Journal of Materials Processing Technology 221 (2015) 279–284

Contents lists available at ScienceDirect

Journal of Materials Processing Technology

journal homepage: www.elsevier.com/locate/jmatprotec

Surface modification of TiNi-based shape memory alloys by dry

electrical discharge machining
Tyau-Song Huang a , Shy-Feng Hsieh a , Sung-Long Chen b , Ming-Hong Lin b , Shih-Fu Ou a,∗ ,
Wei-Tse Chang a
a
Department of Mold and Die Engineering, National Kaohsiung University of Applied Sciences, Kaohsiung 807, Taiwan
b
Department of Mechanical Engineering, National Kaohsiung University of Applied Sciences, Kaohsiung 807, Taiwan

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

Article history: This study attempts to decrease the martensite transformation temperature of Ti50 Ni50 shape memory
Received 3 September 2014 alloy (SMA) for its use in biomedical applications by Cr addition. In addition, surface modification of
Received in revised form 2 February 2015 Ti50 Ni50 and Ti50 Ni49.5 Cr0.5 SMAs using electrical discharge machining (EDM) is proposed. Nitrogen gas
Accepted 11 February 2015
is used as a dielectric medium, and a pure titanium pipe is used as the tool electrode. The machining
Available online 24 February 2015
characteristics and surface properties of Ti50 Ni50 and Ti50 Ni49.5 Cr0.5 SMAs after EDM in nitrogen gas were
investigated. Many electrical discharge craters and recast materials are observed on the EDMed surface of
Keywords:
these SMAs. Material removal rate, electrode wear rate, and surface roughness increase with increasing
Shape memory alloys
Dry electrical discharge machining
pulse current and duration, and they share an inverse relationship with the thermal conductivity of these
Surface modification SMAs. After EDM, the SMAs continue to exhibit good shape recovery, and even the recast layers have high
surface hardness. The recast layers, comprising TiN and CrN, with high hardness and good adhesion are
expected to improve the SMAs’ wear and corrosion resistance.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction
Shape memory alloys (SMAs) are used in many fields such as
mechanical, aerospace, and military applications (Van Humbeeck,
1999). From among SMAs, Ti–Ni SMAs are widely applied in
biomedical engineering because of their unique superelasticity
(Otsuka and Ren, 2005), superior shape memory effect (Yoneyama
et al., 1992), excellent corrosion resistance (Liu and Xiang, 1998),
low elastic modulus (Wever et al., 1998), and non-ferromagnetic
property (Duerig et al., 1999). However, from the viewpoint of long-
term implantation, Ni release from Ti–Ni SMAs may cause allergy
in the human body. Therefore, proper surface treatment of Ti–Ni
implants is important to reduce Ni release and improve corrosion
resistance.
Hydroxyapatite (Lobo et al., 2011), zirconia (Qiu et al., 2010),
titanium oxide (Qiu et al., 2011), titanium nitride (Jin et al., 2013),
and apatite-collagen composite (Sun et al., 2011), are coated on
Ti–Ni SMAs to improve the biocompatibility. Among these coating,
∗ Corresponding author. Tel.: +886 7 3814526x5415; fax: +886 7 3814526.
E-mail addresses: htsong@kuas.edu.tw (T.-S. Huang), sfhsieh@cc.kuas.edu.tw
(S.-F. Hsieh), slchen@kuas.edu.tw (S.-L. Chen), mhlin@kuas.edu.tw (M.-H. Lin),
m9203510@gmail.com (S.-F. Ou), 1099316141@kuas.edu.tw (W.-T. Chang).
titanium nitride (TiN), possessing high hardness and good wear
resistance, has been used for hip prostheses (Piscanec et al., 2004).
Therefore, many surface treatment technologies, i.e., gas nitrid-
ing (Wu et al., 1999), filtered arcing ion plate technique (Jin
et al., 2013), and powder immersion reaction assisted coating
(Starosvetsky and Gotman, 2001), are proposed to coat TiN on
Ti–Ni SMA surfaces. In order to develop better surface treatment
technologies, the present study introduce a method to coat TiN
on Ti–Ni SMAs by dry electrical discharge machining (EDM). Until
now, many researchers have attempted to modify titanium and
its alloys’ surface (Manjaiah et al., 2014) by EDM. However, to
the best of our knowledge, EDM applied to Ti–Ni SMAs is hardly
reported.
In our previous study, TiO and TiC were formed on the sur-
face when Ti–6Al–4V alloys were EDMed in kerosene and distilled
water, respectively (Chen et al., 1999). In EDM, the work-piece is
melted, vaporized, and then cooled rapidly by a dielectric fluid;
this leads to the formation of a recast layer on the substrate sur-
face. In order to improve the biocompatibility of Ti–Ni SMAs, this
study aims to fabricate nitride films on Ti50 Ni50 and Ti50 Ni49.5 Cr0.5
SMAs by dry EDM. Nitrogen gas was chosen as the dielectric
fluid to improve material removal rate and keep the work-piece
contamination-free. The microstructure, composition, hardness,
and roughness of the EDMed surfaces were investigated.

