Download as pdf or txt
Download as pdf or txt
You are on page 1of 9

journal of the mechanical behavior of biomedical materials 20 (2013) 407–415

Available online at www.sciencedirect.com

www.elsevier.com/locate/jmbbm

Opinion Piece

Biocompatibility of Ti-alloys for long-term implantation

Mohamed Abdel-Hady Gepreela,n, Mitsuo Niinomib


a
Department of Materials Science and Engineering, Egypt-Japan University of Science and Technology (E-JUST), Alexandria, Borgelarab
21934, Egypt
b
Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan

art i cle i nfo ab st rac t

Article history: The design of new low-cost Ti-alloys with high biocompatibility for implant applications,
Received 17 July 2012 using ubiquitous alloying elements in order to establish the strategic method for suppres-
Received in revised form sing utilization of rare metals, is a challenge. To meet the demands of longer human
6 November 2012 life and implantation in younger patients, the development of novel metallic alloys
Accepted 17 November 2012 for biomedical applications is aiming at providing structural materials with excellent
Available online 6 December 2012 chemical, mechanical and biological biocompatibility. It is, therefore, likely that the next

Keywords: generation of structural materials for replacing hard human tissue would be of those

Implants Ti-alloys that do not contain any of the cytotoxic elements, elements suspected of causing

Compatibility neurological disorders or elements that have allergic effect. Among the other mechanical

Long-term implantation properties, the low Young’s modulus alloys have been given a special attention recently, in

Ti-alloys order to avoid the occurrence of stress shielding after implantation. Therefore, many

Low cost implants Ti-alloys were developed consisting of biocompatible elements such as Ti, Zr, Nb, Mo, and
Ta, and showed excellent mechanical properties including low Young’s modulus. However,
a recent attention was directed towards the development of low cost-alloys that have a
minimum amount of the high melting point and high cost rare-earth elements such as Ta,
Nb, Mo, and W. This comes with substituting these metals with the common low cost, low
melting point and biocompatible metals such as Fe, Mn, Sn, and Si, while keeping excellent
mechanical properties without deterioration. Therefore, the investigation of mechanical and
biological biocompatibility of those low-cost Ti-alloys is highly recommended now lead
towards commercial alloys with excellent biocompatibility for long-term implantation.
& 2012 Elsevier Ltd. All rights reserved.

1. Background Brånemark System implants have been placed in human


bodies (Nabeel, 2012), over 1,000,000 spinal rod implantations
The continual growth of the world population and the have been done between 1980–2000, and 250,000 total hip
increase in traffic accidents especially for young people, more replacements are performed annually in United States only
pronounced in the developing countries (WHO, 2012), have (Christian, 2004). Not only the replacement surgeries have
brought an ever-increasing need for materials specially suited increased, but also the revision surgeries of hip and knee
for bio-implant applications. Up till now, over 7 million implants. These revision surgeries which cause pain for the

n
Corresponding author. Tel.: þ20 11 47375539; fax: þ20 304599520.
E-mail address: geprell@yahoo.com (M. Abdel-Hady Gepreel).

1751-6161/$ - see front matter & 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jmbbm.2012.11.014
408 journal of the mechanical behavior of biomedical materials 20 (2013) 407 –415

patient are very expensive, besides, their success rate is from alloys, namely, stainless steels, cobalt–chromium alloys,
rather small. The total number of hip revision surgeries is and titanium alloys (Geetha et al., 2009).
expected to increase by 137% and that of knee revision Various metallic materials have been used for total hip
surgeries by 607% between the years 2005 and 2030 (Kurtz replacements as well as other joint replacement surgeries,
et al., 2007). Nowadays, researchers are working hard to i.e., knees, shoulders, bone plates. Additional applications
develop materials for long life implantation in human body. include trauma and spinal fixation devices, cardiovascular
This is because the commercial biomaterials have exhibited stents, and most recently replacement of spinal discs (Rack
tendencies to fail after long-term use due to various reasons and Qazi, 2006; Semlitisch, 1987).
such as low fatigue strength, high modulus compared to that Stainless steel shows moderate mechanical properties and
of bone, low wear and corrosion resistance and lack of good corrosion resistance in human body fluid environment;
biocompatibility. The various causes for revision surgery therefore, it is most often used in implants that are intended
and the key solutions are schematically illustrated in Fig. 1. to help in fractures repair, such as bone plates, bone screws,
Another acceptable reason for the increase in the number of pins, and rods. Cobalt–chromium alloys are also strong, hard,
revision surgeries is the higher life expectancy. The implants biocompatible, and corrosion resistant; hence, they are used
are now expected to serve for much longer period or until in a variety of joint replacement implants, as well as some
lifetime without failure or revision surgery. The development fracture repair implants, that require a long service life.
of appropriate material with high longevity and excellent In recent years, titanium and titanium alloys are extensively
biocompatibility is highly essential. used as bone replacement implants due to their excellent
Generally, the most common materials used in orthopedic mechanical properties, corrosion resistance and biocompat-
implants are metals and a type of plastic called polyethylene. ibility as compared to the other metallic materials (Liu et al.,
These two material types are combined in most joint implants, 2004; Tian et al., 2010).
that is, one component is made from metal, and one from Below is a systematic discussion on the main concepts
polyethylene. When properly designed and implanted, the two driving the progress in metallic implants research in the last
components can rub together smoothly while minimizing two decades ended with results of newly developed alloys.
wear. Although some pure metals have excellent character- This discussion will focus on the importance of both the
istics for use as implants, most metallic implants are made biological and mechanical biocompatibility for the long-life

