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Titanium alloys for biomedical applications

H.J. Rack, J.I. Qazi


*
School of Materials Science and Engineering, Clemson University, Clemson, SC 29634-0971, USA
Available online 12 October 2005
Abstract
Titanium alloys, because of their excellent mechanical, physical and biological performance, are finding ever-increasing application in
biomedical devices. This paper provides an overview of titanium alloy use for medical devices, their current status, future opportunities and
obstacles for expanded application. The article is divided into three main sections, the first discussing recent efforts focused on commercial purity
titanium. This is followed by considering effects of chemistry, grain size and a/h morphologies on mechanical properties of a+h alloys. Finally,
the third section reviews the status of metastable h alloys specifically designed for biomedical applications emphasizing their aging behavior and
its effects on mechanical properties.
D 2005 Elsevier B.V. All rights reserved.
Keywords: Biomaterials; Titanium alloys; Implants; Mechanical properties
1. Introduction
Continual aging of the US population has brought with it
an ever-increasing need for materials specifically suited for
bio-device application. For example, it is projected that
approximately 272,000 total hip replacements will annually
be performed by 2030. Additionally of the 152,000 total hip
replacements performed in 2000 approximately, 12.8%
involved revisions of previous hip replacements. The fact
that such a high percentage of hip replacements performed
every year are revision surgeries, although troubling, is not
surprising when the life expectancy of the implant versus the
ever-increasing life expectancy of the patient is considered.
Consistently, over 30% of those requiring total hip replace-
ments have been below the age of 65 and even those over
the age of 65 now have a life expectancy of 17.9 years.
Moreover female patients, who make up the majority of
those receiving total hip replacements, have a life expectancy
of 19.2 years at the age of 65. With a normal implant
longevity of 12 to 15 years, the majority of those that receive
hip implants at age of 65 will require at least one revision
surgery.
Various metallic materials have been used for total hip
replacements as well as other joint replacement surgeries, i.e.,
knees, shoulders. Additional applications include trauma and
spinal fixation devices, cardiovascular stents, and, most
recently, replacement spinal discs. The material list includes
stainless steel, CoCr Mo alloys, titanium alloys and other
more specialized alloys, e.g., AuPd. Of these titanium
alloys, the subject of the present article, offers several
benefits, including lower elastic modulus, excellent corrosion
resistance and enhanced biocompatibility [1]. The former is
particularly important for hard tissue replacement where stress
shielding, a phenomenon where reabsorption of natural bone
and implant loosening arises because of the difference in
elastic modulus between natural bone and hard tissue implant,
is one of the primary causes requiring revision surgery [2].
Another well-documented and related cause is bone necrosis.
This phenomenon has been associated with wear debris
generated from articulating components at a tabular cup.
Such wear debris has been shown to migrate and position
itself at the bone-implant stem interface thereby further
promoting bone cell death.
The present review builds on several excellent prior
summaries [1,35] and shows that this arena remains a
fruitful area for titanium research and development. It begins
by examining recent efforts focused at enhancing long used
