Key Engineering Materials Submitted: 2017-03-06

ISSN: 1662-9795, Vol. 750, pp 180-183 Revised: 2017-04-28

doi:10.4028/www.scientific.net/KEM.750.180 Accepted: 2017-04-28
© 2017 Trans Tech Publications, Switzerland Online: 2017-08-22

New High Entropy Alloy for Biomedical Applications

Brandusa GHIBAN1,a, Gabriela POPESCU1,b,
Daniela DUMITRESCU2,c, Vasile SOARE2,d
1
University Politehnica Bucharest, 313 SplaiulIndependentei, Bucharest, Romania
2
National R&D Institute for Nonferrous And Rare Metals, 102 BiruinteiBl, Pantelimon, Romania
a
ghibanbrandusa@yahoo.com, bgabriela.popescu@upb.ro (corresponding author),
c
danieladumitrescu@yahoo.com, dvivisoare@imnr.ro

Keywords: high entropy titanium alloy, low modulus of elasticity, corrosion resistance, biomaterial.

Abstract. High Entropy Alloys (HEAs) represent a new concept of metallic materials, that contain
5 or more elements, in proportions from 5 at.% to 35 at.%, and form simple solid solutions (BCC
and/or FCC) instead of complicated intermetallic phases. The high degree of randomness atomic
HEA, gives them excellent properties: electrical, mechanical, electrochemical, ductility, anti-
corrosion properties, stable structure etc, with applications in peak thus representing a growing
research. These specific features provides HEA with excellent hardness, strength and wear strength,
malleability, oxidation and corrosion resistance, with potential applications in diverse industrial
areas [1÷4]. Considering these properties we decide to improve biomedical alloys with this new
class of HEAs.

Introduction
High Entropy Alloys (HEAs) represent a new concept of metallic materials, that contain 5 or
more elements, in proportions from 5 at.% to 35 at.%, and form simple solid solutions (BCC and/or
FCC) instead of complicated intermetallic phases [1,2]. The high degree of randomness atomic
HEA, gives them excellent properties: electrical, mechanical, electrochemical, ductility, anti-
corrosion properties, stable structure etc, with applications in peak thus representing a growing
research. These specific features provides HEA with excellent hardness, strength and wear strength,
malleability, oxidation and corrosion resistance, with potential applications in diverse industrial
areas [3,4]. Considering these properties we decide to improve biomedical alloys with this new
class of HEAs. The present tendency in the newest titanium alloys generation is the decrease of
elasticity modulus, with the maintaining of high mechanical characteristics [5,6,7]. The modulus of
elasticity of main types of biomedical alloys in comparison with bone is illustrated in figure 1.

Materials and Methods

M.C.Gao studied TiZrCuNiFe, TiZrCuNiBe and TiCuNiSnBeZr [4,8], for various
technological applications. Metallic glasses of Ti-Ni-Cu-Sn-Be-Zr, Ti-Zr-Cu-Ni-Sn and Ti-Zr-Cu-
Pd-Sn [10], obtained by arc melting/casting in Cu molds, were studied for medical applications. At
national level, studies were performed for deposition of (TiZrNbHfTa)C thin films by magnetron
sputtering and AlxCrFeyMnNiz by cladding, and also were started few researches by powder
metallurgy (mechanical grinding and alloying).
The influence of alloying elements of the mechanical properties of the newest generation of
beta titanium alloys is illustrated in table 1. The decreasing of tantalum content in the range of
0÷20% leads to increasing of elongation, reduction in area and of elastic modulus of elasticity.
Also, the tensile strength and yield strength may increase with the decreasing of niobium in the
range of 20÷35%.

