JMEPEG (2014) 23:2362–2367 The Author(s). This article is published with open access at Springerlink.

com
DOI: 10.1007/s11665-014-1068-7 1059-9495/$19.00

Microstructure, Phase Transformations, and Properties

of Hot-Extruded Ni-Rich NiTi Shape Memory Alloy
Z. Lekston, M. Zubko, K. Prusik, and D. Stróz_

(Submitted October 14, 2013; in revised form May 4, 2014; published online May 23, 2014)

Processing of NiTi shape memory alloys strongly influences their microstructure, phase transformations,
mechanical, and shape memory properties. Hot forging, hot swaging, or hot rolling are efficient techniques
for obtaining the desired shape, but during multiple operations the material must be heated and worked in
the temperature range from 700 to 900 °C. During these processes, intense oxidation takes place. In order
to reduce it, the hot-pack working is applied. The hot extrusion is more effective for reduction of ingot,
billet, and rod diameters than hot forging, hot swaging, or hot rolling. Also, during hot extrusion the
material surface undergoes considerably less oxidation. In the present work, results of the characterization
by differential scanning calorimetry, low-temperature x-ray powder diffraction, and three-point bending
and free recovery ASTM F2082-06 tests of the samples after hot direct extrusion and heat treatment are
presented. The obtained alloy after hot direct extrusion exhibits desired shape memory effect. The phase
transformations during cooling and heating cycle occur with the presence of the R phase. The range of the
characteristic temperatures for the obtained material gives possibility for further medical applications.
After annealing at 400 and 500 °C, the characteristic temperatures shift to higher values.

melting process (Ref 13). The main advantage of VIM method is

Keywords hot direct extrusion, LTXRD, NiTi shape memory
alloy, one-way shape memory effect, phase transitions the obtained homogeneity of chemical composition of the ingot,
because electrical eddy currents and electrodynamic forces
induced in the graphite crucible and in the metallic charges result
in the whirling and mixing of the melt (Ref 12, 16). High-quality
NiTi alloys can be produced by VAR method, however, multiple
1. Introduction re-melts are required to achieve acceptable homogeneity (Ref 16)
The larger size ingots in the industrial production of NiTi shape
memory alloys are routinely produced using the VIM/VAR
NiTi alloys with near-equiatomic composition, commonly
double-melt process (Ref 16). After casting and homogenization
known as Nitinol alloys, exhibit shape memory and superelastic
heat treatment, the ingots must be hot worked to semi-finished
effects (Ref 1, 2). They are also materials used in the medical
products. Depending on the final product shape, various tech-
applications (Ref 3-10). For their wider usage development of
niques such as press forging, rotary forging, extrusion, swaging,
easier and more effective ways of metalworking is necessary.
bar rolling, and sheet rolling, wire drawing may be used in the hot
Melting, casting, metalworking, and heat treatments of NiTi shape
working stage (Ref 11, 13). Following hot working, Nitinol alloys
memory alloys strongly influence their microstructure, phase
are cold worked and heat-treated to obtain final dimension and
transformations, mechanical, and shape memory properties
shape and with desired physical and mechanical properties. During
(Ref 11, 12). Due to the fact that molten titanium is highly
cold drawing of wires, multiple reductions of diameters and
reactive, the NiTi alloys must be melted in high vacuum or in an
frequent inter-pass annealing at 600-800 C is require (Ref 16).
inert gas atmosphere (Ref 12, 13). Vacuum induction melting
During the hot working intense, oxidation of the material
(VIM) and vacuum arc remelting (VAR) are commonly used for
surface takes place. To prevent oxidation, the NiTi billets have
production of NiTi shape memory alloys. In VIM process usually
been canned in mild steel for hot working. This technique was
high-purity, high-density, and low-porosity graphite crucibles and
used for swaging, forging, and extrusion (Ref 13). The direct
molds are used (Ref 11, 13-15). CaO crucibles are preferred for
and indirect extrusion are applied to production of tubes and
extenuation of carbon content in NiTi melts. Unfortunately, such
hot working of ingots and billets (Ref 17, 18). Direct extrusion
crucibles are not resistant to thermal shock and often crack during
of NiTi ingots could be performed without protective sleeve at
temperatures of 950-1050 C with the extrusion ratios of 11:1
This article is an invited paper selected from presentations at the and 6:1 (Ref 18). During indirect extrusion, the NiTi billets
International Conference on Shape Memory and Superelastic were canned into a protective Cu alloy and processed at
Technologies 2013, held May 20-24, 2013, in Prague, Czech temperature of about 900 C with extrusion ratios from 27:1 to
Republic, and has been expanded from the original presentation. 18:1 (Ref 19). The wire of functionally graded TiNi shape
Z. Lekston, M. Zubko, K. Prusik, and D. Stró_z, Institute of Materials memory alloy which varies in Ti-Ni compositions along the
Science, University of Silesia, ul. 75 Pułku Piechoty 1a, 41-500 wire axis was laboratory fabricated by new pulse current
Chorzow, Poland. Contact e-mails: [email protected], pressure sintering and the subsequent hot extrusion process. A
[email protected], [email protected], and danuta.stroz@ billet of 5 mm in diameter was hot extruded into a wire of
us.edu.pl.

