Materials Science and Engineering A243 (1998) 244 249

Design and mechanical properties of new b type titanium alloys

for implant materials
Daisuke Kuroda a, Mitsuo Niinomi b,*, Masahiko Morinaga c, Yosihisa Kato d,
Toshiaki Yashiro d
b

a
Graduate Student of Toyohashi Uni6ersity of Technology, 1 -1 Hibarigaoka, Tempaku-cho, Toyohashi 441, Japan
Department of Production Systems Engineering, Toyohasi Uni6ersity of Technology, 1 -1 Hibarigaoka, Tempaku-cho, Toyohashi 441, Japan
c
Department of Materials Science and Engineering, Nagoya Uni6ersity, Furo-cho, Chikusa-ku, Nagoya 464 -01, Japan
d
Market De6elopment Department, Daido Steel, 10 Ryugu-cho, Minato-ku, Nagoya 455, Japan

Abstract
Pure titanium and Ti6Al4V alloy have been mainly used as implant materials. V-free titanium alloys like Ti 6Al7Nb and
Ti5Al2.5Fe have been then developed because toxicity of V has been pointed out. Al- and V-free titanium alloys as implant
materials have been developed. Most of them are, however, a + b type alloys. b type titanium alloys with lower moduli of
elasticity and greater strength have been developed recently. Design of new b type titanium alloys composed of non-toxic elements
like Nb, Ta, Zr, Mo or Sn with lower moduli of elasticity and greater strength were, therefore, studied based on the d-electron
alloy design method, and the basic mechanical properties of designed alloys of button ingots melted by tri-arc furnace in the
laboratory were investigated in this study. b type alloys, Ti Nb Ta Zr, Ti Nb Ta Mo and Ti Nb Ta Sn system alloys
designed in this study are expected to have greater performance for implant materials. The Youngs moduli of these alloys are
lower compared with that of Ti6Al4V ELI which has been used as an implant material. The alloys on which some heat
treatments have been conducted offer suitable tensile properties as implant materials. The tensile strength and elongation of
designed alloys in this study are equivalent or greater than required values already reported. 1998 Elsevier Science S.A. All
rights reserved.
Keywords: Biomedical titanium alloys; d-electron alloy design method; Mechanical properties; Youngs modulus; Biocompatibility

1. Introduction
The possibility of substituting the hard tissue instrumentations like artificial bones, artificial hip joints,
artificial teeth and dental implants for functionally disordered hard tissues like bone and teeth is growing.
Ti 6Al4V ELI has been the most widely used for an
orthopedic implant material to date because of its
excellent combination of biocompatibility, corrosion
resistance and mechanical properties. V-free titanium
alloys like Ti6Al 7Nb and Ti 5Al 2.5Fe have been
developed because toxicity of V has been reported [1,2].
Al- and V-free titanium alloys as implant materials
have been developed. However, in terms of mechanical
properties, they are quite similar to Ti 6Al 4V ELI
since they belong to the a +b type titanium alloy
family. Their moduli of elasticity are still greater com* Corresponding author. Tel.: +81 532 446706; fax: + 81 532
446690; e-mail: r2mnlo@edu.tut.cc.tut.ac.jp
0921-5093/98/$19.00 1998 Elsevier Science S.A. All rights reserved.
PII S 0 9 2 1 - 5 0 9 3 ( 9 7 ) 0 0 8 0 8 - 3

pared with that of bone. The titanium biomaterials

research is done by focussing on b type titanium alloys
because processing variables can be controlled to produce selected results. Enhanced properties such as lower
modulus of elasticity, increased corrosion resistance
and improved tissue response are possible when compared with a+ b type alloys. b type titanium alloys
with lower moduli of elasticity and greater strength
have been developed recently. The cytotoxicity of pure
metals and the relationship between biocompatibility
and polarization resistance of surgical implant materials
have been reported by Steinemann [3]. Kawahara has
reported that metallic Al, V and Fe are higher cytotoxic
elements to date [3]. Therefore, in this study, new b
type titanium alloys composed of non-toxic elements
such as Nb, Ta, Zr, Mo and Sn with lower moduli of
elasticity, greater strength and greater corrosion resistance were designed using a new alloy design method
based on the molecular orbital calculation of electronic

D. Kuroda et al. / Materials Science and Engineering A243 (1998) 244249

245

Fig. 1. Biological safety of metals (a): cytotoxicity of pure metals, and (b): relationship between polarization resistance and biocompatibility of
pure metals, Co Cr alloy and stainless steels.

structures proposed by Morinaga et al. [4]. The designed alloys were melted by a tri-arc furnace in the
laboratory. The tensile tests were conducted at room
temperature in order to investigate the basic mechanical
properties of the designed alloys.

