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Abstract
Quaternary Ti(2026)Nb(28)Zr(3.511.5)Sn (wt%) alloys were investigated to evaluate the effects of Zr and Sn on Youngs modulus
and superelasticity of TiNb-based alloys. X-ray diffraction analysis showed that solution-treated alloys have + , + , + , , or
microstructures. Zr and Sn increase the lattice parameters of the phase; for orthorhombic matensite, they increase the lattice parameter a but
decrease both b and c. The martensitic start temperature of the is depressed by Zr and Sn additions, whereas the formation of athermal is
dependent on Zr and Sn contents. Differential scanning calorimetry (DSC) measurements show that 1 wt% of Nb, Zr or Sn addition decreases the
martensitic start temperature by 17.6, 41.2 or 40.9 K, respectively, due to their negative effect on lattice parameter ratios of the martensite (c/a and
b/a). Tensile tests were used to evaluate Youngs modulus and superelasticity of the solution-treated alloys. Of the studied alloys Ti24Nb4Zr7.5Sn
with single microstructure has the lowest Youngs modulus of 52 GPa and recoverable elastic strain of about 2% at room temperature after cyclic
strain.
2006 Elsevier B.V. All rights reserved.
Keywords: Youngs modulus; Superelasticity; Biomedical titanium alloy; Martensitic transformation; Alloying effect
1. Introduction
Titanium and its alloys have been widely used as biomedical
materials to replace disfunctioned hard tissue in human body
due to their light weight, low elastic modulus, high strength
and excellent biocompatibility and corrosion resistance. During
the past decade, both near -type and -type titanium alloys
comprising only non-toxic and non-allergic elements have been
developed in an effort to match high strength with low modulus
so as to further ease stress shielding problem [1,2]. The addition of high concentration of stabilizers to some of the newly
developed alloys resulted in martensite with orthorhombic
structure under the condition of quenching [35]. The presence
of martensite, however, reduces hardness and tensile and
fatigue strengths of the alloys [48]. To avoid impairment to
service life, therefore, alloys containing the martensite are
generally considered unsuitable for making implant devices for
hard tissue replacement.
Corresponding author. Tel.: +86 24 2397 1961; fax: +86 24 2390 2021.
E-mail address: ylhao@imr.ac.cn (Y.L. Hao).
0921-5093/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2006.09.051
On the other hand, the martensitic and reverse transformations concerning the can be exploited to develop shape
memory titanium alloys for bio-functional applications, as pioneered by Baker and by Duerig et al. [911]. Their results
suggested that shape memory effect is quite sensitive to heating rate and the maximum recovered strain is about 3% under
the condition of salt bath heating with heating rate higher than
10 C/s. Increasing concern over allergic and toxic effects of
Ni ions released from TiNi led to recent research efforts toward
developing Ni-free shape memory or superelastic titanium alloys
[1219].
In -type titanium alloys, athermal phase is generally
formed in as-quenched conditions [20]. The influence of the
phase on shape memory effect and superelasticity of titanium alloys, however, is not well understood. Moffat and Larbalestier [21] investigated systematically the competing formation between the martensite and the phase in quenched
binary TiNb alloys. Their results suggested that the phase
precipitates would not favour the formation of martensite
and would impair shape memory effect and super-elastic properties of titanium alloys. Recent experimental findings [22,23] of
super-elastic deformation in the absence of martensite is not
Y.L. Hao et al. / Materials Science and Engineering A 441 (2006) 112118
22Nb
+
+
+
+
+
24Nb
+
+
+
+
26Nb
+
+
Table 2
Chemical analysis of TiNbZrSn alloys (wt%)
Composition
Nb
Zr
Sn
Nominal
Analysed
Nominal
Analysed
24
24.0
26
26.1
4
3.93
4
3.89
7.5
7.54
7.5
7.35
0.069
0.0076
0.0049
0.063
0.0079
0.0044
113
using Perkin-Elmer Pyris Diamond Type calorimeter. Phase constitutions and their lattice parameters in as-quenched specimens
were determined by 2/ coupling method of X-ray diffraction
analysis along the longitudinal direction of specimens using
D/max 2500PC Rigaku diffractometer. In order to avoid artifact of stress-induced martensitic transformation, the specimens
were heavily etched in a water solution with 8 vol.% of HF to
remove surface layer with internal stress introduced by grinding
and polishing. In order to increase accuracy of lattice parameter measurement, a low scanning speed of 1 /min was adopted
in this study. Specimens for optical microscope observation
were etched at the boiling temperature of a water solution with
40 vol.% HCl. Transmission electron microscopy (TEM) specimens were prepared from mechanically-thinned plates by electropolishing in a solution of 21% perchloric acid, 50% methanol
and 29% n-butyl alcohol at about 40 C. The thin foils were
examined on a Philips EM420 transmission electron microscope
operating at 100 kV.