http://dx.doi.org/10.1016/j.jmatprotec.2015.02.025
0924-0136/© 2015 Elsevier B.V. All rights reserved.
280 T.-S. Huang et al. / Journal of Materials Processing Technology 221 (2015) 279–284
Fig. 1. Schematic diagram of the dry EDM equipment.
2. Experimental procedure
2.1. Ti–Ni SMAs preparation
The conventional tungsten arc-melting technique was
employed to prepare the Ti50 Ni50 and Ti50 Ni49.5 Cr0.5 SMAs. Ti
(purity, 99.7 wt.%), Ni (purity, 99.9 wt.%), and Cr (purity, 99.8 wt.%)
totaling to about 150 g were melted and remelted at least six times
in argon atmosphere. In addition, pure Ti buttons were melted
and used as getters. The mass loss during melting was negligible.
The as-melted buttons were homogenized at 950 ◦ C for 72 h. The
homogenized buttons were cut into several discs (ϕ 6 mm × 1 mm)
using a low-speed diamond saw. The disk specimens were evac-
uated in quartz tubes and annealed at 900 ◦ C for 2 h, followed by
quenching in water. Before EDM, the specimens were mechanically
polished with SiC sandpaper (180, 240, 400, 600, and 800 grit).
2.2. EDM process
The specimens were electrical discharge – machined using a die-
sinking EDM machine (model LS-250C) made by Lien-Sheng Co.
Fig. 2. DSC curves of (a) Ti50Ni50 and (b) Ti50Ni49.5Cr0.5 SMA.
in Taiwan. Fig. 1 illustrates the configuration of EDM equipment.
Highly pure nitrogen gas (99%) was jetted from pipe tool electrode
under a pressure of 97.1 KPa as the dielectric medium. A cylindrical
Ti pipe (99.7 wt.%) with outer and inner diameters of 6 mm and
5 mm, respectively, was used as the tool electrode. The rotational
speed of the Ti pipe electrode was 120 rpm. In this study, EDM was
used to fabricate fine-machined products. Hence pulse currents of
3, 5, and 7 A with pulse durations of 15, 30, 45, 60, and 75 ␮s were
selected.
2.3. Characteristics of Ti–Ni SMAs before and after EDM
The martensitic transformation temperatures of SMAs were
measured by differential scanning calorimetry (DSC, TA Q10) at a
controlled heating/cooling rate of 10 ◦ C min−1 . The shape recov-
ery effect was examined by conducting a bending test (Lin and
Wu, 1992). The microstructures of the EDMed surfaces were
examined with X-ray diffraction (XRD, Siemens D5000) at 2 scan-
ning rate of 3 min−1 . The morphologies of EDMed surface were
observed using scanning electron microscopy (SEM, JOEL 6330 TF).
Cross-sectional specimens were prepared by polishing and sub-
sequent etching using the following solution: HF (1 ml) + HNO3
(2 ml) + HCl (2 ml) + H2 O (100 ml). The etching periods for Ti50 Ni50
and Ti50 Ni49.5 Cr0.5 were 30 s and 90 s, respectively. A Talysurf pro-
filometer was used to evaluate quantitatively the roughness of the
EDMed surface, denoted as Ra. The cut-off was selected as 0.8 mm.
For each piece, the average of the readings taken at seven points on
the machining plane was considered the surface roughness value.
The surface hardness was measured using a micro Vickers hardness
tester (FUTURE.TECH FM.700) under a load of 20 g for 15 s. For each
specimen, the average of at least five test readings was calculated.
The recast layer-SMA adhesion was tested using a scratch tester
(MFT-4000).
3. Results and discussion
3.1. Characteristics of Ti50 Ni50 and Ti50 Ni49.5 Cr0.5 SMAs
Fig. 2(a) and (b) show the DSC curve of Ti50 Ni50 and
Ti50 Ni49.5 Cr0.5 in both forward and reverse transformation, respec-
tively. It is indicated that decreased martensite transformation
temperatures (M* and A*) can be achieved by adding a small
amount of Cr. Both SMAs exhibit almost 100% shape recovery at
various bending strains, can be inferred from Table 1. Furthermore,
Ti50 Ni49.5 Cr0.5 has higher hardness than Ti50 Ni50 SMA, which can
be ascribed to Cr solid-solution hardening (Hsieh et al., 2012). This
hardening phenomenon is appeared in Ti52 Ni47 Al1 alloy (Hsieh and
Wu, 1999) as well.
 T.-S. Huang et al. / Journal of Materials Processing Technology 221 (2015) 279–284 281

