Ti Alloys For Biomedical Applications
Ti Alloys For Biomedical Applications
Ti Alloys For Biomedical Applications
www.elsevier.com/locate/msec
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.
1. Introduction Various metallic materials have been used for total hip
replacements as well as other joint replacement surgeries, i.e.,
Continual aging of the US population has brought with it knees, shoulders. Additional applications include trauma and
an ever-increasing need for materials specifically suited for spinal fixation devices, cardiovascular stents, and, most
bio-device application. For example, it is projected that recently, replacement spinal discs. The material list includes
approximately 272,000 total hip replacements will annually stainless steel, Co – Cr –Mo alloys, titanium alloys and other
be performed by 2030. Additionally of the 152,000 total hip more specialized alloys, e.g., Au –Pd. Of these titanium
replacements performed in 2000 approximately, 12.8% alloys, the subject of the present article, offers several
involved revisions of previous hip replacements. The fact benefits, including lower elastic modulus, excellent corrosion
that such a high percentage of hip replacements performed resistance and enhanced biocompatibility [1]. The former is
every year are revision surgeries, although troubling, is not particularly important for hard tissue replacement where stress
surprising when the life expectancy of the implant versus the shielding, a phenomenon where reabsorption of natural bone
ever-increasing life expectancy of the patient is considered. and implant loosening arises because of the difference in
Consistently, over 30% of those requiring total hip replace- elastic modulus between natural bone and hard tissue implant,
ments have been below the age of 65 and even those over is one of the primary causes requiring revision surgery [2].
the age of 65 now have a life expectancy of 17.9 years. Another well-documented and related cause is bone necrosis.
Moreover female patients, who make up the majority of This phenomenon has been associated with wear debris
those receiving total hip replacements, have a life expectancy generated from articulating components at a tabular cup.
of 19.2 years at the age of 65. With a normal implant Such wear debris has been shown to migrate and position
longevity of 12 to 15 years, the majority of those that receive itself at the bone-implant stem interface thereby further
hip implants at age of 65 will require at least one revision promoting bone cell death.
surgery. The present review builds on several excellent prior
summaries [1,3 – 5] and shows that this arena remains a
fruitful area for titanium research and development. It begins
* Corresponding author. Kemet Electronics Inc., 2835 KEMET Way
by examining recent efforts focused at enhancing long used
Simpsonville, SC 29681, USA. Tel.: +1 864 228 4442; fax: +1 864 228 4264. biomedical titanium alloys, i.e., commercial purity titanium
E-mail address: [email protected] (J.I. Qazi). 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
1270 H.J. Rack, J.I. Qazi / Materials Science and Engineering C 26 (2006) 1269 – 1277
1000 #3
(a)
800
#2
σ, MPa
+
#1
600 *
+
*
+
CG
400 *
200
400 nm 2 3 4 5 6 7 8
lg N
Fig. 2. Fatigue response of ultra-fine grained grade 2 commercial purity
(b) titanium with (CG) coarse grained, (#1) equiaxed cellular, (#2) elongated and
(#3) sub-grain microstructures [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 60 238 T 10
UFG #1 (Equiaxed, submicron-grained) 2700 710 625 14 60 403 T 8
UFG #2 (Fibrous, with high dislocation density) 2821 960 725 10 45 434 T 5
UFG #3 (subgrained with internal cells) 2850 1100 915 9 40 500 T 8
Ti – 6Al – 4V ELI (annealed) – 965 875 10 – 15 25 – 47 515
H.J. Rack, J.I. Qazi / Materials Science and Engineering C 26 (2006) 1269 – 1277 1271
Cell adhesion/arbitrary units 2 for total joint replacement. This led to the early introduction of
CG UFG
annealed Ti– 6Al –4V, which today remains the largest single
1.5 titanium alloy used for biomedical device manufacture.
Continued concern with respect to the biological response of
1 vanadium containing materials has moreover led to the
development and introduction of Ti –6Al – 7Nb [10], the level
0.5 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
0
Grain size reduced modulus alpha-beta titanium alloys has resulted in the
development of Ti –13Nb – 13Zr [11], its strength properties
Fig. 3. Enhanced osteoblast adhesion on ultra-fine grained (UFG) compared to being comparable to Ti –6Al – 4V.
conventional grained (CG) commercial purity titanium, cell adhesion results
being normalized to adhesion on wrought Ti foil. Data are mean + std; n = 3;
Present application of these materials tends to be limited to
*p < 0.1 compared to the titanium foil [9]. 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
6Al –4V ELI. This suggests that substitution of ultra-fine illustrates the three distinct microstructures, lamellar, equiaxed
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 (a)
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 50μm
authors suggested that these results may be related to the
increased number of grain boundary sites in ultra-fine grained (b)
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. 50μm
Finally, some evidence exists that the frictional behavior of
ultra-fine grained commercial purity titanium is superior to
(c)
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.
