Materials Letters 91 (2013) 202205

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Grain renement of NiTi shape memory alloy thin lms by W addition

Navjot Kaur, Davinder Kaur n
Functional Nanomaterials Research Lab, Department of Physics and Centre of Nanotechnology, Indian Institute of Technology Roorkee, Roorkee 247667, Uttarakhand, India

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 3 September 2012
Accepted 23 September 2012
Available online 29 September 2012

The present research explores the novel approach to achieve grain renement in NiTi shape memory
alloy thin lms by adding W in the matrix of NiTi. It involves production of NiTiW shape memory alloy
thin lms by Co-sputtering of NiTi and W targets. The grain size of B2-NiTi decreases with increasing W
content, due to the immiscible W layer obstructing its grain growth. Moreover addition of W induces
the B2R single step transformation by suppressing thermally induced martensite phase due to
grain size renement below 40 nm. With W content ranging from 2.6 at% to 4.5 at%, the lms are
strengthened and can reach highest hardness and elastic modulus of 32.8 72.7 GPa and 167.837
8.64 GPa, respectively. With further increase in W content, the mechanical properties of lms decrease
gradually. This behavior can be explained in terms HallPetch theory and lattice distortion of NiTi
crystals with increasing the W content.
& 2012 Elsevier B.V. All rights reserved.

Keywords:
Thin lms
Sputtering
Grain size
Elastic modulus

1. Introduction
Nanocrystalline materials have been the subject of considerable
research in recent years for their novel and enhanced properties
[1,2]. The nanocrystalline NiTi shape memory alloys were synthesized in their bulk form by severe plastic deformation (SPD),
including high pressure torsion (HPT), equal-channel angular pressing (ECAP), and multi-step SPD deformations [3]. Grain renement of
NiTi enhances its mechanical properties and modify the phase
transformation path to B2R having smaller hysteresis, low transformation strains and higher work output as compared to B2RB190
present in coase grained NiTi [4]. Because of the small hysteresis, a
quick response is expected in microactuators using such an R-phase
transformation. Thus the application of grain renement by various
techniques is a powerful tool to design microstructures with superior
properties and performance. However above mentioned mechanical
methods of grain renement are limited to bulk samples only. The
present research explores the novel approach to achieve grain
renement in NiTi thin lms by adding W in matrix of NiTi. Effect
of grain renement on structural, phase transformation and mechanical properties of NiTi was investigated.

2. Experimental procedure
NiTiW thin lms were deposited on Si substrates by magnetron sputtering using Dc magnetron Co-sputtering system (Excel
n

Corresponding author. Tel.: 91 1332 2285407; fax: 91 1332 273560.

E-mail address: dkaurfph@iitr.ernet.in (D. Kaur).

0167-577X/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.matlet.2012.09.073

Instruments, India), which is equipped with two magnetron guns.

High purity (99.99%) NiTi (50 at% Ni; 50 at% Ti) and W (tungsten)
metal targets of 50 mm diameter and 3 mm thickness were used.
Amount of W added to the matrix of NiTi could be precisely
controlled with power to each target. The target power was
typically set at 112 W for NiTi and varied from 3 W to 50 W for
W (tungsten) target and thus series of NiTiW shape memory alloy
lms with different W content were deposited.
The structure, surface morphology and chemical composition
of lms were studied using X-Ray diffraction (XRD), atomic force
microscope (AFM), eld emission scanning electron microscope
(FESEM) and energy dispersive X-Ray Spectrometry (EDX). Four
probe resistivity methods were used to study the shape memory
effect. Hardness and elastic modulus of NiTiW thin lms were
measured by Nanoindenter device (Micromaterials, UK) using
Berkovich indenter. The results were averaged by 12 independent
indentations on each sample.

3. Results and discussion

Fig. 1(c) shows the XRD spectra of pure NiTi and NiTiW shape
memory alloy thin lms. Pure NiTi lm reveals the formation of
fully austenite phase with dominant reection from (110) plane.
With increasing the W content, the intensity of NiTi (110) diffraction peak decreases gradually while its width increases (Table 1).
This reveals that grain size of NiTi decreases gradually with increase
of W content. R phase reection is also present in XRD curves of all
the NiTiW thin lms but the diffraction peak of B2 and R-phase are
very close and is not possible to separate them. Hence they were
treated as same (110) B2/(300) R in XRD pattern. From XRD results

N. Kaur, D. Kaur / Materials Letters 91 (2013) 202205

203

Fig. 1. Inuence of W content on (a) unit cell volume change DV/V0, (b) lattice parameter and lattice distortion, (c) X-ray diffractograms and (d) AFM and FESEM images of
NiTiW sputtered thin lms.