biomedical titanium alloys, i.e., commercial purity titanium
and Ti 6Al 4V, these having been adapted from the
0928-4931/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.msec.2005.08.032
* Corresponding author. Kemet Electronics Inc., 2835 KEMET Way
Simpsonville, SC 29681, USA. Tel.: +1 864 228 4442; fax: +1 864 228 4264.
E-mail address: javaidqazi@kemet.com (J.I. Qazi).
Materials Science and Engineering C 26 (2006) 1269 1277
www.elsevier.com/locate/msec
aerospace community, and then discusses newer metastable
beta titanium alloys specially designed for biomedical
application.
2. Commercial purity titanium alloys
Commercial purity titanium has long been used for
biomedical devices, for example cardiovascular stents, lead
wires and spinal/trauma fixation devices. When maintained at
low Fe content there is little concern about adverse interaction
between the implant and the human body. Notwithstanding
these positive attributes, the mechanical strength of commercial
purity titanium remains below the normal thresholds consid-
ered for hard tissue replacement. Indeed the desire for
enhanced strength has led to the increasing use of grade 4
commercial purity titanium for biodevices, the strength
increase above that of grade 2 being achieved through an
increase in the oxygen content.
An alternative and potentially more attractive method for
enhancing the mechanical performance of commercial purity
titanium has recently been reported by Valiev et al. [6]. These
investigators have investigated the strengthening of grade 2
commercial purity titanium utilizing equal channel angular
pressing (ECAP) in combination with other deformation
processes. Procedures examined include ECAP (8 passes) at
400 -C (#1), ECAP+65% cold rolling (#2), and ECAP+rolling
followed by annealing at 300 -C, for 1 h (#3). Ultra-fine
grained (UFG) structures, Fig. 1, can range from an equiaxed
cellular microstructure to a sub-grain structure with a defined
boundary structure. In all cases the microhardness of severely
deformed commercial purity titanium was superior to that of
the original coarse-grained commercial purity titanium, Table
1. The yield and ultimate tensile strengths also exhibit this
enhancement, a 140% increase in ultimate tensile strength vis a
vis coarse-grained commercial purity titanium being observed.
Notably this increase was achieved while maintaining an
elongation to failure of 9%.
Table 1 also shows that the fatigue limit of ultra-fine grained
commercial purity titanium depends strongly on its micro-
structure state. For example, ultra-fine grained grade 2
commercial purity titanium processed via path 3 had a fatigue
limit of 500 MPa, almost 100% higher than its coarse-grained
commercial purity titanium counterpart. Additionally, ultra-fine
grained titanium exhibited a higher fatigue strength than
coarse-grained titanium in both the low and high cyclic fatigue
range, Fig. 2. A comparison between ultra-fine grained grade 2
commercial purity titanium processed via path 3 indicates that
its strength, ductility and fatigue limit are comparable to Ti
200 nm
400 nm
(a)
(b)
Fig. 1. Micrographs showing the ultra fine grained structure in CPtitanium
grade 2 produced by (a) ECAP and (b) ECAP+rolling [6].
Table 1
Microhardness, tensile mechanical properties and fatigue limit of grade 2 Cp Ti in different states [6]
State (structure type) Hv, (MPa) UTS, (MPa) YS (MPa) El. (%) RA (%) Fatigue limit (MPa)
Coarse-grained 1800 460 380 26 60 238T10
UFG #1 (Equiaxed, submicron-grained) 2700 710 625 14 60 403T8
UFG #2 (Fibrous, with high dislocation density) 2821 960 725 10 45 434T5
UFG #3 (subgrained with internal cells) 2850 1100 915 9 40 500T8
Ti 6Al 4V ELI (annealed) 965 875 1015 2547 515
200
400
600
800
1000
2 3 4 5 6 7 8
lg N