2. Experimental procedures

2.1. Selection of alloying elements for designing new b

type titanium alloys
Ti6Al4V ELI is the most widely used orthopedic
titanium alloy because of its excellent corrosion resistance and good mechanical properties. The toxicity of
V has been, however, reported. Al is a questionable
element on certain disease. The cytotoxicity of pure
metals and the relationship between biocompatibility
and polarization resistance of typical pure metals and
surgical implant materials have been reported by
Steinemann [3]. The high cytotoxicity of V and tissue
response of capsule (scar tissue) type due to Al are
demonstrated, while Ti, Nb, Ta and Zr exhibit excellent
biocompatibility and belong to the loose connective
vascularized (vital) group in the type of tissue reaction.
Kawahara has also reported that metallic V and Fe are
high cytotoxic elements, while Ti, Nb, Ta, Zr and Sn
are low cytotoxic elements [3]. These trends reported by
Steimemann and Kawahara are shown in Fig. 1(a) and
(b). The non-toxic elements like Nb, Ta, Zr, Mo and Sn
were, therefore, selected for designing new b type tita-

Table 1
Values of Bo and Md in designed alloys
Alloy number

Chemical composition (mass%)

Bo

Md

1
2
3
4
5
7

Ti 29Nb 13Ta 4.6Zr

Ti 16Nb 13Ta 4Mo
Ti 29Nb 13Ta
Ti 29Nb 13Ta 4Mo
Ti 29Nb 13Ta 2Sn
Ti 29Nb 13Ta 6Sn

2.878
2.843
2.866
2.815
2.856
2.853

2.462
2.436
2.446
2.413
2.438
2.434

Fig. 2. Phase stability index diagram based on Bo and Md parameters.

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D. Kuroda et al. / Materials Science and Engineering A243 (1998) 244249

nium alloys with lower moduli of elasticity, greater

strength and greater corrosion resistance.

2.2. A method for theoretical alloy design [4]

Employing a molecular orbital method, electronic
structures were calculated for b.c.c. Ti alloyed with a
variety of elements, and two alloying parameters were
determined theoretically. One is the bond order (hereafter referred to as Bo) which is a measure of the
covalent bond strength between Ti and an alloying
element. The other is the metal d-orbital energy level
(Md) which correlates with the electronegativity and the
metallic radius of elements. For alloys, the average
values of Bo and Md are defined by taking the compositional averages of the parameters and denote them Bo
and Md, respectively. Bo and Md values, and the chemical compositions of the designed alloys in this study
are given in Table 1. Fig. 2 is a phase stability map
(called the Bo Md map) in which the areas of a, a+ b
and b type alloys are separated clearly. The stability
region of the b type alloys extends to the higher Bo and
to the lower Md region. Positions of titanium and
titanium alloys are shown by the numbers surrounded
by the open circles in Fig. 3. The values of moduli of
elasticity are also shown in parentheses. The values of
moduli of elasticity for these alloys are decreased with

increasing Bo and Md values in b type alloys region on

the Bo Md map. The alloy position moves in the
Bo Md map as the alloy composition varies as shown
in Fig. 4. For a TiMo system, for example, it moves
to the left (the lower Md region) with increasing Mo
content. Such a vector varies in direction and magnitude, depending on alloying elements, as is shown in
the map. Once a specific Bo Md region and a specific
alloy system are set in the map, the corresponding alloy
composition is simply determined following the rule of
the vector sum. The trial and error experiments are no
longer needed in order to optimize the alloy composition.

2.3. Specimen preparation and tensile tests

The designed alloys were melted by tri-arc furnace
from appropriate mixtures of sponge Ti and alloying
elements. The 45 g button-shaped samples were homogenized at 1273 K for 21.6 ks, and were then cold rolled
to 75% reduction. Thermomechanical processes for designed alloy production are shown in Fig. 5. Each
designed alloy was solutionized at 1117 K for 1.8 ks
after homogenization, and then were aged at 673, 723
and 773 K for 10.8 ks, respectively. Heating and cooling process were carried out in argon atmosphere.
Several tensile test specimens with the size of 5612

Fig. 3. Phase stability index diagram based on Bo and Md parameters. Modulus (GPa) in each alloy is shown in the parenthesis.