it appears that W solubility in NiTi is limited for W content less

than 4.5 at% as no peak of b-W phase was observed in the XRD
pattern of NiTiW (2.6) and NiTiW (4.5) lms. However with
increase in W concentration above solubility limit (which is
approximately less than 5 at% in present case), the b-W phase is
clearly evidenced in XRD curves of NiTiW (9.1), NiTiW (12.8) and
NiTiW (33.6) thin lms. Fig. 1(b) shows the variation of lattice
constant and relative lattice distortion of NiTi thin lms with
increasing W content. The incorporation of W in NiTi lattice up to
4.5 at%, gives rise to lattice contraction also indicated by decrease in
lattice constant. This is because smaller W (0.068 nm) atoms
replace larger Ti (0.076 nm) atoms in NiTi lattice. As the W content

is further increased lattice constant increases indicating dialation of

lattice. This increase in lattice parameter of B2NiTi is due to
interfacial strain energy which arises due to lattice mist between
b-W (due to its stabilization at higher W content) and B2NiTi
lattice. Accordingly the unit cell volume of NiTiW thin lms was
also found to be changed relative to NiTi (Fig. 1(a)). For the NiTiW
samples with 2.6 and 4.5 at%W content, the unit cell volume change
(DV/V0) is negative; i.e., the lattice structure is contracted, while the
lattice is dilated or expanded beyond 4.5 at% W addition indicated
by positive values of DV/V0. Fig. 1(d) shows the AFM and FESEM
images of pure NiTi and different NiTiW thin lms. The lms
were very dense, smooth and crackfree. The lms show granular

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N. Kaur, D. Kaur / Materials Letters 91 (2013) 202205

Table 1
Various parameters of NiTi and NiTiW shape memory alloy thin lms.
Sample name

Structural properties
Grain size (nm)

Pure NiTi
NiTiW (2.6)
NiTiW (4.5)
NiTiW (9.1)
NiTiW (12.8)
NiTiW (33.6)
a

XRD

FESEM

AFM

25.2
7.16
6.23
4.16
3.34
2.76

80.4
24.1
20.1
13.8
11.1
9

87.9
24.9
21.7
14.3
11.4
9.6

Mechanical properties
Average
roughness (nm)

Total deptha
hmax (nm)

Residual deptha
hr (nm)

Elastic recovery
ratioa, d

Hardnessa
H (GPa)

Elastic modulusa
E (Gpa)

H3/E2a
r (GPa)

20.5
7.5
6.3
3.53
3.03
2.41

114.417 0.72
74.55 7 0.31
71.57 7 0.56
98.36 7 0.71
103.99 7 0.92
107.49 1.33

88.6 7 1.68
51.61 7 1.27
43.63 7 1.94
70.41 7 2.64
75.9 7 2.13
79.56 7 2.15

0.225 7 0.015
0.3087 0.017
0.39 7 0.029
0.284 7 0.026
0.27 7 0.021
0.259 7 0.022

8.05 70.29
23.44 71.14
32.8 72.76
12.59 70.97
10.8 70.64
9.86 70.38

85.67 1.98
162.977 5.94
167.837 8.64
100.947 3.76
93.27 6.01
89.47 5.98

0.0717 0.006
0.484 7 0.096
1.25 7 0.376
0.196 7 0.053
0.145 7 0.036
0.119 7 0.028

210
280
Temperature (K)

350

The values are mean 7 standard deviation for n 12.

0.72

0.348

Resistance (ohm)

Resistance (ohm)

0.68

0.64

0.344

0.340

0.60

0.56
100

0.336
150

200
250
300
Temperature (K)

350

70

400

140

420

Fig. 2. Phase transformation behavior of pure NiTi and NiTiW sputtered thin lms.

morphology with average granule size and surface roughness

decreasing with increasing W content (Table 1).
Fig. 2 shows the RT plots of NiTi and NiTiW thin lms
explaining their phase transformation behavior. As, Af, Rs, Rf, Ms,
Mf represent the transformation temperatures where A: austenite
(B2); R: martensite (R-phase); M: martensite (B190 ); s: start
temperature and f: nish temperature. It is evident from the RT
curve of NiTi that, it undergoes B2RB190 transformation exhibiting wide (28 K) thermal hysteresis. However addition of W into
NiTi above its solid solubility limit (W44.5 at%) results in single
step B2R reversible phase transformation. Fig. 2 shows the RT
curve of NiTiW (9.1) thin lm exhibiting B2R phase transformation with much reduced thermal hysteresis of 11 K. The change in
phase transformation behavior observed in this lm is correlated
to grain size of B2NiTi phase. In NiTiW (9.1) thin lm, immiscible
b-W phase obstructs grain growth of the B2NiTi grains. This
leads to grain size renement of B2NiTi resulting in high density
of grain boundaries which act as obstacles that hinder the growth
of martensite and autocatalytic nucleation potency. Therefore
retarded grain growth can effectively suppress the B190 martensite transformation as compared to R-phase transformation. This
is according to the reported result that below a grain size of
50 nm, the B190 martensite was completely suppressed [5]. The
reason for the suppression of martensite as compared to R phase
is that nanograins contain only small lattice strains which can
accommodate only R phase because transformation strains of the
R-phase (about 1%) are smaller than those of B190 (about 10%) [5].
Fig. 3(a) shows the hardness (H) and elastic modulus (Er) of
pure NiTi and NiTiW thin lms as function of W content. It can be
seen that the hardness of pure NiTi lm is about 8.05 70.29 GPa.
After adding some W into NiTi lm, the hardness increases