The mechanical behavior of biomedical grade commercial Fig. 4. Different microstructures that can be produced in Ti – 6Al – 4V; (a)
purity titanium is generally considered to lie below that desired lamellar, (b) equiaxed and (c) bimodal [12].
1272 H.J. Rack, J.I. Qazi / Materials Science and Engineering C 26 (2006) 1269 – 1277
Table 2 Table 3
Tensile properties the Ti – 6Al – 4V [13] Tensile properties the Ti – 6Al – 4V ELI [6]
Microstructure YS UTS El. RA KIC State UTS (MPa) YS (MPa) El. (%)
(MPa) (MPa) (%) (%) MPa/m 1 Annealed 970 900 20
Equiaxed (Std) 951 1020 15 35 61 2 1 + ECAP at 700 -C, E = 6.5. 1160 1110 12
Lamellar (Std) 884 949 13 23 78 3 2 + upset at 600 -C, E = 55% 1450 1420 11
Equiaxed (ELI) 830 903 17 44 91
Equiaxed (CMG) 1068 1096 15 40 54
Oxygen content: Std: 0.15 – 0.2%; Eli: 0.13 Max; Cmg: 0.18 – 0.2%. remaining above that typically required for biomedical
YS: Yield Strength; UTS: Ultimate Tensile Strength; El.: Elongation; RA:
application ( 10%). Additional enhancement can be achieved
Reduction in area.
by combining severe plastic deformation by equal channel
angular extrusion with upsetting.
and bimodal, that can be produced in Ti– 6Al– 4V through Studies of the reciprocating sliding wear performance of
control of solution annealing temperature, cooling rate and Ti –6Al – 4V processed similarly to that described above again
final aging temperature. The lamellar structure shown in Fig. suggests that this procedure may not offer marked improve-
4a is typically produced following solution treatment above the ment. For example recent efforts show that the enhancement of
h transus, followed by air cooling, and aging between 700 and ultra-fine grained Ti– 6Al– 4V’s dynamic frictional coefficient
800 -C. Solution annealing below the h transus, e.g., between and the steady-state wear rate are marginal, with a slight
800 and 925 -C results in an equiaxed structure, Fig. 4b. enhancement of the former at higher apparent contact stress,
Finally, the bimodal structure, Fig. 4c, may be developed by Figs. 6 and 7. Certainly further effort examining and
solution treatment below the h transus, typically between 900 – understanding these phenomena are warranted.
950 -C followed by air cooling and aging below 700 -C. Table Finally in vivo studies of cell functionality, in ultra-fine
2 shows that equiaxed alpha microstructures provide high grained Ti– 6Al –4V have confirmed the enhancement in
strength and ductility and relatively low fracture toughness, osteoblast adhesion previously shown for ultra-fine grained
whereas lamellar structure provides good fracture toughness commercial purity grade 2 titanium [9]. The interpretation of
but with some compromise on strength and ductility. Finally, this data is however, further complicated when compared to
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 (a)
0.7
performance followed by the equiaxed structure, with the UFG Ti 6Al-4V
Dynamic Friction coeff
0.4
0.3
0.2
0.1
0
1 10 100 1000 10000
Number of cycles
Fig. 6. 2-D friction traces (dynamic friction coefficient at maximum velocity)
Fig. 5. Influence of microstructure on high cycle fatigue strength of Ti – 6Al – for Ti – 6Al – 4V as a function of the number of dry reciprocating – sliding cycles
4V [14]. 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) 1269 – 1277 1273
5.5 (a) 90
Nano hardness (GPa)
80
Elongation & RA (%)
4.5 70
60 RA El
50
3.5
40
30
Alpha Beta
2.5 20
0 300 600 900
20 30 40 50 60 70 80 90 100
Temperature (ºC) Grain Size (μm)
(b)
400 (b)
700
Micorhardnes (VHN)
600
Strength (MPa)
350
500
400 YS UTS
300
300
200
250
0 150 300 450 600 750 900 100
Temperature (ºC) 20 30 40 50 60 70 80 90 100
Grain Size (μm)
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 Fig. 9. Effect of grain size on (a) elongation and reduction in area, and (b) on
microhardness [16]. yield and ultimate tensile strengths of Ti – 29Nb – 13Ta – 4.6Zr [17].