D. Kuroda et al. / Materials Science and Engineering A243 (1998) 244249

1.5 mm3 were machined from each ingot sample of

designed alloy. The tensile tests were conducted at
room temperature in order to investigate the basic
mechanical properties of the designed alloys. Ultimate
tensile strength, 0.2% yield strength, moduli of elasticity
and elongation were determined. After evaluation of
mechanical properties, the specimens were etched with
a solution containing hydrofluoric acid, HF (32 cm3);
nitric acid, HNO3 (20 cm3) and H2O (77 78 cm3) to
reveal the microstructure. The microstructure of each
designed alloy was observed by light microscopy.

247

Fig. 5. Schematic drawing of thermomechanical processes for designed alloys; S.T., solution-treatment; C.W., cold-working.

3. Results and discussion

3.1. Microstructural obser6ation

Typical as-solutionized microstructure of designed
alloy, Ti29Nb 13Ta 4.6Zr, is shown in Fig. 6. The
average b grain size of this alloy was :23 mm. The
average b grain size of another designed alloy, Ti
16Nb13Ta4Mo, which contained Mo instead of Zr
was :30 mm. The average b grain size of Ti 29Nb
13Ta4Mo, whose Nb content was increased, was
: 26 mm. The average b grain size of the other designed
alloy, Ti29Nb 13Ta 2Sn, which contained Sn instead of Zr was :28 mm. The differences of the
average b grain size between the designed alloys were
slight.

Fig. 6. Typical light micrograph of Ti 29Nb 13Ta 4.6Zr alloy after

solution treatment.

3.2. Mechanical properties of designed alloys

Fig. 4. Bo Md lines drawn for various TiM binary alloys. M

indicates an alloying element.

Ultimate tensile strength, 0.2% proof stress and elongation of designed alloys are shown in Fig. 7. The
moduli of elasticity of designed alloys were also indicated in Fig. 8. Each as-solutionized designed alloy has
lower strength and equivalent or greater elongation
when compared with those of conventional titanium
alloys such as Ti6Al4V ELI and Ti13Nb13Zr.
The tensile strength of Ti29Nb13Ta4.6Zr after aging at 673 K for 10.8 ks is equivalent to or greater than
conventional titanium alloys. The tensile strength of
Ti16Nb13Ta4Mo after aging at 673 K for 10.8 ks
is the greatest among the designed alloys in this study.
This designed alloy was, however, more brittle. The
tensile strength of Ti29Nb13Ta4Mo, whose Nb
content is increased, is lower compared with that of
Ti16Nb13Ta4Mo alloy. It is, in general, known
that the v-phase precipitates at lower temperature aging in b alloys with a lower equivalent% Mo. It is also
known that the tensile strength increases with increas-

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D. Kuroda et al. / Materials Science and Engineering A243 (1998) 244249

Fig. 7. Comparison of mechanical properties in each alloy.

ing v-phase while the elongation decreases. The designed alloys were aged with a lower temperature aging
(673773 K). The precipitation of the v-phase will,
therefore, cause an increase in tensile strength and a
decrease in elongation of Ti 16Nb 13Ta 4Mo. The
moduli of elasticity of as-solutionized designed alloys
are lower compared with those of conventional titanium alloys for medical implants as shown in Fig. 8. In
the aged (at 673 K for 10.8 ks) condition, Ti29Nb
13Ta4.6Zr has equivalent or lower modulus of elasticity compared with those of conventional titanium
alloys. TiNbTa Sn system alloys in as-solutionized
conditions have also lower moduli of elasticity compared with those of conventional titanium alloys. The
tensile strength of Ti 29Nb 13Ta 4.6Sn alloy is the
greatest among the Ti Nb Ta Sn system alloys after
aging at 673 K for 10.8 ks. The elongation of this alloy
is lowest among other aged Ti Nb Ta Sn system

alloys. The moduli of elasticity of TiNbTaSn system alloys are equivalent or lower compared with those
of conventional titanium alloys for implant materials.

4. Conclusions
(1) The tensile strength and elongation of Ti29Nb
13Ta4.6Zr alloy is equivalent to or greater than those
of conventional titanium alloys for implant materials.
(2) The Youngs moduli of the designed alloys are
much lower compared with that of Ti6Al4V ELI
which has been, in general, used for an implant material.
(3) b type titanium alloys, TiNbTaZr, TiNb
TaMo and TiNbTaSn system alloys, designed in
this study are expected to have greater performances
for implant materials.

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249

Fig. 8. Modulus of each alloy.

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