Fig. 1 – Various causes for failure of implants that leads to revision surgery, footed with a proposed system for better
performance.
journal of the mechanical behavior of biomedical materials 20 (2013) 407 –415 409

implants. In order to prevent failure after implantation, the conditions (i.e., pH, chloride ion concentration, temperature,
mechanical biocompatibility emphasizing the importance of etc.), mechanical factors (i.e., pre-existing cracks, surface abra-
low Young’s modulus and how to achieve it, are also presented. sion, and film adhesion), electrochemical effects (i.e., applied
Finally, some economical considerations for the production of potential, galvanic effects, pitting, or crevices), and the dense
new metallic implants will be discussed. This review will help cell concentrations around implants (Oshida, 2006).
materials researchers to develop competitive materials for Reported in Table 1 are the common metals and alloys that
implant applications, as well as its importance for surgeons to are used in implant applications, their microstructure and
choose the most proper materials for specific application. their mechanical properties. As shown in this table, the
majority of implants contain; vanadium, aluminum, cobalt,
copper, chromium, molybdenum, nickel, titanium and var-
2. Biological biocompatibility of implants ious elements. It is well known that any metal surrounded by
biological systems will suffer corrosion to some extent
As explained above, the most common implants used long time (Hallab et al., 2001). The biological biocompatibility of any
ago are made from stainless steel, titanium and Ti-alloys implant, which is defined by its toxicity, carcinogenicity, and
(mainly due to their high corrosion resistance) and Co–Cr-based metal sensitivity from the release of metal ions, must be
alloys (mainly due to their high wear and corrosion resistance.) quantified to decrease the patient’s risk and failure of
In other words, these alloys are considered chemically stable implants. Corrosion and the release of metal ions due to
with respect to the internal chemistry of the human body the wear of the implant inside the human body are the source
(i.e., good chemical biocompatibility). Even though the metals of many adverse pathophysiological effects (Gotman, 1997).
used in implants are quite corrosion-resistant, there are still That is why, the biological effect of elements, metals, and
some interchanges of metal ions into the tissues or tissue fluids alloys are being extensively studied.
(Orden et al., 1982). The amount of metal ions released is related For example, the cytotoxicity of typical surgical implant
to the corrosion resistance of the metal, the environmental alloys and pure metals have been studied by many

Table 1 – Selected orthopedic alloys developed and/or utilized as biomedical implants and their mechanical properties
(E ¼elastic modulus, YS ¼ yield stress, UTS¼ultimate tensile strength).

Alloy designation (mass%) Microstructure E (GPa) YS (MPa) UTS (MPa) Fatigue limit (MPa)a

Bone Viscoelastic composite 10–30 90–140


nn
Stainless steel 316L Austenite 200
Annealed [1] 170 480 145
Hot forged [1] 140 585 295
nn
CoCrMo Austenite 200–230
Cast [1] 450 565 400
Wrought [1] 860 1200 500
nn
cp Ti (grade 4) a 105
Annealed [2] 480 550 350
nn
Ti–6Al–4V aþb 110
Annealed [1] 680 780 400
Hot forged [1] 900 1000 600
nn
Ti–6Al–7Nb aþb 105
Annealed [3] 800 900 500
nn
Ti–5Al–2.5Fe aþb 110
Cast [3] 820 900 425
Annealed [3] 780 860 725
nn
Ti–13Nb–13Zr aþb 79
annealed[2] 900 1030 500
nn
Ti-11.5Mo–6Zr–4.5Sn (BIII) b
Annealed [3] 79 620 690 525
nn
Ti–15Mo–5Zr–3Al b 80
Annealed [2] 900 930 540
Ti–15Mo–3Nb–0.3O b 82
Annealed [4] 1020 1020 490
nn
Ti–35Nb–5Ta–7Zr (TNZT) b 55
Annealed [4] 530 590 265
nn
Ti–35Nb–5Ta–7Zr–0.4O (TNZTO) b
Annealed [4] 66 976 1010 450
Ti–29Nb–13Ta–4.5Zr b 65
(TNTZ) annealed[5] 400 420 325

[1] Ref. (Semlitsch and Willert, 1980) [2] Ref. (Li, 2000) [3] Ref. (Boyer et al., 2007) [4] Ref. (Narayan, 2012) [5] Ref. (Niinomi and Nakai, 2011).
a
At 107 cycles.
nn
Commercially used in biomedical applications.
410 journal of the mechanical behavior of biomedical materials 20 (2013) 407 –415