Table 1 results in an increase in the ratio of cation flow in the plasma

The measured shape recovery (RSME ), hardness, and critical load measured during
channel (Dibitonto, 1989), thus increasing the amount of electrical
scratch test of Ti50 Ni50 and Ti50 Ni49.5 Cr0.5 SMAs before and after EDM.
discharge energy acting on the work-piece.
Shape recovery, Hardness Critical load (N) Fig. 5 shows the XRD patterns of the surfaces of the EDMed
RSME (%) (Hv) 5 A, 15 ␮s
SMAs. For the EDMed Ti50 Ni50 SMA, the XRD patterns show peaks
Bending strain, εs 2% 5% 8% from the recast layer (TiN) and the substrate (B19 and B2), while
Ti50 Ni50 100 100 95 207 – the recast layer of the EDMed Ti50 Ni49.5 Cr0.5 SMA consists of TiN
Ti50 Ni50 (EDM) 95 87 67 723 58.32 and CrN. The recast layer was formed because the work-piece was
Ti50 Ni49.5 Cr0.5 100 100 94 253 – melted and re-solidified in dielectric medium during EDM. The
Ti50 Ni49.5 Cr0.5 (EDM) 94 84 65 746 64.57 composition of the recast layer varied with work-piece material
and electrolyte composition. In study of EDM Ti alloys in kerosene,
kerosene is decomposed to carbon and therefore Ti alloys’ surfaces
3.2. Surface morphology and composition analysis of TiNi-based are carbonized (Hasçalık and Çaydaş, 2007). Similarly, when dis-
SMAs after EDM tilled water is used as EDM dielectric medium, water is decomposed
into hydrogen and oxygen and hence Ti oxide is formed (Chen
Fig. 3(a) and (b), respectively, show SEM micrographs of the et al., 1999). In this study, electrical discharge induces nitrogen
Ti50 Ni50 SMA surfaces after EDM under the following conditions: decomposition and enhances high energetic nitrogen to react with
pulse current (IP ) = 3 A and pulse duration ( P ) = 15, 75 ␮s. Many dis- work-piece (Czerwiec and Bergmann, 1998). Moreover, work-piece
charge craters, melting drops, and recast materials were observed is melted due to the localized high temperature, which results in
in the EDMed surfaces. Fig. 3(c) and (d) show the EDMed surfaces of increased nitridation of work-piece. The composition of biomed-
Ti50 Ni49.5 Cr0.5 SMA, which are similar to those of EDMed Ti50 Ni50 ically used material surface is very important because it affects
SMA. In Fig. 3(b) and (d), cracks can be seen on the surfaces of material’s biocompatibility. According to the results of cytotoxic-
both EDMed SMAs, and cracking appears to have occurred more ity tests, TiN coatings on TiNi SMA (Jin et al., 2013) and stainless
frequently on the EDMed surfaces subjected to longer pulse dura- steel (Park et al., 2003) show good biocompatibility. CrN coatings
tion. Comparing these findings with results of EDM in distilled on CoCr alloys show decreased cytotoxic effect on cells compared
water (Hasçalık and Çaydaş, 2007) and kerosene (Tang and Du, to commercially used CoCr alloys (Williams et al., 2003).
2014), there is no significant difference in surface characteristics
of alloys EDMed in gas and liquid electrolytes. The cross-sectional 3.3. Machining characteristics and surface roughness of
SEM micrographs of the EDMed Ti50 Ni50 SMAs (Fig. 4(a) and (b)) TiNi-based SMAs after EDM
show recast layers formed on SMA surfaces, and the recast layer
thickness increases with increasing pulse duration. In addition, this Fig. 6(a) and (b) shows the relationship between the mate-
phenomenon is found for EDMed Ti50 Ni49.5 Cr0.5 SMA, as shown rial removal rate (MRR) and the pulse duration for Ti50 Ni50 and
in Fig. 4(c) and (d). The recast layer thickness depends mainly Ti50 Ni49.5 Cr0.5 , respectively. For both SMAs, the MRR increases with
on the electrical discharge energy. Increasing the pulse duration increasing pulse duration and current. In general, increasing the