1274 H.J. Rack, J.I. Qazi / Materials Science and Engineering C 26 (2006) 1269 – 1277
(a) Table 4
1200 Tensile properties of Ti – 35Nb – 7Zr – 5Ta [21]
4 hrs Thermal treatment YS (MPa) UTS (MPa) El. (%) RA (%)
Yield Strength (MPa)
30 24 hrs
modulus of 65 GPa [17]. Further examination has shown that
48 hrs
20
the average h grain size and the volume fraction of martensite
has an important influence on this material’s mechanical
10 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
0 phase transforming to a//, the alloy having a yield strength of
200 300 400 500 600 700 ¨250 MPa and elongation of ¨45%. Reducing the solution
Aging Temperature (ºC) treatment temperature to 750 -C and time to 0.5 h results in a
(c) grain size reduction to 25 Am, reduces the volume fraction of
105 martensite considerably, increases the yield strength to 400
Young's modulus (GPa)
100 4 rs MPa and reduces the elongation to 30%, without any apparent
95 24 hrs influence on elastic modulus [18].
90 48 hrs The strength of this alloy can also be increased signifi-
85 cantly by aging, this increase in strength coming at the
80
expense of ductility and elastic modulus. Yield strengths as
75
high as 1100 MPa have been attained after long aging
70
treatments, e.g. aging at 450 -C for 48 h resulting in a yield
65
60
strength of ¨1150 MPa. However, this increase occurs at the
200 300 400 500 600 700 expense of elongation, which is reduced to less than 3%, Fig.
Aging Temperature (ºC) 10, and an increase in elastic modulus to 85 GPa. Micro-
structure analysis indicated that the observed increase in the
Fig. 10. Effect of aging time and temperature on tensile (a) elongation, (b) yield
strength after aging results from N and/or a phase precipita-
strength and (c) Young’s modulus of Ti – 29Nb – 13Ta – 4.6Zr [18].
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.
973 Finally, aging at temperature above 475 -C results in only a
β phase precipitation [18].
Temperature (K)
873
α+β 700
0.06% O 0.46% O
Bending Stress (MPa)
773
600
α+β+ω
673
500
573 β+ω 400
473 300
0 28.8 57.6 86.4 115.2 144 172.8 201.6
Time (ks) 200
1 10 100 1000 10000
Fig. 11. Time temperature transformation diagram of Ti – 29Nb – 13Zr – 4.6Ta. Cycles of Fatigue (x104)
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 Fig. 12. Stress-controlled fatigue response for Ti – 35Nb – 7Zr – 5Ta with two
vol.% of a phase, respectively [18]. T(-C) = T(K) 273. different oxygen contents [22].
H.J. Rack, J.I. Qazi / Materials Science and Engineering C 26 (2006) 1269 – 1277 1275
α (102 ) α (212) The oxygen content of Ti –35Nb – 7Zr –5Ta strongly influ-
(c) ences its aging behavior and hence its mechanical properties.
Solution treatment in h phase field followed by water
500 quenching results in complete h phase retention in alloys
containing up to 0.68 wt.% oxygen, some diffuse N being
(b)
present in low (0.06 wt.%) oxygen alloys [23]. Oxygen
ω(212)
addition restricts the motion of linear defects in metastable h
ω(211 ) ω(301)
titanium alloys thus hindering the collapse of alternating (111)
(a) planes, the latter being required for N phase formation. Thus
0
34 36 38 40 42 48 52 56 76 78 80 82 84
2θ
Fig. 13. X-ray diffraction patterns of Ti – 35Nb – 7Zr – 5Ta containing (a) 0.06,
(b) 0.46 and (c) 0.68 wt.% O aged at 427 -C for 8 h [21].
(a)
α (102 ) α (212)
(c)
ω(301)
500 ω(212)
(b) ω(211 )
β (110) 4μm
(a)
0
34 36 38 40 42 48 52 56 72 76 80 84
2θ
Fig. 15. Scanning electron micrographs illustrating the microstructure of Ti –
Fig. 14. X-ray diffraction patterns of Ti – 35Nb – 7Zr – 5Ta containing (a) 0.06, 35Nb – 7Zr – 5Ta containing (a) 0.06 (b) 0.46 and (c) 0.68 wt.% oxygen aged at
(b) 0.46 and (c) 0.68 wt.% O aged at 260 -C 4 h/427 -C for 8 h (DA) [21]. 593 -C for 8 h [24].
1276 H.J. Rack, J.I. Qazi / Materials Science and Engineering C 26 (2006) 1269 – 1277
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