solidification frontfront
the solidification protruded into the
protruded intonozzle. UponUpon
the nozzle. the following stroke,
the following this
stroke,
skinskin
this remained solidsolid
remained in spite of being
in spite covered
of being with
covered melt
with (indicated
melt byby
(indicated thethe
arrow).
arrow).(b)(b)
Crack
Crackonona
secondary witness mark.
a secondary witness mark.

For a smoother surface with shallow witness marks, the temperature temperature in the mould must be high
enough. Sufficiently
Sufficiently high
high temperature
temperature assures
assures that the solidification front cannot advance into the
nozzle (consequently, no, no, oror very
very shallow
shallow primary
primary witness
witness marks
marks occur).
occur). It also assures complete
remelting of the edges of static static and dynamic skin (consequently, very shallow or almost invisible
secondary
secondary witness
witnessmarks
marksoccur).
occur).However,
However,the temperature
the temperature must notnot
must be too high
be too either.
high It must
either. be low
It must be
enough
low enough to prevent sticking
to prevent to the
sticking tomould. Sticking
the mould. damages
Sticking damagesthe mould
the mouldand and
shortens its service
shortens life.
its service
On
life.the
Onother hand,
the other sticking
hand, increases
sticking increasespulling forces,
pulling andand
forces, therefore, a thicker
therefore, solid
a thicker skin
solid must
skin form
must formto
withstand
to withstand thethe
pulling force
pulling at the
force startstart
at the of the nextnext
of the stroke. To obtain
stroke. a thicker
To obtain solidsolid
a thicker skin,skin,
the cooling rate
the cooling
must increase.
rate must Finding
increase. the optimum
Finding the optimumcombination of casting
combination parameters
of casting and materials
parameters for the crucible,
and materials for the
nozzle
crucible,and mould
nozzle tomould
and fulfil alltothese
fulfilconditions at the same
all these conditions timesame
at the will time
require further
will requireeffort.
further effort.

3.2. SEM and

3.2. SEM and Phase
Phase Analysis
Analysis
Strands
Strands 22and
and3 were subjected
3 were to electron
subjected microscopy
to electron and phase
microscopy andanalysis.
phase Strand 1 had
analysis. inadequate
Strand 1 had
chemical
inadequate chemical composition, and was, therefore, irrelevant. In trial 4, the alloy produced in was
composition, and was, therefore, irrelevant. In trial 4, the alloy produced in trial 3 trial
reused, and therefore,
3 was reused, apart from
and therefore, the
apart worse
from thesurface, no significant
worse surface, differences
no significant compared
differences to strandto
compared 3
were expected.
strand 3 were expected.
The
The microstructure
microstructureofofstrand 2 consisted
strand of three
2 consisted phases.
of three The two-phase
phases. areas prevailed
The two-phase strongly,
areas prevailed
and only some small areas containing a few dark particles of a third phase were observed
strongly, and only some small areas containing a few dark particles of a third phase were observed (Figure 6).
The dark,
(Figure 6).almost blackalmost
The dark, particles were
black identified
particles as Ti-carbides.
were identified asThe EDS analysis
Ti-carbides. Theshowed approximately
EDS analysis showed
approximately 12.6 wt. % C, 84.6 wt. % Ti and 2.9 wt % Ni. The ratio C:Ti corresponded very well to
the TiC, and the EBSD patterns obtained from these particles were also characteristic for cubic TiC.
The grey areas were recognised as cubic NiTi, and the lightest, almost white phase, was identified as
hexagonal Ni3Ti.
Metals 2020, 10, 505 10 of 14

12.6 wt. % C, 84.6 wt. % Ti and 2.9 wt % Ni. The ratio C:Ti corresponded very well to the TiC, and the
EBSD patterns obtained from these particles were also characteristic for cubic TiC. The grey areas were
Metals 2020, 10,asx FOR
recognised PEER
cubic REVIEW
NiTi, and the lightest, almost white phase, was identified as hexagonal Ni310
Ti.of 14

Figure 6.
Figure Microstructure of
6. Microstructure of strand
strand 2:
2: SEM
SEM image. Three phases
image. Three phases were
were observed. Strongly prevailing
observed. Strongly prevailing
cubic NiTi (light grey), hexagonal Ni Ti (almost white), and some small groups of TiC-particles (dark,
cubic NiTi (light grey), hexagonal Ni33Ti (almost white), and some small groups of TiC-particles (dark,
almost black). Kikuchi patterns of these three phases, obtained by the EBSD system, are presented on
almost black). Kikuchi patterns of these three phases, obtained by the EBSD system, are presented on
the top.
the top.