,

M
P
a
CG
#1
#2
#3
*
*
*
+
+
+
Fig. 2. Fatigue response of ultra-fine grained grade 2 commercial purity
titanium with (CG) coarse grained, (#1) equiaxed cellular, (#2) elongated and
(#3) sub-grain microstructures [6].
H.J. Rack, J.I. Qazi / Materials Science and Engineering C 26 (2006) 12691277 1270
6Al 4V ELI. This suggests that substitution of ultra-fine
grained grade 2 commercial purity should be possible, thereby
eliminating any possible concern of the vanadium containing
Ti 6Al 4V [7,8]. Finally further enhancements in mechanical
performance should also be possible with other grades of
commercial purity titanium, this evaluation being presently
underway.
Recently Yao et al. [9] have shown that the aforementioned
ultra-fine grained structure produced by treatment #2 addition-
ally, influences the in vitro functionality of cells on a
commercial purity titanium implant surface. These results,
Fig. 3, provide evidence of increased osteoblast adhesion after
a 4 h exposure on ultra-fine grain commercial purity titanium
when compared to conventional grade 2 titanium. These
authors suggested that these results may be related to the
increased number of grain boundary sites in ultra-fine grained
materials or to an increase in the reactive site activity thereby
promoting cell adhesion. While the underlying mechanisms of
increased cell adhesion on ultra-fine grained titanium are still
under investigation, earlier studies of nano-grained metals
prepared by powder-metallurgy techniques do emphasis the
important role of grain boundaries, enhanced osteoblast
adhesion having been observed at grain boundaries. Further
efforts focused on in vivo investigations and including a study
of subsequent deposition of calcium-containing minerals, as
found in bone, are also currently underway.
Finally, some evidence exists that the frictional behavior of
ultra-fine grained commercial purity titanium is superior to
coarse-grained material. However it is not clear that the long
time response of tribo couples, where an effective ultra-fine
grain size is developed within the near surface regions during
wear, even in normal grain commercial purity titanium, will
lead to enhancement. This dependence may of course be
influenced by the specific tribo couple examined and the
particular methodology used to achieve the ultra-fine grain
microstructure.
3. Alphabeta titanium alloys
The mechanical behavior of biomedical grade commercial
purity titanium is generally considered to lie below that desired
for total joint replacement. This led to the early introduction of
annealed Ti 6Al 4V, which today remains the largest single
titanium alloy used for biomedical device manufacture.
Continued concern with respect to the biological response of
vanadium containing materials has moreover led to the
development and introduction of Ti 6Al 7Nb [10], the level
of niobium substitution for vanadium being specified so that
the proportion of the alpha and beta phases during routine
processing mimics that of Ti 6Al 4V. Recent interest in
reduced modulus alpha-beta titanium alloys has resulted in the
development of Ti 13Nb13Zr [11], its strength properties
being comparable to Ti 6Al 4V.
Present application of these materials tends to be limited to
the solution annealed condition, only slight attention being
given to enhancing the properties of Ti 6Al 4V by control of
the alpha/beta volume fraction and morphology. Fig. 4
illustrates the three distinct microstructures, lamellar, equiaxed
0
0.5
1
1.5
2
Grain size
C
e
l
l

a
d
h
e
s
i
o
n
/
a
r
b
i
t
r
a
r
y

u
n
i
t
s
CG UFG
Fig. 3. Enhanced osteoblast adhesion on ultra-fine grained (UFG) compared to
conventional grained (CG) commercial purity titanium, cell adhesion results
being normalized to adhesion on wrought Ti foil. Data are mean+std; n =3;
*p <0.1 compared to the titanium foil [9].
(a)

50m

(b)


(c)