Fig. 3. SEM micrographs of EDMed Ti50Ni50 SMA surfaces under (a) 3 A × 15 ␮s and (b) 3 A × 75 ␮s. SEM micrographs of EDMed Ti50Ni49.5Cr0.5 SMA surfaces under (c)
3 A × 15 ␮s and (d) 3 A × 75 ␮s.
282 T.-S. Huang et al. / Journal of Materials Processing Technology 221 (2015) 279–284
Fig. 4. Cross-sectional SEM micrographs of EDMed Ti50Ni50 SMA under (a) 3 A × 15 ␮s and (b) 3 A × 75 ␮s. Cross-sectional SEM micrographs of EDMed Ti50Ni49.5Cr0.5 SMA
under (c) 3 A × 15 ␮s and (d) 3 A × 75 ␮s.
pulse duration can lead to sustained work-piece surface melt-
ing and, therefore, a higher MRR. Fig. 6(c) shows that the MRR
of EDMed Ti50 Ni50 SMA is higher than that of Ti50 Ni49.5 Cr0.5 for
pulse durations of 15–75 ␮s. A previous study has reported that
the MMR is inversely related to the product of melting temper-
ature () and thermal conductivity (K˛) of work-piece (Lin et al.,
2001). The  × K˛ values of Ti50 Ni50 and Ti50 Ni49.5 Cr0.5 SMA are
111.8 and 310.1 W/cm ◦ C, respectively. According to Fig. 6(c), the
MRRs of Ti50 Ni50 and Ti50 Ni49.5 Cr0.5 follow the abovementioned
relationship.
Fig. 7(a) and (b) shows that the electrode wear rate (EWR)
increases with increasing pulse duration for both EDMed Ti50 Ni50
and Ti50 Ni49.5 Cr0.5 SMAs. When the pulse duration is 15 ␮s, the
EWR is very low and no significant difference in the EWR between
variant pulse current (5 A and 7 A). The low EWR is due to TiN
formed on the surface of tool electrode (Ti) and the melting point
of TiN (3200 ◦ C) is higher than Ti (1668 ◦ C). Theoretically, the tool
Fig. 5. XRD patterns of EDMed surfaces of Ti50Ni50 and Ti50Ni49.5Cr0.5 SMA.
electrode has high melting temperature results in low electrode
wear rate (Hasçalık and Çaydaş, 2007). In addition, the variation in
EWR with pulse duration exhibits a tendency similar to that of MRR
with pulse duration, as shown in Fig. 6.
The EWR during the machining of Ti50 Ni49.5 Cr0.5 was lower
than the EWR measured during the machining of Ti50 Ni50 under
high discharge current (5 and 7 A) and long pulse duration (60 and
75 ␮s). This is because Ti50 Ni49.5 Cr0.5 has a high  × K˛ value, and it
absorbs most of the thermal energy, thus reducing the heat trans-
ferred to the electrode. In addition, in this study, nitrogen gas flow
from the hollow electrode helps prevent debris from adhering to
the electrode.
Fig. 8(a) and (b) show the change in the roughness of the
EDMed surfaces with pulse duration at IP = 3, 5, 7 A for Ti50 Ni50 and
Ti50 Ni49.5 Cr0.5 SMA, respectively. The roughness of the EDMed sur-
face increases with increasing pulse current and pulse duration.
Furthermore, the roughness is affected by the electrical discharge
energy mode in EDM, and the relationship can be represented as
Ra = C(Ip ×  p )␤ . The constants C and ␤ in this empirical equation
were obtained from Fig. 9. In this study, the surface roughness (Ra)
of the EDMed surface for Ti50 Ni50 and Ti50 Ni49.5 Cr0.5 SMA follow the
relationships Ra = 283.68(Ip ×  p )0.607 and Ra = 295.63(Ip ×  p )0.625 ,
respectively. The constants C and ␤ are related to the electrical
discharging energy mode and tool–work-piece material charac-
teristics, for example, mechanical properties (Rebelo et al., 2000),
material structure, and thermal properties (Jeswani, 1978).
3.4. Surface mechanical properties of TiNi-based SMAs after EDM
According to Table 1, after EDM, the shape recovery ability
of SMAs is reduced, and this reduction is attributed to increased
surface hardness of the EDMed SMAs. The increased hardness is
associated with TiN and CrN (Fig. 5) formed on the recast layer
during EDM. Hsieh et al. (2009) concluded that after wire EDMed
in distilled water, the surface hardness of TiNiZr alloy increase
 T.-S. Huang et al. / Journal of Materials Processing Technology 221 (2015) 279–284 283