researchers as reported in Biesiekierski et al. (2012); Davidson resistance, is a crucial property of implant materials. Shown
and Kovacs (1989); Kuroda et al. (1998); Okazaki et al. (1996), in Table 1 are the strength and fatigue strength of common
Steinemann (1980). Vanadium is classified in the sterile alloys used in implant manufacture. The strength and so
abscess (toxic) group, and aluminium in the capsule (scar fatigue strength of alloys are related to the alloy composition
tissue) group. Ti, Zr, Nb and Ta exhibit excellent biocompat- and prior thermo-mechanical processing history. Fatigue
ibility and are in the loose connective vascularized (vital) strength is also highly affected by surface processing, finish-
group regarding tissue reaction. Kawahara reported that Ti, ing and treatments. Hence, the alloys show a range of such
Zr, Ta and Pd are low cytotoxic elements (Kawahara et al., important mechanical properties and can be controlled with
1963). From the above information it is concluded that the proper processing and heat treatments. It is well known that
ideal biomaterial should possess good biological biocompat- the higher the fatigue strength of an alloy is, the longer
ibility by being free of toxic elements. Therefore, the stainless lifetime for an implant made of it is in service. Generally,
steel, Co–Cr-based and Ti–6Al–4V alloys, the most common Co–Cr alloys and (aþb)-type Ti-alloys show high fatigue
implants alloys, are not the ideal alloys to be used for long resistance when compared to other metallic biomaterials.
term implantation in human body from the biological point Recently, TNTZ (a b-type Ti-alloy) showed high fatigue
of view, due to their high content of high cytotoxic elements strength too with proper thermomechanical treatments
such as (V, Ni, Coy). Nickel is also known as allergenic (Niinomi and Nakai, 2011). It is worthy to highlight here that
carcinogen element that exhibits one of the highest sensitiv- the notch sensitivity, which is changing with microstructure
ities in metallic allergen tests (Koster et al., 2000). control, is a very important aspect, since it can lead to poor
Therefore, the research on development of Ni-free fatigue performance in some materials which have high
Co-based (Yamanaka et al., 2011) and Ti-based (Oak et al., 2009) strength and fatigue strength (Li, 2000).
alloys are being done. In the same way, intensive efforts are In addition, the other mechanical properties (such as
being done to substitute Ti–6Al–4V alloy with V-free titanium Young’s modulus and wear resistance) should be also con-
alloys for biomedical applications. For this reason Ti–6Al–7Nb sidered, because they may limit the usage of the alloys in
and Ti–5Al–2.5Fe have been developed (Semlitsch et al., 1985; manufacturing implants even if the strength and fatigue
Zwicker et al., 1980). However, it was reported that Al is an strength are mechanically biocompatible.
element involved in severe neurological, e.g., Alzheimer’s Stainless steel and Co–Cr alloys show good wear resistance
disease and metabolic-bone disease, e.g., osteomalacia and relatively high strength compared to that of bone, as
(Boyce et al., 1992). So, V- and Al-free Ti-alloys are being shown in Table 1. In addition, good fatigue resistance is
developed too. One of the important V- and Al-free Ti-alloys achievable, through microstructure control. However, these
is Ti–13Nb–13Zr alloy (Steinemann et al., 1993) being free of materials still suffer from a large degree of biomechanical
toxic elements and showing improved bone biocompatibility incompatibility, due to their high elastic modulus (about
and corrosion resistance compared to that of Co–Cr-based 200 GPa), compared to that of the bone (max. 30 GPa).
and Ti–6Al–4V alloys (Davidson et al., 1994). Due to other
concerns such as mechanical biocompatibility, as will be
discussed below, many other b-type Ti alloys composed of 3.2. Stiffness of implants
the high biocompatible elements (i.e., Ta, Nb, Zr, Mo, W, Sn, ..)
were developed such as Ti–29Nb–13Ta–4.6Zr (TNTZ) (Kuroda As mentioned above, when these alloys with low stiffness
et al., 1998), Ti–35Nb–5Ta–7Zr (TNZT), Ti–12Mo–6Zr–2Fe mismatch with bone are used as a hip implant, e.g., a femoral
(Steinemann, 1980), Ti–Mo and many others. stem, the implant takes over a considerable part of body
loading, which shields the bone from the necessary stressing
required to maintain its strength, density, and healthy struc-
3. Mechanical biocompatibility of implants ture. Such an effect, usually termed ‘‘stress shielding’’,
eventually causes bone loss, implant loosening, and prema-
The metallic implants, in many cases, should not only avoid ture failure of the artificial hip (Mansour et al., 1995).
short-term rejection and infection, but should also provide Therefore, these alloys are not recommended in general in
long-term biocompatibility and avoid long-term materials manufacturing implants that transfer loads to bone for long
limitations. Besides the biological biocompatibility discussed term implantation (more than 10 years) (Oshida, 2006).
above, the mechanical biocompatibility is vital for long term The stiffness of titanium and its alloys is substantially
implantation (He and Hagiwara, 2006). In this section, the lower than that of other conventional metallic implant
mechanical biocompatibility (i.e., high strength, long lifetime, materials such as stainless steel or Co–Cr–Mo alloys, as
high-wear resistance and low Young’s modulus) is discussed. shown in Table 1. Therefore, compared to stainless steel
and Co–Cr alloys, Ti-based alloys are excellent biomaterials
for long-term implantation due to their relatively low Young’s
3.1. Fatigue and wear resistance modulus, good fatigue resistance and excellent biological
passivity (Song et al., 1999a). However, the most common Ti
The cyclic loading is applied to orthopedic implants during alloys used in bio-implantation are of a and aþb type alloys
body motion, resulting in alternating plastic deformation of that still show relatively high elastic modulus (about 120 GPa)
microscopically small zones of stress concentration produced when compared with that of bone (max. 30 GPa), these
by notches or microstructural inhomogeneities. Therefore, materials still suffer from a considerable degree of biome-
the long lifetime of implant, which is related to its fatigue chanical incompatibility.
journal of the mechanical behavior of biomedical materials 20 (2013) 407 –415 411