25m

50m
Fig. 4. Different microstructures that can be produced in Ti 6Al 4V; (a)
lamellar, (b) equiaxed and (c) bimodal [12].
H.J. Rack, J.I. Qazi / Materials Science and Engineering C 26 (2006) 12691277 1271
and bimodal, that can be produced in Ti 6Al 4V through
control of solution annealing temperature, cooling rate and
final aging temperature. The lamellar structure shown in Fig.
4a is typically produced following solution treatment above the
h transus, followed by air cooling, and aging between 700 and
800 -C. Solution annealing below the h transus, e.g., between
800 and 925 -C results in an equiaxed structure, Fig. 4b.
Finally, the bimodal structure, Fig. 4c, may be developed by
solution treatment below the h transus, typically between 900
950 -C followed by air cooling and aging below 700 -C. Table
2 shows that equiaxed alpha microstructures provide high
strength and ductility and relatively low fracture toughness,
whereas lamellar structure provides good fracture toughness
but with some compromise on strength and ductility. Finally,
the high cycle fatigue response of Ti 6Al 4V can be modified
through microstructure control. Fig. 5 shows that the bimodal
microstructure, previously discussed, has the highest high cycle
performance followed by the equiaxed structure, with the
lamellar microstructure having the lowest high cycle fatigue
resistance. Furthermore, within each of these microstructure
categories, finer microstructures result in higher high cycle
fatigue strength.
Preliminary efforts employing the severe plastic deforma-
tion procedures previously implemented in commercial purity
titanium have also shown promise for enhancing the mechan-
ical properties of alpha-beta titanium alloys, e.g., Ti 6Al 4V.
Table 3 shows that severe plastic deformation resulted in a
minimum 20% increase in yield and ultimate tensile strength
vis a vis annealed Ti 6Al 4V, with the tensile elongation
remaining above that typically required for biomedical
application (10%). Additional enhancement can be achieved
by combining severe plastic deformation by equal channel
angular extrusion with upsetting.
Studies of the reciprocating sliding wear performance of
Ti 6Al 4V processed similarly to that described above again
suggests that this procedure may not offer marked improve-
ment. For example recent efforts show that the enhancement of
ultra-fine grained Ti 6Al 4Vs dynamic frictional coefficient
and the steady-state wear rate are marginal, with a slight
enhancement of the former at higher apparent contact stress,
Figs. 6 and 7. Certainly further effort examining and
understanding these phenomena are warranted.
Finally in vivo studies of cell functionality, in ultra-fine
grained Ti 6Al 4V have confirmed the enhancement in
osteoblast adhesion previously shown for ultra-fine grained
commercial purity grade 2 titanium [9]. The interpretation of
this data is however, further complicated when compared to
Table 2
Tensile properties the Ti 6Al 4V [13]
Microstructure YS
(MPa)
UTS
(MPa)
El.
(%)
RA
(%)
K
IC
MPa/m
Equiaxed (Std) 951 1020 15 35 61
Lamellar (Std) 884 949 13 23 78
Equiaxed (ELI) 830 903 17 44 91
Equiaxed (CMG) 1068 1096 15 40 54
Oxygen content: Std: 0.150.2%; Eli: 0.13 Max; Cmg: 0.180.2%.
YS: Yield Strength; UTS: Ultimate Tensile Strength; El.: Elongation; RA:
Reduction in area.
Fig. 5. Influence of microstructure on high cycle fatigue strength of Ti 6Al
4V [14].
Table 3
Tensile properties the Ti 6Al 4V ELI [6]
State UTS (MPa) YS (MPa) El. (%)
1 Annealed 970 900 20
2 1+ECAP at 700 -C, E =6.5. 1160 1110 12
3 2+upset at 600 -C, E =55% 1450 1420 11
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
1 10 100 1000 10000
Number of cycles
1 10 100 1000 10000
Number of cycles
D
y
n
a
m
i
c

F
r
i
c
t
i
o
n

c
o
e
f
f
UFG Ti 6Al-4V
Annealed Ti-6Al-4V
(a)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
D
y
n
a
m
i
c

F
r
i
c
t
i
o
n

c
o
e
f
f
(b)
UFG Ti 6Al-4V
Annealed Ti-6Al-4V
Fig. 6. 2-D friction traces (dynamic friction coefficient at maximum velocity)
for Ti 6Al 4Vas a function of the number of dry reciprocatingsliding cycles
at an apparent contact stress of (a) 1.5 MPa and (b) 5 MPa [15].
H.J. Rack, J.I. Qazi / Materials Science and Engineering C 26 (2006) 12691277 1272
the latter material since several levels of refinement are
possible in two phase Ti 6Al 4V, e.g., the alpha and beta
particle size, the uniformity of dispersion (primarily of the
beta phase) and the internal alpha and beta grain size. These
are not single valued functions of the processing history, Fig.
8, showing that low temperature annealing may have a
measureable effect on the nanohardness of the individual
alpha and beta phases without major affects on the micro-
hardness response.
These preliminary studies suggest that UFG structures have
superior mechanical and biological response in comparison to
their regular grained counterparts. Utilization of these proces-
sing routes to produce UFG structures for enhancement of the
mechanical and biological behavior of recently developed
titanium alloys containing only biocompatible alloying ele-
ments (e.g. Nb, Zr, Ta, etc.), remains an area for further
exploration.
4. Metastable beta titanium alloys
While commercial purity and alphabeta titanium alloys
remain the primary titanium materials used for current
biomedical application the past decade has shown a substantial
increase in the synthesis of metastable beta titanium alloys
designed specifically for this field. Originally intended to
address the dual requirement of low modulus, approaching that
of bone, and enhanced biocompatibility, these systems are now
being considered for other applications (spinal, trauma, etc.)
which maintain the latter requirement while enhancing the
mechanical performance through artificial aging. Three alloys
were essentially developed simultaneously, Ti 29Nb13Ta
4.6Zr, Ti 12Mo6Zr 2Fe (TMZF), Ti 35Nb7Zr 5Ta
(TiOsteum) in Japan and the United States.
0
0.2
0.4
0.6
0.8
1
1.2
1.5MPa 5MPa
Apparent Contact Stress
S
t
e
a
d
y

