See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/247915775

The Effect of Chemical Composition on Microstructure and Transformation

Behavior of NiTi Shape Memory Alloy Prepared by Vacuum Arc Melting

Article  in  Journal of Biomimetics Biomaterials and Tissue Engineering · July 2008

DOI: 10.4028/www.scientific.net/JBBTE.1.91

CITATIONS READS

0 72

4 authors:

Mandana Bornapour Yahya Motemani

McGill University Saint-Gobain
12 PUBLICATIONS   307 CITATIONS    29 PUBLICATIONS   307 CITATIONS   

SEE PROFILE SEE PROFILE

Mahmoud Nili-Ahmadabadi Shahram Raygan

University of Tehran University of Tehran
189 PUBLICATIONS   1,892 CITATIONS    98 PUBLICATIONS   615 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

maraging steels View project

Bulk Metallic Glasses View project

All content following this page was uploaded by Mandana Bornapour on 25 May 2016.

The user has requested enhancement of the downloaded file.

Journal of Biomimetics, Biomaterials and Tissue Engineering Vol.1 (2008) pp 91-97
online at http://www.scientific.net
© (2008) Trans Tech Publications, Switzerland
Online available since 2008/Jul/14

The Effect of Chemical Composition on Microstructure

and Transformation Behavior of NiTi Shape Memory Alloy
Prepared by Vacuum Arc Melting

M. Bornapour1,a, Y. Motemanni1,b, M. Nili-Ahmadabadi1,c, Sh. Raygan1,d

1
School of Metallurgy and Materials Engineering, Faculty of Engineering,
University of Tehran, Iran, PO. Box: 14395-731
a
mandana.bornapour@gmail.com, b Y_motemanni@engmail.ut.ac.ir, cnili@ ut.ac.ir,
d
shraygan@ut.ac.ir

Keywords: NiTi shape memory alloy, Martensitic phase transformation and Differential scanning
calorimetry

Abstract. NiTi shape memory alloys are a group of materials which have a lot of applications
especially in aerospace industries and medical equipments because of their excellent properties.
Shape memory effect (SME), pseudo-elasticity (PE), high corrosion resistance and biocompatibility
is special properties of these alloys which lead to their extensive applications. The superior behavior
of NiTi alloy is due to thermoelastic martensitic phase transformation. In the present paper, two NiTi
shape memory alloys were prepared by non-consumable vacuum arc melting technique in copper
water cooled crucible. One of them had commercial elements and the other had high purity elements.
Metallographic investigation, chemical analysis, XRD and DSC were carried out on two alloys.
Metallographic observation and XRD shows that structure at ambient temperature consists of
austenite phase besides Ti2Ni, Ni3Ti intermetallic compounds and martensite phase. Transformation
investigation determines that the impurity such as iron in commercial alloy causes two stage phase
transformation B2→R→B19′.

Introduction
Equiatomic Nickel-Titanium (NiTi or Nitinol) is characterized by a unique combination of properties,
including superelasticity and shape memory that make it very attractive for biomedical applications.
The use of Nitinol for medical purposes was first reported in the early 1970s (Cutright et al. 1973).
However, it was only in the mid-1990s that the first widespread commercial stent applications of
Nitinol were introduced. Nitinol was the first “functional biomaterial” to become available, and is
now a subject of active interest in the medical field (Ryhänen 2000). Nowadays, it is applied in
various fields as functional materials, because of its excellent properties in comparison with any other
shape memory alloys, such as large recoverable strain, corrosion resistance, and biocompatibility
[1–3]. NiTi has been used for implants in orthopedics and wires in orthodontics for several decades
and it is responsible for major improvements in these fields. The growth in the use of Nitinol in the

All rights reserved. No part of contents of this paper may be reproduced or transmitted in any form or by any means without the written permission of the
publisher: Trans Tech Publications Ltd, Switzerland, www.ttp.net. (ID: 80.66.187.248-26/07/08,06:58:26)
92 Journal of Biomimetics, Biomaterials and Tissue Engineering Vol.1

medical industries has exploded in the recent years [4, 5]. The shape memory phenomenon is
attributed to the thermoelastic martensitic transformation [6]. The two-step transformation is also
observed because of the formation of an intermediate phase [7]. The intermediate phase appears in the
equiatomic NiTi alloys with increasing the number of thermal cycling, nickel rich NiTi alloys aged at
an appropriate temperature, and in ternary NiTi alloys with an element added [8]. Martensitic phase
transformation temperatures are sensitive to chemical analysis and alloying elements. In the present
paper, two NiTi shape memory alloys were prepared by non-consumable vacuum arc melting
technique in copper water cooled crucible. One of them was prepared by commercial elements while
the other was prepared with more pure elements. Metallographic investigation, Chemical analysis,
XRD and DSC were carried out on two alloys to determine the effect of impurity on microstructure
and transformation behavior.