One of the examples is the application of Ti–6Al–4V as a Mo and Sn were designed based on molecular orbital calcula-
femoral stems in total hip replacements. This alloy has a tions of electronic structures. Niimomi et.al. has developed
relatively high elastic modulus (about 110 GPa) and stress Ti–29Nb–13Ta–4.6Zr (TNTZ) alloy that shows Young’s modu-
shielding is reported when it is used as femoral stem (Oshida, lus as low as 60 GPa. However, TNTZ and other recently
2006). Moreover, the existing alloy can release toxic ions (e.g., developed alloys with relatively low Young’s modulus, such
V and Al) into the body, leading to undesirable long-term as Ti–35Nb–5Ta–7Zr (TNZT), Ti–15Mo–2.8Nb–3Al and others,
effects (Cui and Guo, 2009; Kuroda et al., 1998; Lopez et al., show relatively low ultimate tensile strength and fatigue
2001; Oshida, 2006). strength, as shown in Table 1. It is important to stress again
Therefore, the decrease of the Young’s modulus of implants here that the strength and fatigue strength of an alloy can be
was an important target for the researchers in the last two improved through the proper post treatments. For example,
decades. It is well known that the Young’s modulus changes the strength and fatigue strength of TNTZ alloy raised
according to the type of the phases existing in the alloy significantly from 420 and 325 MPa in the solution treatment
(Matlakhova et al., 2005; Zhou et al., 2004a). For example, it condition to 1100 and 775 MPa after thermomechanical treat-
has been reported that the o-phase has the highest Young’s ments, respectively (Niinomi and Nakai, 2011). However, this
modulus, and the martensite a00 -phase has a lower modulus is on the expense of an increase in the Young’s modulus from
than the martensite a0 -phase, and the b-phase has the lowest 65 to 85 GPa after the treatments.
modulus among these phases in most Ti alloys (Matlakhova Therefore, considerable efforts have been devoted by mate-
et al., 2005; Zhou et al., 2004b). Thus, extensive investigations rials engineers and researchers to develop new b-titanium
have been carried out to develop b-type alloys with a low with high strength and low modulus.
Young’s modulus, superelasticity, shape memory effect and
satisfactory biocompatibility for the replacement of human
bone (Ikehata et al., 2004; Matlakhova et al., 2005; Niinomi,
2003; Saito et al., 2003). 3.3. Ti-alloys with low Young’s modulus
The research of biomedical titanium alloy focused on
b-type titanium alloys which contain non-toxic elements The Young’s modulus changes with bphase stability as was
such as Nb, Ta, Zr, Mo and Sn in order to obtain lower elastic discussed in details in previous studies (Abdel-Hady et al.,
modulus, higher corrosion resistance and improved tissue 2006, 2007, 2008, 2009). The least stable single bphase alloys
response (Hallab et al., 2001; Oshida, 2006). Therefore, show minimum values in Young’s modulus in the btype
b-titanium alloys can now replace the Ti–6Al–4V alloy which alloys (Abdel-Hady et al., 2006). Also, it was reported that the
is considered the most important biomedical titanium alloy. Zr addition (Abdel-Hady et al., 2007; 2009) as well as small
Various b-type Ti-alloys have been developed and meet the addition of oxygen enhanced the elastic properties of the
above mentioned needs of showing low Young’s modulus and Ti-alloys. Also, both Zr and O worked as bstabilizers in the
being free of toxic elements or elements that cause allergic btype Ti-alloys (Abdel-Hady et al., 2006, 2009). With the aid
effect. Namely, Ti–15Mo–5Zr–3Al (Semlitsch et al., 1985), of BoMd diagram, the present author has developed new
Ti–12Mo–6Zr–2Fe (Okazaki et al., 1996), Ti–15Mo, Ti–29Nb– high Zr-content alloys free of toxic elements. These alloys
13Ta–4.6Zr (Kuroda et al., 1998), Ti–35Nb–5Ta–7Zr and Ti– showed high strength (more than 1200 MPa) and low Young’s
13Zr–13Nb (Steinemann et al., 1993), have been developed modulus (less than 50 GPa) under different treatments, as
for medical implant applications. All these alloys show low shown in Fig. 2. Detailed discussion of the mechanical and
Young’s modulus as compared to that of Ti–6Al–4V alloy. physical properties of these alloys is presented elsewhere
Moreover, the superelastic and shape memory behavior (Abdel-Hady and Morinaga, 2009a; 2009b)). Here, Bo is the
observed in Ti–Ni alloy have made it widely applied to average bond order between atoms, and Md is the average d-
biomedical uses. But Ni is a toxic element, as explained orbital energy level (eV) of the elements in the alloy. In the
above, that is why the development of Ni-free superelastic same way, Ti–24Nb–4Zr–7.9Sn alloy was developed and
and shape memory alloys was a recent target of many showed high strength (850 MPa) and low Young’s modulus
researchers too. For example, Ti–Nb–X (X¼ Zr, Ta, Mo, Au, (42 GPa) (Hao et al., 2007). Many researchers are concerned
Pd, Pt, Al, Ga, Ge, Sn, Sc, O), Ti–Mo–Y (Y¼ Ta, Nb, Zr, Au, Pd, Pt, with increasing the strength and decreasing the Young’s
Al, Ga, Ag) and Ti–V–Z (Z¼ Nb, Sn, Al) alloys were designed to modulus of biocompatible b-type Ti-alloys through alloy
improve the superelastic and the shape memory property of design, thermomechanical treatments and manufacturing
the biomedical Ti-alloy (Duerig et al., 1982; Hosoda et al., methods.
2003; Kim et al., 2004; 2005; Kuramoto et al., 2006; Song et al., It is important to note that cold deformation of b-type
1999a; 1999b; Zhou et al., 2004a; 2004b). Ti-alloys contributes in controlling the Young’s modulus of
However, most of these compositions were formulated prin- the alloy depending on the deformation technique and the
cipally by trial and error, which by no means represents the final microstructure, since deformation and/or recrystalliza-
optimum choices. There has been little theoretical investigation tion textures are developed under some thermomechanical
to guide alloy development for high strength and low modulus schemes, as observed here in Fig. 2. Controlling the grain size
biomedical applications using, for example, the d-electrons and introducing texture in the alloy through the proper
concept (Kuroda et al., 1998; Matsugi et al., 2010), and first thermomechanical treatments have been reported by many
principles electronic calculations (Song et al., 1999a) and others. authors (Hosoda et al., 2006; Kim et al., 2006; Kuramoto et al.,
In a recent study (Kuroda et al., 1998), some btype 2006) and considered as very effective tool to reach the target
titanium alloys composed of non-toxic elements Nb, Ta, Zr, in developing more mechanical-biocompatible implants.
412 journal of the mechanical behavior of biomedical materials 20 (2013) 407 –415