2362—Volume 23(7) July 2014 Journal of Materials Engineering and Performance

2 mm in diameter. Hot extrusion process was carried out at free recovery ASTM F2082-06 (TPBFR) tests of the samples
800 C with extrusion ratio 6.25 (Ref 20). Recently, the after hot direct extrusion and heat treatment are presented.
laboratory direct extrusion test was performed to provide the
cold work of the Cu-Zn-Al shape memory alloy in the as cast
rod condition. The diameter was reduced from 12 to 10 mm at
extrusion ratio 1.44 (Ref 21).
2. Material Processing
In the present studies, the shape memory alloy with nominal
composition Ni50.8Ti49.2 obtained by conventional VIM tech- The studied alloy was prepared from high purity
nique is presented. The alloy has promising characteristics for (>99.99 wt.%) nickel and titanium rods using Balzers VSG-
medical application. The hot direct extrusion without protective 10 vacuum induction melting furnace. In order to reduce the
sleeve was applied for processing of the studied material. The aim carbon contamination of the ingot the high-quality, low-
of this study was to examine the possibility of using hot extrusion porosity, and high-density graphite crucible and graphite mold
for rough metalworking of NiTi ingots obtained by VIM method were used. The melting process was started when in the furnace
at the laboratory scale and to determine the phase composition, 5 9 103 Pa vacuum was obtained. The ingot of 900 g (Fig. 1)
temperature, and the sequence of phase transitions and to was homogenized in the electrical vacuum furnace at 900 C
investigate the shape memory effect. In this work, the charac- for 48 h in the vacuum of 2 9 105 Pa. After homogenization,
teristic temperatures of phase transformations hysteresis and one- the ingot was cut into two parts. One of them was packed in
way shape memory effect obtained by differential scanning steel pipe and subsequently hot forged and the second one was
calorimetry (DSC) method, low-temperature x-ray powder hot direct extruded using laboratory 1000 kN press equipped
diffraction (LTXRD) technique, and three-point bending and with electrical furnace for heating the samples up to 1100 C
(Fig. 2). The extrusion process was carried out at about 900 C.
As a lubricant MoS2 was used. The extrusion die and the rod
obtained after hot direct extrusion is presented on Fig. 3. In the
last step, the obtained rod was straightened and thin oxidation
layer was removed by machining. The diameter of material was

Fig. 1 The 900 g NiTi ingot obtained after vacuum induction melting

Fig. 3 Extrusion die and a rod after hot direct extrusion

Fig. 2 Laboratory press (1000 kN) equipped with attachment for

hot direct extrusion. By A the steel ram is marked, B is the con-
tainer, C is the mounting position of extrusion die inside in con-
tainer. By D electrical furnace for heating samples up to about Fig. 4 Billet and extruded rod of studied material after removing of
1100 C is marked oxide layer. The reduction of diameter is from 25 to 15 mm

Journal of Materials Engineering and Performance Volume 23(7) July 2014—2363

reduced from 25 to 15 mm at extrusion ratio 2.34 (Fig. 4). diffractometer equipped with Anton Paar TTK450 low-tem-
Samples for further studies were cut from the obtained resulting perature chamber at temperatures from 180 to 250 C. The
material (Fig. 5). measurements were performed with 5 C steps resulting
heating rate of 0.7 C/min. DSC measurements were performed
on Mettler Toledo DSC1 calorimeter during cooling and
heating at rate of 10 C/min. Shape recovery studies were
3. Experimental carried out using three-point bending and free recovery ASTM
F2082-06 tests with heating rate of 10 C/min. The micro-
The x-ray powder diffraction measurements in 2h range structure was studied by optical microscope Olympus GX-51
from 37 to 47 were performed on a PANalytical Empyrean and JEOL JSM 6480 scanning electron microscope attached
with the IXRF energy dispersion detector.