3. Results and discussions
3.1. Microstructures and phase constitutions of
TiNbZrSn alloys
Fig. 1 shows three typical microstructures (optical
micrographs) of as-quenched quaternary alloys, represented
by Ti24Nb4Zr7.5Sn, Ti24Nb4Zr3.5Sn and Ti20Nb
4Zr7.5Sn alloys. They appear to have single microstructure
(Fig. 1(a)), or matrix with high and low amount of the
martensite (Fig. 1(b and c)). The small dark spots in Fig. 1(a) are
often observed on metallographic samples of heavily deformed
-phase titanium alloys and are probably dislocation etch pits.
These metallographs also show that the average grain size of the
phase is about 80 m.
Systematic X-ray diffraction analyses revealed that alloys of
the studied range of composition have + , + , + ,
, or microstructures (Table 1). It is clear from Table 1 that,
for identical Zr and Sn contents, the martensite is depressed
with the increase of Nb content. This is consistent with experimental results for binary TiNb alloys [21]. A similar trend
was also observed in the effects of Zr and Sn on the martensitic
transformation, as demonstrated by X-ray diffraction profiles of
Ti24Nb-based alloys presented in Fig. 2: under the condition
of 7.5 Sn addition, the martensite forms in the alloy with 2%
Zr (Fig. 2(e)) but is suppressed in the alloys with 4 and 8% Zr
(Fig. 2(c and d)). For 4Zr addition, the martensite appears in
alloy with low Sn addition (Fig. 2(b)) but disappears with the
increase of Sn contents (Fig. 2(a and d)). Clearly, the addition
of Nb, Zr and Sn decreases the stability of the martensite, as
confirmed by the variation of lattice parameters with chemical
compositions to be described in the next section.
The effects of Zr and Sn on phase formation are complicated. Data presented in Table 1 and Fig. 2 show that, for
Ti24Nb7.5Sn base composition, the phase appears if
Zr addition is 8% but disappears for lower Zr contents (2%
and 4%); for Ti24Nb4Zr base composition, the phase is
suppressed for 3.5% and 7.5% Sn addition but forms if Sn
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Y.L. Hao et al. / Materials Science and Engineering A 441 (2006) 112118
titanium alloys. Moffat and Larbalestier [21] conducted transmission electron microscopy (TEM) analysis of alloys with
different Nb contents and concluded that the modes of
phase decomposition to both the phase and the martensite are mutually exclusive. The phase forms generally in
metastable type titanium alloys if the formation of the
martensite is suppressed during water quenching from above
the transus [24]. In the present investigation, TEM analysis
(Fig. 3) did not find characteristic diffraction spots due to the
phase in Ti24Nb4Zr7.5Sn alloy that features single phase
microstructure (Figs. 1(a) and 2(d)). This suggests that appropriate amounts of Zr and Sn have the advantage of suppressing
the formation of both the martensite and the phase when the
alloy is cooled to room temperature.