rapidly and reaches maximum value of 32.872.76 GPa when W

content is 4.5 at%. With further increase in W content, it decreases
rst rapidly and then gradually. The change of elastic modulus of
NiTiW lms has the same trend as that of hardness. It reaches a
maximum value of 167.8378.64 GPa at 4.5 at% W and then
gradually decreases to about 89.4 75.98 GPa with further
increase in W content. The indentation induced superelastic effect
can be characterized by the elastic recovery ratio which is
obtained from the loaddisplacement curves as
ER

hmax hr
hmax

where hmax is the penetration depth at maximum load, and hr is

the residual depth when the load returns to zero during unloading [6]. H3/E2r is also an important material parameter which
indicates the resistance of the coating to plastic deformation or to
crack formation and propagation, when the lm is exposed to
external load [7]. Fig. 3(b) shows the elastic recovery ER and H3/E2r
ratio of NiTiW lms as a function of W content. ER and H3/E2r also
increases with increase in W content and reaches maximum at
4.5 at% W, indicating better elastic recovery and toughness of
these lms. Drastic decrease is also observed in these parameters
beyond 4.5 at% W addition. This variation in mechanical properties could be explained by two possible mechanisms:
 One is grain size renement with increasing the W content.
 Other is lattice distortion of NiTi lattice with increasing the
W content.
Increase in hardness from 8.0570.29 GPa for pure NiTi to
32.872.76 GPa with 4.5 at% W addition is expected to be due to

N. Kaur, D. Kaur / Materials Letters 91 (2013) 202205

Hardness (H) (GPa)

(E r )
120

28

80

21

40

14

Elastic Modulus (Er) (GPa)

160

Hardness

35

7
0

10

15

20

25

30

35

W content (at.%)
40

4. Conclusions

1.2

30
0.9
20

0.6

H 3/E r 2

Elastic Recovery Ratio ER(%)

where G is the shear modulus, b is the Burgers vector,n is the Poisson

ratio and sapp is the applied stress. The calculated value of dc is
 15 nm, below which hardness and other mechanical properties are
expected to decrease and agrees well with experimental results.
Lattice structure of the nm-sized crystallites may play an
important role in mechanical properties of nanocrystalline materials. A lm under lattice contraction resists the penetration of the
indenter thereby decreasing the indentation depth (Table 1) and
inhabiting the crack propagation. This leads to increase in hardness and toughness of thin lms. However, under the lattice
expansion, opposite trend is observed. As shown in Fig. 1(b),
when the lattice contracts, the interatomic spacing is compressed,
and a larger applied force is needed to break bonds; in contrary
under lattice expansion, the spacing is extended, and a smaller
force is needed. Thus as aforementioned, the mechanical properties of the NiTiW lms undergoing lattice contraction were
measured better than that undergoing lattice expansion [10].

1.5
ER (%)
H 3/E r 2

0.3
10
0.0
0

-0.3
0

10

15

20

25

30

35

W content (at.%)
Fig. 3. (a) Hardness and elastic modulus, (b) elastic recovery ratio (ER%) and toughness
(H3/E2r ) vs. W content of various NiTiW thin lms.

signicant grain size renement (Table 1). It is widely recognized

that strengthening with grain size renement is attributed to the
propagation of slip across grain boundaries by pile up of dislocation
described by the HallPetch relationship [8]. Grain renement by W
addition results in large number of grain boundaries which restricts
the plastic deformation of the lms to large extent by acting as
barriers to dislocation motion thereby increasing the elastic recovery and toughness of the lms. Drastic decrease in mechanical
properties with increasing the W content beyond 4.5 at% is due to
grain size renement below critical length  15 nm as shown in
Table 1. As the grain size is reduced to critical length scale,
dislocation sources and pile-ups are not expected to exist within
the individual grains due to spatial connement and high volume
fraction of grain boundaries. As can be expected, grain boundary
sliding and grain boundary rotation play dominant role in deformation mechanism, leading to inverse HallPetch effect [9] as
observed experimentally. This departure from HallPetch relation
below 15 nm can be conrmed by calculating the critical grain size
of NiTi lms with maximum hardness according to following
relation [8]:
dc

205

Gb

p1usapp

The present paper investigates the effect of grain renement

on structural, phase transformation behavior and mechanical
properties of NiTi thin lms. This is done by adding W into the
matrix of NiTi by Co-sputtering of NiTi and W targets. Addition of
W into NiTi above its solid solubility limit induces B2R single
step transformation having much less thermal hysteresis. Hardness
and elastic modulus increase with increasing W reaching maximum
values of 32.872.76 GPa and 167.8378.64 GPa respectively. With
further increase in W content mechanical properties are reduced
gradually.

Acknowledgment
The nancial support provided by Ministry of Communications
and Information Technology (MIT), India, under Nanotechnology
Initiative Program with Reference no. 20(11)/2007-VCND is
highly acknowledged.

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