4. Results

The optical micrograph of the central part of the extruded

rod is shown in Fig. 6. The average grain size is about
50-80 lm. Significant differences of microstructure have not
been observed on cross sections of the central part, head, and
Fig. 5 The straight-extruded NiTi rod after removing the oxide lay- foot parts of the rod after extrusion. The images show
er by the machining. Cut samples prepared for investigations are elongation of some grains after hot extrusion. Additionally,
also shown

Fig. 8 DSC measurements recorded during cooling and heating

Fig. 6 Microstructure of the extruded alloy—longitudinal cross- cycle for samples after hot extrusion and after further annealing at
section (optical microscopy) 400 and 500 C for 30 min

Fig. 7 SEM image of the eutectics region (a) and the Ti (b) and Ni (c) distribution along the red line in (a)

2364—Volume 23(7) July 2014 Journal of Materials Engineering and Performance

some eutectics in the grain boundary regions were observed. Ms temperature shifts toward lower values whereas Af temper-
Since x-ray diffraction did not show any other than B2 phase in ature shifts toward higher values increasing the hysteresis loop.
these samples, the EDS experiments along the line passing the Figure 9 shows x-ray powder diffraction patterns recorded
eutectics region were carried out (Fig. 7). It occurred that the at 35 C for samples after extrusion and further annealing at
second phase in the eutectics is slightly enriched in titanium 400 and 500 C for 30 min. In all the presented diffraction
and reduced in nickel. However, the changes are very small. patterns only B2(110) peak is observed which indicates that the
Generally, it looks as if during extrusion the sample undergoes studied material below human body temperature has structure
dynamical recrystallization. The structure and phase composi- of B2 parent phase and is suitable for medical applications.
tion of the extruded samples will be the subject of following Color maps of the temperature dependence of LTXRD
study. patterns collected during cooling cycle (Fig. 10) show phase
Performed DSC measurements (Fig. 8) show that the transformations. The B2 fi R transition is visible as B(110)
samples after hot direct extrusion and further annealing at peak splitting into R(011) and Rð101Þ peaks. R fi B19¢ phase
400 and 500 C undergo two-step phase transformation during transition is visible as appearance of martensite diffraction
cooling and heating which can be explained by the existence of peaks (marked by M) and slowly disappearing of R phase peak
the R phase transition. During cooling, the phase transitions are doublet. During heating, the phase transformation occurs also
not resolved as clearly as upon heating. From the DSC with the existence of the R phase but the phases coexist in a
measurements, it is also visible that the characteristic temper- smaller temperature range. LTXRD measurements have advan-
atures shift slightly with increasing annealing temperature. The tage over the DCS measurements because they provide also
additional information about phases coexistence during phase
transformations (Ref 22). Based on the LTXRD measurements,
it is possible to determine the narrow temperature range where
only R phase is present during cooling as well as during heating
cycle.
LTXRD measurements can be also used in order to obtain
the characteristic temperatures of phase transitions. In our
studies, the obtained from this method Af temperatures are
lower than the ones from DSC and shape recovery measure-
ments (Table 1). This is caused by different heating rates used
in both cases (Ref 23). In the x-ray measurements, the rate of
the temperature change was 0.7 C/min while in the DSC and

Table 1 Comparison of Af temperatures obtained

from DSC, shape recovery, and LTXRD measurements
DSC, °C Shape recovery, °C XRD, °C

After extrusion 31.9 28.5 21.5

Fig. 9 X-ray powder diffraction patterns recorded at temperature of Annealed at 400 C 35.9 35.5 22.8
35 C for samples after hot extrusion and after further annealing at Annealed at 500 C 39.4 40.8 23.9
400 and 500 C for 30 min

Fig. 10 Color maps of the temperature dependence of LTXRD patterns collected during cooling cycle for sample after hot extrusion (left) and
after additional annealing at 500 C for 30 min (right)

Journal of Materials Engineering and Performance Volume 23(7) July 2014—2365

 tendency has been confirmed in the shape recovery measure-
ments. For the studied alloy, the Af temperature is below human
body temperature which makes them useful in medical applica-
tion. The forged and extruded rods are currently processed by hot
rotary forging and hot or cold drawing and annealing to wires of
different diameters.

Acknowledgments
This work was financially supported by the Polish National
Science Centre within the frame of the project Nr N N507 296339.

Open Access
This article is distributed under the terms of the Creative
Commons Attribution License which permits any use, distribution,
Fig. 11 Shape recovery curves of the studied samples and reproduction in any medium, provided the original author(s)
and the source are credited.

shape recovery measurements it was 10 C/min. High heating/

cooling rates might influence the transformation detection.
Therefore, it looks that the x-ray studies in which the
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