80
ST CR 1200

Young'smodulus (GPa)
60
900

UTS (MPa)
40 600

20 300

0 0
Z00 Z01 Z11 Z00 Z01 Z11

Fig. 2 – Effect of phase stability and thermomechanical treatment on the Young’s modulus (a), and the ultimate tensile
strength (UTS) (b), of theTi67Zr20Nb10Ta3, Z00, Ti66Zr20Nb10Ta3O1, Z01, and Ti65Zr20Nb10Ta3Fe1O1, Z11, alloys after solution
treatment (ST) and after 90%CR (CR).

alloys (i.e., Ti–30Zr–8Mo) (Niinomi and Nakai, 2011). Interest-


ing is Z11 alloy show nonlinear elasticity and the actual
elastic strain of this alloy is more than 2%. Z11 alloy seems
promising for future long-life implant applications since it
shows elastic admissible strain even higher than that of bone
itself.
Also the production technique and the implant structure
became recently tools to reduce the Young’s modulus of
metallic implants. Much research is being carried out to
Fig. 3 – Elastic admissible strain plotted against Young’s produce metallic implants with cellular structure that show
modulus of bone compared to the commercial biomedical very low Young’s modulus. For example, Ti–6Al–4V alloy with
alloys (namely; stainless steel, SUS-316L, Co–Cr based alloy, cellular structure showed low Young’s modulus as low as
CoCrMo, Ti–6Al–4V, Ti–64ELI, commercial pure Ti, Cp–Ti, 50 MPa (Cansizoglu et al., 2008; Li et al., 2006). The strength
Ti–35Nb–5Ta–7Zr–0.4O, TNZTO, and Ti–13Zr–13Nb) and the and Young’s modulus of cellular structures are well
recently developed alloys (namely; Ti–29Nb–13Ta–4.6Zr, TNTZ, controlled through struts width, angles and relative density
Ti–30Zr–8Mo, Ti-8Mo Ti65Zr20Nb10Ta3Fe1O1, Z11, and Ti–5Fe– of the structure (Cansizoglu et al., 2008; Li et al., 2006;
3Nb–3Zr, TFNZ), all in the annealing condition, are promising Schwerdtfeger et al., 2010).
for future long-term implant applications as they show elastic
admissible strain higher than the commercial alloys.
4. Low cost implants

As discussed above, the future long term metallic implants


should be made of those alloys that show high mechanical
A useful relation between strength and Young’s modulus compatibility (i.e., high strength, high wear resistance and
that guides materials selection for bio-implant applications is low Young’s modulus) and are composed of non-toxic ele-
presented as the elastic admissible strain of an alloy. The ments. The most promising alloys for implant applications
elastic admissible strain, defined as the yield stress-to- are btype titanium alloys. That is why, many btype
modulus ratio, is a quite important parameter considered in titanium alloys composed of non-toxic elements Nb, Ta, Zr,
orthopedic applications. The higher the elastic admissible Mo, Hf, Au, Pd, Pt, Ag, Ga, Ge, Sc, and Sn were developed in
strain is, calculated from this relation, the more suitable the the last two decades (Cui and Guo, 2009; Kuroda et al., 1998;
materials for such applications are (Song et al., 1999a; 1999b). Lopez et al., 2001; Niinomi, 2003).
It is important to mention here that the Young’s modulus of However, most of these developed b-titanium alloys con-
alloys is measured at loads close to zero. However, some of tain considerable amounts of the expensive, high melting
the recently b-type Ti-alloys show nonlinear elasticity (Saito point, and high density metals (such as; Nb, Ta, Zr, and Mo).
et al., 2003; Abdel-Hady et.al., 2008). Hence, these alloys These elements are also rare ones due to their low abun-
are showing higher elastic strain than calculated from dances in the earth’s crust. In contrast, titanium is consid-
this relation and become more suitable for orthopedic ered to be a ubiquitous element since it has the tenth highest
applications. Fig. 3 shows the elastic admissible strain of Clarke number of all the elements. This leads to high cost of
the most common bio-implant alloys in addition to the most the raw materials and difficulty in the alloy preparation due
promising b-type Ti-alloys developed recently for implant to the high melting points of the constituent elements that
applications. The recently designed alloys Z11 (ST and CR) leads to macro- and micro-segregations (Narita et al., 2012;
showed elastic admissible strain higher than other low Zhou et al., 2006). Generally, the production cost and/or
Young’s modulus Ti-alloys including the high Zr-content difficulty of any alloy limit its range of applications and are
journal of the mechanical behavior of biomedical materials 20 (2013) 407 –415 413