The fact that no carbon was detected with XRF chemical analysis can be explained with the low
The fact that no carbon was detected with XRF chemical analysis can be explained with the low
concentration of carbon, below the detection limit of the method. In spite of the iron-content, no binary
concentration of carbon, below the detection limit of the method. In spite of the iron-content, no
or ternary Fe-compounds were detected, either by XRD or by scanning electron microscopy. This can be
binary or ternary Fe-compounds were detected, either by XRD or by scanning electron microscopy.
explained with the substantial solubility of iron in Ni-Ti compounds, especially in Ni3 Ti and NiTi2 [46],
This can be explained with the substantial solubility of iron in Ni-Ti compounds, especially in Ni3Ti
in which, according to several authors [46,47], iron occupies Ni-sites predominantly.
and NiTi2 [46], in which, according to several authors [46,47], iron occupies Ni-sites predominantly.
In strand 3, only two phases were observed, Figure 7. They were identified as cubic NiTi and
In strand 3, only two phases were observed, Figure 7. They were identified as cubic NiTi and
cubic NiTi .
cubic NiTi22.
XRD analysis confirmed the presence of the phases identified by EBSD in strands 2 and 3. The X-ray
diffractograms are available in the supplementary file S2 “X-ray diffractograms”.
Martensitic Ni-Ti has a monoclinic structure [1], and it was not detected in our strands. The cubic
structure of the detected NiTi indicates that martensitic transformation did not take place. Consequently,
if the eutectoid decomposition is possible at all, it should have taken place, and the microstructure of
all our strands should contain no NiTi, but apart from impurities, solely Ti2 Ni and TiNi3 . However,
strand 2, containing more than 55.08 wt.% (i.e., more than 50 at % Ni) and some iron, consisted of cubic
NiTi, TiNi3 and TiC, while strand 3, containing less than 55.08 wt. % Ni, consisted of cubic NiTi and
Ti2 Ni. Taking into account the analysed chemical compositions, such microstructures are consonant
with the theory that no eutectoid reaction takes place [1,34].

Figure 7. Microstructure of strand 3. SEM image. Two phases were observed. Strongly prevailing
cubic NiTi (grey), cubic NiTi2 (dark, almost black). Kikuchi patterns of NiTi and NiTi2, obtained by
the EBSD system, are presented on the top.

XRD analysis confirmed the presence of the phases identified by EBSD in strands 2 and 3. The
X-ray diffractograms are available in the supplementary file S2 “X-ray diffractograms.”
concentration of carbon, below the detection limit of the method. In spite of the iron-content, no
binary or ternary Fe-compounds were detected, either by XRD or by scanning electron microscopy.
This can be explained with the substantial solubility of iron in Ni-Ti compounds, especially in Ni3Ti
and NiTi2 [46], in which, according to several authors [46,47], iron occupies Ni-sites predominantly.
Metals In
2020, 10, 5053, only two phases were observed, Figure 7. They were identified as cubic NiTi
strand 11 of
and14

cubic NiTi2.

Figure 7.7. Microstructure

Figure Microstructure ofof strand
strand 3.3. SEM
SEM image.
image. Two
Two phases
phases were
wereobserved.
observed. Strongly
Strongly prevailing
prevailing
cubic NiTi (grey), cubic NiTi (dark, almost black). Kikuchi patterns of NiTi and NiTi , obtained
cubic NiTi (grey), cubic NiTi2 (dark, almost black). Kikuchi patterns of NiTi and NiTi2 , obtained by the
2 2 by
the EBSD
EBSD system,
system, are presented
are presented ontop.
on the the top.

4. Conclusions
XRD analysis confirmed the presence of the phases identified by EBSD in strands 2 and 3. The
X-rayThe
diffractograms are conclusions
following main available in can
the supplementary file S2
be drawn from this “X-ray diffractograms.”
study:
(1) Smelting of pure Ni and pure Ti in a medium frequency VIM furnace using a graphite crucible
is difficult. The crucible heats much faster than the metallic batch, and therefore, it is hard to prevent
a stormy exothermic reaction between the Ni and Ti and excessive sputtering.
(2) Stirring of the melt in a graphite crucible in a medium frequency VIM furnace is rather
inefficient. Therefore, if nitinol is produced by smelting of pure metals, the alloy is inhomogeneous.
(3) Utilisation of a clay-graphite crucible solves the problem of energy-input control efficiently
during the exothermic reaction, and facilitates efficient stirring of the melt. However, the acceptability
of clay-graphite with respect to melt purity remains to be confirmed by chemical analysis-methods
with lower detectability limits for carbon and oxygen than used in this research.
(4) Continuous casting of nitinol strands of a relatively small diameter, 12 mm, and acceptable
surface quality directly from the melting crucible, was possible. Yet, finding the optimum combination
of casting parameters and materials for the crucible, nozzle and mould, requires further effort.
(5) The microstructures of continuously cast nitinol strand 2 consisting of Ti2 Ni and cubic NiTi,
and strand 3 consisting of TiNi3 and cubic NiTi, support the theory that the eutectoid decomposition
NiTi → Ti2 Ni + TiNi3 at 630 ◦ C does not exist.

Supplementary Materials: Supplementary files are available online at http://www.mdpi.com/2075-4701/10/4/505/s1.

Supplementary information S1: Continuous casting device. Supplementary information S2: X-ray diffractograms.
Author Contributions: This article was conceptualised by G.L., A.S. and R.R.; methodology, G.L. and R.R.;
validation, G.L., A.S. and R.R.; formal analysis, B.Š.B.; investigation, G.L., A.S. and R.R.; writing—original draft
preparation, G.L., A.S. and R.R.; writing—review and editing, G.L., A.S. and R.R.; supervision, R.R.; project
administration, R.R.; funding acquisition, R.R. All authors have read and agreed to the published version of
the manuscript.
Funding: This research was partially funded by the Slovenian Research Agency, Infrastructure Core Funding
number I0-0029, Research Core Funding number P2-0120 and Applied Project L2-5486.
Acknowledgments: The authors thank Črtomir Donik for performing the XRD analyses at the Institute of Metals
and Technology, Ljubljana, Slovenia. The authors also thank the companies Magneti Ljubljana d.d. Slovenia and
Akrapovič d.d. Ivančna Gorica, Slovenia for supporting this study by providing nickel and titanium.
Conflicts of Interest: The authors declare no conflict of interest.
Metals 2020, 10, 505 12 of 14

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