The absence of (1 1 1) and (0 1 2) superlattice diffraction
peaks of the phase in X-ray diffraction profiles of all
studied alloys suggests that the phase is disordered. This
is consistent with the results for Ti29Nb13Ta4.6Zr and
Ti39Nb13Ta4.6Zr alloys examined by TEM [24]. By contrast, Banerjee et al. [25] recently reported that the metastable
phase in Ti34Nb9Zr8Ta alloy is ordered.
3.2. Effects of Zr and Sn on lattice parameters of the and
Lattice parameters of both the phase and the martensite determined by X-ray diffraction analysis are listed in
Y.L. Hao et al. / Materials Science and Engineering A 441 (2006) 112118
115
Table 5
Lattice strains of to transformation in TiNbZrSn alloys
24Nb-2Zr7.5Sn
22Nb4Zr7.5Sn
26Nb4Zr3.5Sn
24Nb4Zr7.5Sna
1 1 1 /
0 0 1 (%)
0 0 1 /
0 1 0 (%)
1 1 0 /
1 0 0 (%)
1.1
0.64
0.35
0.16
4.6
5.0
5.9
3.8
5.2
5.2
6.0
4.3
Fig. 3. Bright field TEM micrograph (a) and {1 1 0} selected area diffraction
pattern (b) of Ti24Nb4Zr7.5Sn alloy.
Table 3
of phase in TiNbZrSn alloys
Lattice parameter (A)
20Nb
2Zr7.5Sn
4Zr7.5Sn
8Zr7.5Sn
4Zr3.5Sn
4Zr11.5Sn
22Nb
24Nb
26Nb
3.295
3.291
3.299
3.308
3.304
3.297
3.299
3.293
3.302
24Nb-2Zr7.5Sn
20Nb4Zr7.5Sn
22Nb4Zr7.5Sn
20Nb4Zr3.5Sn
22Nb4Zr3.5Sn
24Nb4Zr3.5Sn
26Nb4Zr3.5Sn
c/a
b/a
3.119
3.089
3.123
3.050
3.074
3.096
3.134
4.868
4.942
4.892
4.981
4.947
4.928
4.888
4.703
4.709
4.691
4.702
4.692
4.674
4.664
1.508
1.524
1.502
1.542
1.526
1.510
1.488
1.561
1.600
1.568
1.633
1.609
1.592
1.560
The temperatures for the to and reverse phase transformations in quaternary alloys were measured by DSC method
between 150 C at cooling and heating rates of 10 C/min. In
sharp contrast with NiTi shape memory alloy, phase transformation peaks of the studied alloys are quite weak; only those
in several compositions can be distinguished and the results are
shown in Table 6. The peak heights of the phase transformation
in the alloys listed in Table 6 are generally lower than 0.02 W/g
and even difficult to distinguish. Fig. 4 gives an example of DSC
measurement of Ti24Nb4Zr7.5Sn alloy. The peak heights of
the studied alloys are also lower than those reported for ternary
TiNbSn alloys [13].
In order to examine the origin of weak phase transformation peaks of DSC measurements, polished Ti24Nb4Zr7.5Sn
Table 6
Temperatures of phase transformation in TiNbZrSn alloys
26Nb4Zr7.5Sn
24Nb4Zr7.5Sn
24Nb4Zr3.5Sn
24Nb2Zr7.5Sn
Ms ( C)
Mf ( C)
77.5
50.1
113.7
32.3
78.8
53.2
112.5
30.2
As ( C)
Af ( C)
44.2
42.4
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Y.L. Hao et al. / Materials Science and Engineering A 441 (2006) 112118
specimens were subjected to in situ optical microstructure observation during cooling and heating between 20 and 150 C.
The results show that the transformation from the matrix to
martensite is quite limited when the specimen is cooled
to 80 C (Fig. 5), 30 C lower than the martensitic finish temperature measured by DSC (Table 6). This suggests
that the martensitic transformation is not fully thermoelastic
Y.L. Hao et al. / Materials Science and Engineering A 441 (2006) 112118
117
Fig. 6. Tensile Youngs modulus (a) and Vickers hardness (b) of water quenched
TiNbZrSn alloys.
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[24]
[25]
[26]
[27]