considered the main reasons behind the ease of commercia- alloying elements in order to establish the strategic method
lization of any Ti-alloys. Many of the recently developed for suppressing utilization of rare metals, it seemed that the
alloys failed to compete with the commercial alloys due to future metallic implants for long-term usage would be those
the difficulty in its production and their high content of btype Ti alloys, composing mainly of low cost common
expensive rare earth metals (i.e., Nb, Ta, Zr, and Mo). metals such as Mn, Sn or Fe, that show high strength, low
In addition, it is important for the strategy of developing Young’s modulus and good cold workability.
titanium alloys for high performance is using ubiquitous
elements of the alloying.
Consequently, there is a great need to develop new btype Acknowledgments
Ti alloys for biomedical applications, composed of non-toxic
and low cost common metals, such as Mn, Fe, Si and Sn Part of the experimental work presented in this paper
(Helsen and Bremr, 1998), that show high strength, high was done at the laboratory and under the supervision of
corrosion resistance and low Young’s modulus. However, Prof. Masahiko Morinaga, Nagoya University, Japan. This
the minimum Young’s modulus reported for the binary study was supported partially by a Grant-in-Aid for Scientific
Ti–M (M¼Mn and Fe) alloys is 95 GPa which, in some sense, Research from the Ministry of Education, Culture, Sports,
is still high compared to that of bone, while Ti–N (N¼Si and Science and Technology of Japan, the Japan Society for the
Sn) binary alloys would intrinsically show high Young’s Promotion of Science, by the 21st centaury Global Center of
modulus. This is because Si and Sn are astabilizing Excellence of Japan (G-COE), and by Science and Technology
elements and they cannot maintain bphase as the predo- Research Fund (STDF), Egypt.
minant phase in the alloy when added alone to the alloys.
Therefore, the co-addition of b-stabilizing elements with r e f e r e nc e s
these elements is essential to have b-type alloys.
The author reported in a previous work that, in b-type
Ti-alloys, the Young’s modulus is decreasing with increasing
Abdel-Hady, M., Fuwa, H., Henoshita, K., Morinaga, M., 2008.
the Bo value of the alloy in the BoMddiagram (Abdel-Hady Change in anisotropy of mechanical properties with b-phase
et al., 2006; Kuroda et al., 1998). In BoMddiagram, the stability in high Zr-containing Ti-based alloys. Materials
alloying vectors of Fe, Mn, Si and Sn are going to lower Science and Engineering A 480, 167–174.
Bo values (Abdel-Hady et al., 2007). Therefore, to design Abdel-Hady, M., Fuwa, H., Henoshita, K., Shinzato, Y., Morinaga,
b-titanium alloys with low Young’s modulus, it is still important M., 2007. Phase stability change with Zr content in b-type
Ti–Nb alloys. Scripta Materialia 57 (11), 1000–1003.
to co-add the elements with high Bo values (i.e., Mo, Nb, Ta,
Abdel-Hady, M., Hinoshita, K., Morinaga, M., 2006. General
Zr and Hf) (Abdel-Hady et al., 2006, 2007) even with small approach to phase stability and elastic properties of
quantities. Using the BoMddiagram would be very useful in beta-type Ti-alloys using electronic parameters. Scripta Materialia
achieving this aim. For example, Ti–Fe–Ta and Ti–Fe–Ta–Zr 55 (5), 477–480.
alloys were developed for bio-implant applications with the Abdel-Hady, M., Morinaga, M., 2009a. Modification of phase
aid of Bo-Mddiagram (Kuroda et al., 2005). Also, with the aid stability and mechanical properties by the addition of O and
Fe into b-Ti alloys. International Journal of Modern Physics B
of BoMddiagram, the present author is developing new low
23 (6), 1559–1565.
cost Ti–Fe–Nb–Zr alloys (TFNZ) that show Young’s modulus of
Abdel-Hady, M., Morinaga, M., 2009b. Controlling thermal expan-
75 GPa and UTS of 1169 MPa, detailed explanation will be sion of Ti alloys. Scripta Materialia 61, 825–827.
presented elsewhere. The TFNZ alloy shows elastic admissi- Biesiekierski, A., Wang, J., Gepreel, M.A., Wen, C., 2012. A new
ble strain higher than TNTZ, Cp Ti, Ti-64 ELI and SUS-316L, look at biomedical Ti-based shape memory alloys. Acta
and comparable to the alloys with high content of the Biomaterialia 8, 1661–1669.
expensive rare earth metals. This means that the proposed Boyce, B.F., Byars, J., McWilliams, S., Mocan, M.Z., Elder, H.Y.,
Boyle, I.T., Junor, B.J., 1992. Histological and electron microprobe
low cost and biocompatible Ti-alloys for long-time implanta-
studies of mineralisation in aluminium-related osteomalacia.
tion can compete with the other commercial alloys and even
Journal of Clinical Pathology 45, 502–508.
the recently developed b-type Ti-alloys from mechanical Boyer, B., Welsch, G., Collings, E.W., 2007. Materials Properties
biocompatibility point of view at least. Handbook: Titanium Alloys, fourth ed. ASM International
Another very important advantage of b-titanium alloys to 790-810.
be commercialized is its high cold workability. This is Cansizoglu, O., Harrysson, O.L., Cormier, D.R., West II, H.A.,
because the production cost of the implants is highly Mahale, T., 2008. Properties of Ti–6Al–4V Non-stochastic lattice
structures fabricated via electron beam melting. Materials
concerned with the easiness of formation or manufacturing.
Science and Engineering A 492, 468–474.
Due to many technical considerations (namely; surface finishing, Christian, P., Delaunay, 2004. Metal-on-metal bearings in cement-
dimensional accuracy, sub-deformation treatments and heating less primary total hip arthroplasty. The Journal of Arthro-
process) the cold forming ability is a cost effective process if plasty 19 (8), 35–40.
compared to the cost of hot forming of Ti-alloys. Cui, W.F., Guo, A.H., 2009. Microstructures and properties of
biomedical TiNbZrFe b-titanium alloy under aging conditions.
Materials Science and Engineering A 527, 258–262.
Davidson, J.A., Kovacs, P., 1989, US Patent Filed, (Ref. 61560:253).
5. Conclusion Davidson, J.A., Mishra, A.K., Kovacs, P., Poggie, R.A., 1994. New
surface-hardened, low-modulus, corrosion-resistant Ti–13Nb–
Considering both the mechanical and biological biocompat- 13Zr alloy for total hip arthroplasty. Bio-Medical Materials and
ibility of implants, the production cost, and using ubiquitous Engineering 4 (3), 231–243.
414 journal of the mechanical behavior of biomedical materials 20 (2013) 407 –415