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 Key Engineering Materials Vol. 750 181

Fig. 1 The elasticity modulus of the main types of biomedical alloys in comparison with bone
During mechanical alloying, brittle titanium hydride (TiH2) particles continuously get
fragmented into nano size particles, whereas some fraction of powders contain relatively larger Nb
particles. Zhang et al. [9] reported that cold welding and severe plastic deformation is the dominant
mechanism which operates during mechanical alloying of ductile Nb powder particles. Due to
severe plastic deformation and cold-welding, Nb particles become hard and brittle, leading to their
fragmentation during subsequent mechanical alloying. As a result, relatively coarser Nb particles
are obtained in the mechanical alloyed (MAed) powder mixture. It would also be worth mentioning
that such a deformation and fracturing of particles leads to the formation of Nb particles with
energetically activated surface. It appears that NbH is formed on the surface of the coarser powder
particles due to the combination of the presence of highly activated surface in the MAed Nb
powders and the tendency of Nb to be highly reactive for hydrogen absorption. Therefore, the
results suggest that only the surface region of the Nb particles is affected by the hydrogen
absorption at first, and the inner core of the Nb remains more or less unaffected by the
hydrogenation.
Since niobium hydride (NbH) is also a brittle phase, similar to TiH2, it fragments into nano-
sized particles during long time of mechanical alloying. Hence, it can be observed that the nano-
sized particles of Nb are the result of pulverization of NbH whereas relatively larger sized particles
are the result of elemental Nb inner core. In the case of long time mechanical alloying, Nb surface
forms NbH continuously and gets fragmented simultaneously due to its brittle nature, leading to the
formation of nanosized NbH particles.
This phenomenon demonstrates that the TiH2 and Nb powder mixture undergoes microstructural
and phase changes owing to the combined effect of fragmentation of hydride phases and plastic
deformation mechanism. A similar kind of fresh surface effect has been reported by Kazuto et al.
[10]. A schematic diagram of the mechanical alloying process is presented in figure 2.
182 Materials Research and Application II

Table 1. Influence of alloying elements of the mechanical properties of the newest beta titanium
alloys

Fig. 2 Schematic diagram showing the fragmentation phenomenon during mechanical alloying
in TiH2, Nb, Ta, Fe an Zr powder mixtures [11]

Results and Interpretations

The trend researchers to continuously improve the quality of materials for applications in
health and the introduction of new materials initiated the idea of using High Entropy Alloys,
materials with outstanding performance that make them possible as biomaterials for medical
applications. On the basis of mandatory requirements that must meet a biomaterial: the biological
compatibility with the human body (composition with the non-toxic) and compatible characteristics
(physical and mechanical characteristics similar to the tissue it replaces) the selection of system
components of the new alloy account for new research directions and requirements of international
and European standards and national legislation in the field, on the characteristics of biomaterials.
The alloy was selected based on biomechanical and tribological properties of titanium alloys. To
ensure better compatibility biological and mechanical (give by Ta and Fe), alloying elements
selected are β-gene (Fe, Ta, Nb) validated as non-toxic and non-allergic for body (Cr, Zr, Nb, Ta)
and the iron is an element with a very low cost. The alloy contains no critical elements. The new
alloy (which was named BIOHEA) is part of the proposed TiZrNbTaFe, the type
Ti40ZrxNbyTa10Fe10, as illustrated in figure 3.
 Key Engineering Materials Vol. 750 183

Fig. 3 Concept of a new BIOHEA

Conclusions
The trend researchers to continuously improve the quality of materials for applications in health
and the introduction of new materials initiated the idea of using High Entropy Alloys (HEAs),
materials with outstanding performance, as biomaterials for medical applications. HEAs represents
a new concept of metallic materials, with 5 or more elements, in proportions from 5 at.% to 35 at.%
that form simple solid solutions (BCC and/or FCC) and have excellent mechanical properties.
The present paper presents the necessity of development of a new generation of titanium alloys
with low modulus of elasticity, the mechanism in which this new alloy will be obtained being
powder metallurgy method. This new concept of HEA is for biomedical applications. The alloy
does not contain critical elements. The alloy is part of the proposed TiZrNbTaFe, the type
Ti40ZrxNbyTa10Fe10.

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