s
t
a
t
e

W
e
a
r

R
a
t
e

(
m
m
/
k
m
)
UFG Ti-6Al-4V
Ti-6Al-4V
Fig. 7. Steady-state wear rate of Ti 6Al 4V during dry reciprocatingsliding
against a hardened steel counterpart [15].
2.5
3.5
4.5
5.5
0 300 600 900
Temperature (C)
Temperature (C)
N
a
n
o

h
a
r
d
n
e
s
s

(
G
P
a
)
Alpha Beta
(a)
250
300
350
400
0 150 300 450 600 750 900
M
i
c
o
r
h
a
r
d
n
e
s

(
V
H
N
)
(b)
Fig. 8. Dependence of hardness on annealing temperature for nano-grained Ti
6Al 4V; (a) shows nano-hardness of a and h phases and (b) shows overall
microhardness [16].
20
30
40
50
60
70
80
90
20 30 40 50 60 70 80 90 100
Grain Size (m)
Grain Size (m)
E
l
o
n
g
a
t
i
o
n

&

R
A

(
%
)
RA El
(a)
100
200
300
400
500
600
700
20 30 40 50 60 70 80 90 100
S
t
r
e
n
g
t
h

(
M
P
a
)
YS UTS
(b)
Fig. 9. Effect of grain size on (a) elongation and reduction in area, and (b) on
yield and ultimate tensile strengths of Ti 29Nb13Ta4.6Zr [17].
H.J. Rack, J.I. Qazi / Materials Science and Engineering C 26 (2006) 12691277 1273
The former, Ti 29Nb13Ta 4.6Zr, following water
quenching from the h-phase field displays a mixture of h
phase and orthorhombic martensite (a
//
) and has an elastic
modulus of 65 GPa [17]. Further examination has shown that
the average h grain size and the volume fraction of martensite
has an important influence on this materials mechanical
properties, Fig. 9. For example, solution treatment at 850 -C
for 1 h, results in an average grain size of 50 Am with some h
phase transforming to a
//
, the alloy having a yield strength of
250 MPa and elongation of 45%. Reducing the solution
treatment temperature to 750 -C and time to 0.5 h results in a
grain size reduction to 25 Am, reduces the volume fraction of
martensite considerably, increases the yield strength to 400
MPa and reduces the elongation to 30%, without any apparent
influence on elastic modulus [18].
The strength of this alloy can also be increased signifi-
cantly by aging, this increase in strength coming at the
expense of ductility and elastic modulus. Yield strengths as
high as 1100 MPa have been attained after long aging
treatments, e.g. aging at 450 -C for 48 h resulting in a yield
strength of 1150 MPa. However, this increase occurs at the
expense of elongation, which is reduced to less than 3%, Fig.
10, and an increase in elastic modulus to 85 GPa. Micro-
structure analysis indicated that the observed increase in the
strength after aging results from N and/or a phase precipita-
tion; aging at temperatures below 400 -C resulting in N phase
precipitation while aging at higher temperatures and/or longer
times, resulting in a mixture of N and a phases, Fig. 11.
Finally, aging at temperature above 475 -C results in only a
phase precipitation [18].
200
400
600
800
1000
1200
200 300 400 500 600 700
Aging Temperature (C)
Aging Temperature (C)
Aging Temperature (C)
Y
i
e
l
d

S
t
r
e
n
g
t
h

(
M
P
a
)
4 hrs
24 hrs
48 hrs
(a)
0
10
20
30
40
200 300 400 500 600 700
E
l
o
n
g
a
t
i
o
n

(
%
)
4 hrs
24 hrs
48 hrs
(b)
60
65
70
75
80
85
90
95
100
105
200 300 400 500 600 700
Y
o
u
n
g
'
s

m
o
d
u
l
u
s

(
G
P
a
)
4 rs
24 hrs
48 hrs
(c)
Fig. 10. Effect of aging time and temperature on tensile (a) elongation, (b) yield
strength and (c) Youngs modulus of Ti 29Nb13Ta4.6Zr [18].
473
573
673
773
873
973
0 28.8 57.6 86.4 115.2 144 172.8 201.6
Time (ks)
T
e
m
p
e
r
a
t
u
r
e