Duerig, T.W., Albrecht, J., Richter, D., Fischer, P., 1982. Formation Liu, X., Chu, P., Ding, C., 2004. Surface modification of titanium,
and reversion of stress induced martensite in Ti–10V–2Fe–3Al. titanium alloys, and related materials for biomedical applica-
Acta Metallurgica 30, 2161–2172. tions. Materials Science and Engineering R47, 49–121.
Geetha, M., Singh, A.K., Asokamani, R., Gogia, A.K., 2009. Ti based Lopez, M.F., Gutierrez, A., Jimenez, J.A., 2001. Surface character-
biomaterials, the ultimate choice for orthopaedic implants—a ization of new non-toxic titanium alloys for use as biomater-
review. Progress in Materials Science 54 (3), 397–425. ials. Surface Science 300, 482–485.
Gotman, I., 1997. Characteristics of metals used in implants. Mansour, H.A., Ray, J.D., Mukherjee, D.P., 1995. Proceeding of the
Journal of Endourology 383, 11–16. Biomedical Engineering Conference, 7–9 Apr, 53.
Hallab, N., Merritt, K., Jacobs, J.J., 2001. Metal sensitivity in Matlakhova, L.A., Matlakhova, A.N., Monteiro, S.N., Fedotov, S.G.,
patients with orthopaedic implants. The Journal of Bone and Goncharenko, B.A., 2005. Properties and structural character-
Joint Surgery 83 (3), 428–436. istics of Ti–Nb–Al alloys. Materials Science and Engineering A
Hao, Y.L., Li, S.J., Sun, S.Y., Zheng, C.Y., Yang, R., 2007. 393, 320–326.
Elastic deformation behaviour of Ti–24Nb–4Zr–7.9Sn for Matsugi, K., Endo, T., Choi, Y.-B., Sasaki, G., 2010. Alloy design of
biomedical applications. Acta Biomaterialia 3 (2), 277–2286. Ti alloys using ubiquitous alloying elements and character-
He, G., Hagiwara, M., 2006. Ti alloy design strategy for biomedical istics of their levitation-melted alloys. Materials Transactions
applications. Materials Science and Engineering C 26, 14–19. 51-54, 740–748.
Helsen, J.A., Bremr, H.J., 1998. Metals as Biomaterials. John Wiley& Nabeel, S., 2012. Editorial - History Of Dental Implants, E- Journal
Sons, New York. Of Dentist. 2010, 4(10). Online. Available from URL: /http://
Hosoda, H., Fukui, Y., Inamura, T., Wakashima, K., Miyazaki, S., www.dentistryunited.com/newsletter/newsletter46.htmS.
Inoue, K., 2003. Mechanical properties of Ti-based shape Narayan, R., 2012. Materials for medical devices, fundamentals of
memory alloys. Materials Science Forum 426–432, 3121–3126. medical implant materials. ASM Handbook 23, 6–16.
Hosoda, H., Kinoshita, Y., Fukui, Y., Inamura, T., Miyazaki, M., Narita, K., Niinomi, M., Nakai, M., Hieda, J., Oribe, K., 2012.
2006. Effects of short time heat treatment on superelastic Development of thermo-mechanical processing for fabricat-
properties of a Ti–Nb–Al biomedical shape memory alloy. ing highly durable b-type Ti–Nb–Ta–Zr rod for use in spinal
Materials Science and Engineering A 438–440, 870–874. fixation devices. Journal of the Mechanical Behavior of Bio-
Ikehata, H., Nagasako, N., Furuta, T., Fukumoto, A., Miwa, K., medical Materials 9, 207–216.
Saito, T., 2004. First-principles calculations for development of Niinomi, M., 2003. Recent research and development in titanium
low elastic modulus Ti alloys. Physical Review B 70, alloys for biomedical applications and healthcare goods.
174113–174118. Science and Technology of Advanced Materials 4, 445–454.
Kawahara, H., et al., 1963. Biological testing of dental materials. Niinomi, M., Nakai, M., 2011. Titanium-based biomaterials for
Journal of the Japan Society for Dental Apparatus and Materi- preventing stress shielding between implant devices and
als 4, 65–70. bone. International Journal of Biomaterials 2011, 836587 -10.
Kim, H.Y., Ikehara, Y., Kim, J.I., Hosoda, H., Miyazaki, S., 2006. Oak, J., Louzguine-Luzgin, D.V., Inoue, A., 2009. Investigation of
Martensitic transformation, shape memory effect and glass-forming ability, deformation and corrosion behavior of
superelasticity of Ti–Nb binary alloys. Acta Materialia 54, Ni-free Ti-based BMG alloys designed for application as dental
423–433. implants. Materials Science and Engineering C 29 (1), 322–327.
Kim, H.Y., Ohmatsu, Y., Kim, J.I., Hosoda, H., Miyazaki, S., 2004. Okazaki, Y., Ito, Y., Kyo, K., Tateisi, T., 1996. Corrosion resistance
Mechanical properties and shape memory behavior of and corrosion fatigue strength of new titanium alloys for
Ti–Mo–Ga alloys. Materials Transactions 45, 1090–1095. medical implants without V and Al. Materials Science and
Kim, J.I., Kim, H.Y., Inamura, T., Hosoda, H., Miyazaki, S., 2005. Engineering A 213, 138–139.
Shape memory characteristics of Ti–22Nb–(2–8)Zr(at.%) bio- Orden, V., Fraker, A.C., Sung, P., 1982. The influence of small
medical alloys. Materials Science and Engineering A 403, variations in composition on the corrosion of cobalt–chromium
334–339. alloys. Proceedings of the Society for Biomaterials 5, 108–112.
Koster, R., Vieluf, D., Kiehn, M., Sommerauer, M., Khler, J., Baldus, Oshida, Y., 2006. Bioscience and Bioengineering of Titanium
S., Meinertz, T., Hamm, C.W., 2000. Nickel and molybdenum Materials. Elsevier Science, Oxford.
contact allergies in patients with coronary in-stent restenosis. Rack, H.J., Qazi, J.I., 2006. Titanium alloys for biomedical applica-
Lancet 356 (9245), 1895–1897. tion. Materials Science and Engineering C26, 1269–1277.
Kuramoto, S., Furura, T., Hwand, J.H., Nishino, K., Saito, T., 2006. Saito, T., et al., 2003. Multifunctional alloys obtained via a
Plastic deformation in a multifunctional Ti–Nb–Ta–Zr–O alloy. dislocation-free plastic deformation mechanism. Science
Metallurgical and Materials Transactions A: Physical Metal- 300, 464–467.
lurgy and Materials Science 37, 657–662. Schwerdtfeger, J., Heinl, P., Singer, R.F., Körner, C., 2010. Auxetic
Kuroda, D., Kawasaki, H., Yamamoto, A., Hiromoto, S., Hanawa, cellular structures through selective electron-beam melting.
T., 2005. Mechanical properties and microstructures of new Physica Status Solidi B: Basic Solid State Physics 247, 269–272.
Ti–Fe–Ta and Ti–Fe–Ta–Zr system alloys. Materials Science and Semlitisch, M., 1987. Titanium alloys for hip joint replacements.
Engineering C 25, 312–320. Clinical Mater 2 (1), 1–13.
Kuroda, D., Niinomi, M., Morinaga, M., Kato, Y., Yashiro, T., 1998. Semlitsch, M., Staub, F., Webber, H., 1985. Titanium–
Design and mechanical properties of new b type titanium aluminium–niobium alloy, development for biocompatible,
alloys for implant materials. Materials Science and Engineering high strength surgical implants. Biomedizinische Technik
A243, 244–249. 30, 334–339.
Kurtz, S., Ong, K., Lau, E., Mowat, F., Halpern, M., 2007. Projections Semlitsch, M., Willert, H.G., 1980. Properties of implant alloys for
of primary and revision hip and knee arthroplasty in the artificial hip joints. Medical and Biological Engineering and
United States from 2005 to 2030. The Journal of Bone and Joint Computing 18, 511–520.
Surgery 89, 780–785. Song, Y., Xu, D.S., Yang, R., Li, D., Wu, W.T., Guo, Z.X., 1999a.
Li, J.C.M., 2000. Microsctructure and properties of materials. Theoretical study of the effects of alloying elements on the
World Scientific 2, 49–55. strength and modulus of beta-type bio-titanium alloys. Materials
Li, J.P., Wijn, J.R., Blitterswijk, C.A., Groot, K., 2006. Porous Ti6Al4V Science and Engineering A 260 (1–2), 269–274.
scaffold directly fabricating by rapid prototyping: preparation Song, Y., Yang, R., Li, D., Hu, Z., Guo, Z., 1999b. Calculation of bulk
and in vitro experiment. Biomaterials 27, 1223–1235. modulus of titanium alloys by first principles electronic
journal of the mechanical behavior of biomedical materials 20 (2013) 407 –415 415