Experimental Method

In this study, two alloys with nominal composition of 55wt%Ni-45wt%Ti were prepared by non-
-consumable vacuum arc melting technique in copper water cooled crucible. One of them had
commercial elements (A) and the other had high purity elements (B). In order to homogenize
chemical composition, two alloys were remelted four times. Then, samples were vacuum-sealed in a
quartz tube and placed in a controlled atmosphere electrical furnace for 48hrs at 1000ºC. Hot forging
and hot rolling carried out on two alloys at 1000ºC. Finally samples were quenched in water.
Metallographic investigation was employed on both alloys. EDS analysis was used for
characterization of intermetallic compounds. A differential scanning calorimeter with a liquid
nitrogen cooling accessory was employed to characterize the transformation behavior. Samples for
DSC tests were cut into disks 1.4mm in height and 2.6 mm in diameter. The measurement conditions
were chosen according to the ASTM standard for shape memory alloys [9] with heating and cooling
rates of 10ºKmin−1 between −100 and +100°C. Chemical analysis was carried out on the alloys by
wet chemical analysis methods . The samples were scanned over 2θ range of 20°-100° in a Philips
x-ray diffractometer. A position sensitive detector was used in conjunction with a CuKα target.
 Journal of Biomimetics, Biomaterials and Tissue Engineering Vol.1 93

Results and Discussion

Figs. 1 and 2 show metallographic images of the samples A and B. Granular structure can be observed
in Fig. 1 and grain boundaries are shown well. Intermetallic compounds with polygonal morphology
are seen on the grains. On the other hand, in Fig. 2, grain boundaries are not clear. However,
intermetallic compounds are observed apparently. It is probable that the sharpness of grain
boundaries in sample A is due to the accumulation of impurities in the grain boundaries.

Figure 1. Microstructure of alloy A Figure 2. Microstructure of alloy B

Fig. 3 shows SEM images of intermetallic compounds in both alloys. These intermetallic
compounds have polygonal morphology and facet interface with matrix. The EDS results of four
intermetallic compounds in alloys A and B are shown in Table 1. Results of analysis indicated that
these intermetallic compounds are Ti2Ni.

15 µm 15 µm

Figure 3. SEM images of Ti2Ni intermetallic compound with polygonal

morphology.
Table 1. EDS analysis results of four intermetallic compounds with polygonal morphology in both
alloys.
Ni [at %] Ti [at %]
1 32.65 67.35
2 33.20 66.80
3 32.31 67.69
4 32.31 67.69
94 Journal of Biomimetics, Biomaterials and Tissue Engineering Vol.1

Table 1 shows the results of chemical analysis of two alloys. Both of them show deviation from
nominal composition. Nickel content of alloy A is lower than nominal while in alloy B the case is
reverse. Inasmuch as Ti is a reactive element, its reduction is possible during remelting [10]. The Ti
reduction is likely the reason of higher Ni content in alloy B. Existence of minor impurity in alloy A
causes the difference between nominal and experimental composition of the alloy.

Table 2. Chemical analysis results of alloy A and B.

Ni [wt %] Ti [wt %] Fe [wt %] Balance [wt %]
Alloy A 54.4 45.2 0.03 0.37
Alloy B 55.5 44.5 0.00 0.00

The transformation behavior of alloy A and B are shown by DSC curves in Figs. 1and 2. The
heating DSC curves indicate that the reverse transformation occurs in one step in both alloys.
However, two stage phase transformation is observed in cooling DSC curve of alloy A, and single
stage phase transformation occurs in alloy B. The previous studies on transformation behavior of
NiTi shape memory alloys show that impurity elements such as Iron and Aluminum cause to occur
R-phase transformation [11]. Thus, it can be assumed that two stage phase transformation in alloy A
is because of presence of impurity such as Iron which is observed in Table 2. Phase transformation
temperatures of both alloys are shown in Table 3.