Fig. 6. Relationship between MMR and pulse duration for (a) Ti50Ni50 SMA, (b) Ti50Ni49.5Cr0.5 SMA, and (c) Ti50Ni50 and Ti50Ni49.5Cr0.5 SMAs EDMed at IP = 7 A.

Fig. 7. Relationship between EWR and pulse duration for (a) Ti50Ni50 SMA, and (b) Ti50Ni49.5Cr0.5 SMA.

from 320 Hv to 980 Hv and it is attributed to the formation of TiO2 ,
TiNiO3 , ZrO2 and the deposition debris in the recast layer. Lin et al.
(2001) proved that the hardness of EDMed TiNiCu alloy increased
from the inner to surface machined surface. The hardening effect is
because of the recast layer consisting of TiO2 , TiNiO3 and debris.
Moreover, a scratch test was performed to evaluate friction and
adhesion between the recast layer and the substrate. The measured
critical load in Table 1 indicates the normal force at which failure
occurs. The recast layer of EDMed Ti50 Ni49.5 Cr0.5 can withstand a
higher critical load than that of EDMed Ti50 Ni50 . Hence, it can be

Fig. 8. Change in roughness of EDMed surfaces with pulse duration for (a) Ti50Ni50 SMA and (b) Ti50Ni49.5Cr0.5 SMA.
284 T.-S. Huang et al. / Journal of Materials Processing Technology 221 (2015) 279–284
Fig. 9. Surface roughness versus product of IP and  P for Ti50Ni50 and
Ti50Ni49.5Cr0.5 SMA.
said that the EDMed Ti50 Ni49.5 Cr0.5 surface has better wear resis-
tance because its recast layer is harder and has higher adhesion. In
Fig. 4, the substrate–recast layer interface cannot be distinguished
clearly, which suggests that the recast layer has good adhesion. This
is because the recast layer solidifies slowly in gas, and the stress
between the recast layer and substrate is well released.
4. Conclusions
In this study, Cr was added to Ti50 Ni50 shape memory alloy
(SMA) to decrease its martensite transformation temperature
in order to make it suitable for biomedical applications. The
machining characteristics and surface properties of Ti50 Ni50 and
Ti50 Ni49.5 Cr0.5 SMAs after EDM in nitrogen gas were investigated.
Material removal rate, electrode wear rate, and surface rough-
ness of Ti50 Ni49.5 Cr0.5 SMA were lower than those of Ti50 Ni50 SMA
because they share an inverse relationship with the thermal con-
ductivity of these SMAs. After EDM, the SMAs exhibited improved
surface hardness while retaining good shape recovery ability. The
recast layer, comprising TiN and CrN, that was well adhered on the
SMAs is expected to provide good wear and corrosion resistance,
and can prevent the metal substrate from contacting body fluid
when EDMed SMAs are implanted in human body.
Acknowledgement
The authors sincerely acknowledge the financial support of this
research by the National Science Council (NSC), Republic of China,
under Grants NSC 101-2221-E-151-009 and NSC 102-2221-E-151-
013.
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