structure theory. Journal of Computer-Aided Materials Design microstructure. Materials Science and Engineering A528 (18),
6, 355–362. 5961–5966.
Steinemann, S.G., et al., 1993. Titanium 92. In: Froes, F.H., Caplan, Zhou, T., Aindow, M., Alpay, S.P., Blackburn, M.J., Wu, M.H., 2004a.
I. (Eds.), Science and Technology. TMS, Warrendale, PA, pp. Pseudo-elastic deformation behavior in a Ti/Mo-based alloy.
2689. Scripta Materialia 50, 343–348.
Steinemann, S.G., 1980. In: Winter, G.D., Leray, J.L., de Goot, K. Zhou, T., Itoh, G., Motohashi, Y., Niinomi, M., 2006. Microstruc-
(Eds.), Evaluation of Biomaterials. Wiley, New York, pp. 1–34. tural modification in a beta titanium alloy for implant appli-
Tian, X.J., Zhang, S.Q., Li, A., Wang, H.M., 2010. Effect of annealing cations. Materials Transactions 47-1, 90–95.
temperature on the notch impact toughness of a laser melting Zhou, Y.L., Niinomi, M., Akahori, T., 2004b. Effects of Ta content
deposited titanium alloy Ti–4Al–1.5Mn. Materials Science and on Young’s modulus and tensile properties of binary Ti–Ta
Engineering A527, 1821–1827. alloys for biomedical applications. Materials Science and
WHO, 2012. World Report on Road Traffic Injury Prevention. Engineering A 37, 283–290.
Chapter 2, The Global Impact, 33-67. Zwicker, R. et al., 1980. Proceeding of the Fourth International
Yamanaka, K., Mori, M., Chiba, A., 2011. Mechanical properties of Conference on Titanium, Kyoto, Japan, The Met. Soc. AIME.
as-forged Ni-free Co–29Cr–6Mo alloys with ultrafine-grained 505.

You might also like