(
K
)

+
++
+
Fig. 11. Time temperature transformation diagram of Ti 29Nb13Zr 4.6Ta.
The open symbols denote samples containing a
//
martensite after quenching
into ice water. The dotted, short dash and long dash lines denote 10, 30, and 50
vol.% of a phase, respectively [18]. T(-C) =T(K) 273.
Table 4
Tensile properties of Ti 35Nb7Zr 5Ta [21]
Thermal treatment YS (MPa) UTS (MPa) El. (%) RA (%)
ST (0.06% O) 530 590 21 69
SA (0.06% O) 630 686 17 42
DA (0.06% O) 697 753 15 35
ST (0.46% O) 937 1014 19 55
SA (0.46%O) 1007 1055 12 27
DA (0.46% O) 1202 1244 8 16
ST (0.68% O) 1081 1097 28 50
SA (0.68% O) 1222 1252 9 13
DA (0.68% O) 1234 1260 7 9
SA: 260 -C 4 h, AC; DA: 260 -C 4 h, AC, 427 -C 8 h, AC; AC: Air cooled.
200
300
400
500
600
700
1 10 100 1000 10000
Cycles of Fatigue (x10
4
)
B
e
n
d
i
n
g

S
t
r
e
s
s

(
M
P
a
)
0.06% O 0.46% O
Fig. 12. Stress-controlled fatigue response for Ti 35Nb7Zr 5Ta with two
different oxygen contents [22].
H.J. Rack, J.I. Qazi / Materials Science and Engineering C 26 (2006) 12691277 1274
In contrast to Ti 29Nb13Ta4.6Zr, water quenching of
Ti 12Mo6Zr 2Fe (TMZF) from the h phase field com-
pletely retains the h phase. In solution treated condition, TMZF
also has much higher tensile yield strength (1000 MPa),
comparable to mill annealed Ti 6Al 4V, along with 18%
elongation. In solution treated condition TMZF has an elastic
modulus of 7984 GPa although bit lower than Ti 6Al 4V,
but much higher than Ti 29Nb13Ta4.6Zr. The tensile yield
strength of TMZF can also be increased by artificial aging with
a concurrent increase in the elastic modulus [19].
Finally, Ti 35Nb7Zr 5Ta, at 0.06 O, has the lowest
elastic modulus, 55 GPa, of the more recently developed alloys
[20]. Table 4 illustrate the tensile properties achievable in this
alloy after different aging treatments for three different oxygen
contents. Yield strength can be increased at fixed oxygen
content, either by single (SA) or duplex (DA) aging, this
increase being accompanied by a slight decrease in tensile
elongation. An increase in the oxygen content from 0.06 to
0.46 wt.% O also increases the solution treated yield strength
from 530 MPa (0.06% O) to 937 MPa with a slight decrease in
elongation from 21% to 19%. It is notable however, that this
increase in the yield strength is accompanied by an increase in
the elastic modulus, 63 GPa [20]. Additionally, this increase in
the oxygen content also increases the high cycle fatigue
strength of the alloy in the solution treated condition from
275 MPa to 450 MPa, Fig. 12 [22].
The oxygen content of Ti 35Nb7Zr 5Ta strongly influ-
ences its aging behavior and hence its mechanical properties.
Solution treatment in h phase field followed by water
quenching results in complete h phase retention in alloys
containing up to 0.68 wt.% oxygen, some diffuse N being
present in low (0.06 wt.%) oxygen alloys [23]. Oxygen
addition restricts the motion of linear defects in metastable h
titanium alloys thus hindering the collapse of alternating (111)
planes, the latter being required for N phase formation. Thus
(a)
(b)
4m
4m
4m
(c)
Fig. 15. Scanning electron micrographs illustrating the microstructure of Ti
35Nb7Zr 5Ta containing (a) 0.06 (b) 0.46 and (c) 0.68 wt.% oxygen aged at
593 -C for 8 h [24].
0
500
1000
34 36 38 40 42
2
I
n
t
e
n
s
i
t
y