Mf(ºC) Ms(ºC) Rf(ºC) Rs(ºC) As(ºC) Af(ºC)

Alloy A 9.00 28.00 32.00 38.00 45.59 63.00
Alloy B 7.73 21.87 35.58 48.42

Figure 4. DSC curve of alloy A Figure 5. DSC curve of alloy B

Table 3. Phase transformation temperatures of alloy A and B

Mf[ºC] Ms[ºC] Rf[ºC] Rs[ºC] As[ºC] Af[ºC]

Alloy A 9.00 28.00 32.00 38.00 45.59 63.00
Alloy B 7.73 21.87 35.58 48.42
 Journal of Biomimetics, Biomaterials and Tissue Engineering Vol.1 95

In NiTi shape memory alloy, transformation temperature is very sensitive to Nickel content as
shown in Fig. 3 [12]. According to Fig. 3, increase of Nickel content more than 50at% (55wt %)
decreases transformation temperature. Ms temperature of alloy A, B, and another alloy with nominal
composition 55wt%Ni have been exhibited in Fig. 3. Fig. 3 shows that Ms temperature of both alloys
is lower than nominal composition (55wt%Ni-45wt%Ti). In the case of alloy B it is reasonable since
Ni content is higher than nominal. In alloy A lower Ms than Ms of nominal composition should be due
impurities. It has been reported that most of impurities reduce Ms temperature [11]. Figs. 4 and 5
show the XRD results in the 2θ range of 20°-100°. In both of them, four specific phases of NiTi are
identified for characterization: austenite (B2), martensite (M), Ti2Ni and Ni3Ti intermetallic
compounds.

Figure 6. Ms temperature as a function of Ni content for binary Ti–Ni alloys [10].

96 Journal of Biomimetics, Biomaterials and Tissue Engineering Vol.1

Figure 8. XRD spectra of alloy B

Figure 7. XRD spectra of alloy A

Conclusions

Ti2Ni intermetallic compound has polygonal morphology with facet interface by matrix. In alloy with
high purity elements, increase of Nickel content because of Ti reduction causes to decrease in
transformation temperature relative to primary nominal composition. The effect of impurities on
transformation temperature is higher than the effect of Nickel content reduction on transformation
temperature in commercial alloy and presence of impurities such as Iron in this alloy, causes B2 →R
→B19′ two step phase transformation. The structure of both alloys consists of austenite phase besides
Ti2Ni, Ni3Ti intermetallic compounds and martensite phase.
 Journal of Biomimetics, Biomaterials and Tissue Engineering Vol.1 97

References

[1] K. Shimizu: Bull. Jpn. Inst. Met Vol. 17 (1978), p. 5.

[2] C. M. Wayman:Bull. Jpn. Inst. Met Vol. 19 (1980), p. 323.

[3] T. Honma: Bull. Jpn. Inst. Met Vol. 19 (1980), p. 366.

[4] T.W. Duerig, A.R. Pelton, D. Stockel: Bio-Medical Materials and Engineering Vol.6 (1996),
p 255-266.

[5] J. Haasters, G. Salis-Solio, G. Bonsmann, in: Engineering Aspects of Shape Memory Alloys,
edited by T.W. Duerig, K.N. Melton, D. Stockel, C.M. Wayman, p.426-444,
Butterworth-Heinemann (1990).

[6] T. Todoroki: Bull. Jpn. Inst. Met Vol. 28 (1982), p. 170.

[7] T. Hara, T. Ohha, E. Okunishi, K. Otsuka: Mater. Trans JIM Vol. 38 (1997), p.11.

[8] T. Saburi , in: Shape Memory Materials, edited by K. Otsuka, C. M. Wayman, Cambridge
University Press, Cambridge (1988).

[9] Standard Test Method for Transformation Temperatures of Nickel– Titanium Alloys by
Thermal Analysis, Designation 2005-00, ASTM, USA (2000).

[10] Y. Motemanni, M. Nili-Ahmadabadi, T. Shahoseini, Sh. Raygan : 18th. Foundrymen Society,

Tehran-Iran, to be published (2006).

[11] K. Otsuka and X. Ren: Progress in Materials Science Vol. 50 (2005), p. 511– 678.
[12] W. Tang: Metall Trans Vol. 28A (1997), p. 537.

View publication stats