(
a
r
b
i
t
r
a
r
y

u
n
i
t
s
)

(110)
(a)
(b)
(c)
48 52 56
(102 )

(200)
(211 )
72 76 80 84
(220)
(201)
(212)
(301)
(212)
Fig. 14. X-ray diffraction patterns of Ti 35Nb7Zr 5Ta containing (a) 0.06,
(b) 0.46 and (c) 0.68 wt.% O aged at 260 -C 4 h/427 -C for 8 h (DA) [21].
0
500
1000
34 36 38 40 42
2
I
n
t
e
n
s
i
t
y

(
a
r
b
i
t
r
a
r
y

u
n
i
t
s
)

(110)
(a)
(b)
(c)
48 52 56

(102 )
(200)
(211 )
76 78 80 82 84
(212)
(301)
(220)
(201)
(212)
Fig. 13. X-ray diffraction patterns of Ti 35Nb7Zr 5Ta containing (a) 0.06,
(b) 0.46 and (c) 0.68 wt.% O aged at 427 -C for 8 h [21].
H.J. Rack, J.I. Qazi / Materials Science and Engineering C 26 (2006) 12691277 1275
oxygen addition suppresses N phase formation. Being a strong
a stabilizer, it promotes a formation as well. Figs. 13 and 14
confirm that the increase in strength after both aging
treatments, at low oxygen content results from fine N phase
precipitation; duplex aging resulting in higher volume fraction
of N phase. In contrast, the increase in yield strength observed
at higher oxygen content (0.46 wt.% O) results from a mixture
of fine N and a phase precipitation [21,23]. Finally, the
increase in the yield strength observed at the highest oxygen
content (0.68 wt.%) results from a precipitation.
Formation of a phase in high oxygen alloys results from
local clustering of oxygen atoms which then acts as a
preferential nucleation site for a phase. Aging of 0.46/0.68
wt.% O alloys at 538 -C or higher results in oxygen diffusion
to grain boundaries from its surrounding areas, which in turn
leads to grain boundary (GB) a formation. This decreases the
oxygen content in the vicinity of grain boundary, hence
suppressing oxygen clustering and thereby resulting in a
denuded zones along the grain boundaries, Fig. 15. These
denuded zones act as a preferred path for crack propagation
resulting in premature failure, Fig. 16.
5. Conclusions and summary
This paper provided a snap-shot of several areas of current
exploration focusing on the synthesis and understanding
required for successful application of titanium alloys for
biomedical applications. Continued activity within this arena
will hopefully bring new materials and techniques to bear,
increasing the quality of patient care and lifestyle. Success in
this exciting endeavor will in the future require an ever
increasing cooperation of individuals with expertise in materi-
als science, biomechanics and cell biologists.
Acknowledgements
The authors would like to acknowledge the many former
and current co-workers, graduate and undergraduate students
for their contributions to our biomaterials activities. These
include Prof. T. Webster, Prof. R. Valiev, Dr. T. Ahmed, Dr. R.
Cooks, Dr. E. Fu, Dr. N. Istephaneous, Dr. M. Long, Dr. T.
Lowe, Dr. V. V. Stolyarov, Dr. V. Tsakiris, Mr. B. Marquadt,
Mr. C. Yao, Ms. M. Richards and Ms. H. C. Chandana. Of
particular note is Dr. J. Black who one day asked if it were
possible to synthesize a titanium alloy whose elastic modulus
approached that of bone. Without much thought the response
was what is the elastic modulus of bone, thus beginning a
dialogue between materials scientists, biomechanics and cell
biologists that continues to this day. The financial support
during the early stages of this study by the Stryker Corporation,
under the guidance of Mr. Paul Serekian and Allegheny
Teledyne ALLVAC, under the guidance of Mr. Howard
Freese and Dr. R. Kennedy are greatly appreciated. Finally the
continuing discussions with Prof. M. Niinomi have kept us
on our toes.
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