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Metallic Biomaterials
Introduction Page 3
1. Corrosion Page 5
References Page 26
The definition of a biomaterial covers a broad area. In fact, any natural or synthetic
material that interfaces with living tissue and/or biological fluids may be classified as a
biomaterial.
However, certain physical, chemical, and mechanical characteristics render some materials
more desirable than others for biological application, depending on its intended use in the
body. For example, the material for a bone implant must exhibit great compressive strength,
while the material for a ligament replacement must display far more flexibility and tensile
strength. In all cases, however, a biomaterial must perform compatibly with the body. In
other words, the biocompatibility and in some cases, bioactivity, of the material comprise key
factors in determining whether a new graft or implant succeeds in the body.
In order to define biocompatibility, it may be easier to define what it is not, rather than
what it is. A biocompatible material disrupts normal body functions as little as possible.
Therefore, the material causes no toxic or allergic inflammatory response when the material is
placed in vivo. The material must not stimulate changes in plasma proteins and enzymes or
cause an immunologic reaction, nor can it leads to carcinogenic or mutagenic effects.
Bioactive materials play a more aggressive role in the body. While a biocompatible material
should affect the equilibrium of the body as little as possible, a bioactive material recruits
specific interactions between the material and surrounding tissue. For example, a bioactive
material can encourage tissue integration to aid in the fixation of an implant in the body.
Many total hip implants operations today rely partially on a porous coating of Hydroxyapatite
(HA), a normal component of bone, to help permanently stabilize the stem of the implant in
the bone. The coating encourages the ingrowth from the surrounding tissue that interlocks
within the pores much like the pieces of a puzzle lock together. Although many current
medical procedures call for inert biocompatible materials, the increasing understanding of
tissue interaction promises many more applications for aggressive bioactive materials.
The closely packed crystal structure and metallic bonding in metals or metal alloys
render them valuable as load bearing implants as well as internal fixation devices in large part
for orthopedic applications as well as dental implants. 316 L stainless steel, titanium alloys,
and cobalt alloys when processed suitably contribute to high tensile, fatigue and yield
Figures 2 et 3 : Immunity, Passivity, corrosion diagram (left) and Pourbaix diagram of Fe (right)
The corrosion region is set arbitrarily at the concentration of greater than 10-6 molar.
Immunity, also called cathodic protection, is defined as equilibrium between metal and its
ions at less than 10-6 molar. In this region, the corrosion is energetically impossible. In the
passivity domain, the stable solid constituent is an oxide, hydroxide, hybrid, or slat of the
metal. Passivity is defined as equilibrium between metal and its reaction products at a
concentration less than 10-6 molar.
There are two diagonal lines in the diagram. The top oxygen line represents the upper limit of
the stability of water and is associated with oxygen rich solution or electrolytes near oxidizing
materials. In the region above this line, oxygen is evolved according to 2H2O O2 + 4H+ +
4e-. In the human body, saliva, intracellular fluid, and interstitial fluid occupy regions near the
oxygen line, since they are saturated with oxygen. The lower hydrogen diagonal line
represents the lower limit of the stability of water. Hydrogen gas is evolved according to
a. Endogenous corrosion
It is linked to the metal which is used and it can be either uniform (in case of quite
homogenous materials) or localised when the heterogeneities are sufficiently spread to give
rise to weak zones on the metal surface. We can give different types of corrosion:
Localised corrosion depends on the environment (O2 content, Cl- concentration, pH,
flow rate) but also on the material itself (segregation phenomenon, presence of different phase
with many grain boundaries or inclusions) and finally on the mechanical stresses that can be
applied to the material.
b. Exogenous corrosion
The causes are not related to the metal itself but to external factors. This corrosion
often appears with the existence of cathodic and anodic zones. The mains defaults are one the
one hand some accidents that can happen during the metal manufacturing (surface default,
local hammer-hardening, residual stresses), and in the other, some defaults in the structure
conception:
- Galvanic coupling: when two dissimilar metals with different electrochemical
potential are in proximity or in contact with each other. One is considered as the
anode, and the second one as the cathode. It results in galvanic corrosion which is the
dissolution of the less noble metal (anode). To reduce this kind of corrosion, we must
absolutely minimise the surface ratio between the cathode and the anode.
- Differential aeration: when two parts of a device are exposed to different amount of
oxygen, for example if the assembling is not waterproof, it can lead to a differential
aeration corrosion battery. The anodic zone which undergoes the corrosion, is the less
aerated.
To reduce corrosion we should choose to right material, but also the right design (no
corners in the device, no stagnant liquid). If we have the choice, we must use the best
environment as possible: it’s always better at lower the temperature and the oxygen content as
well as the chloride content… But of course it is not possible to change anything in the body,
and then we must use other techniques to prevent from corrosion, either kinetic or
thermodynamic:
- Use of inhibitors: they act directly on the reaction mechanism and modify the active
surfaces.
- Use of coatings or protective layers: they act like a physical barrier between the
aggressive milieu and the metal to be protected. There can be metallic coatings (Ni,
Cr, Zn, Al, stainless steels …) or non metallic coatings (paintings, varnishes, enamel,
glass, plastic materials … )
- Use of passivable metals and anodic protection: when a passive film is formed, this
causes a marked drop in current density due to the resistance of the film and its effect
as a barrier to diffusion
- Thermodynamic methods to place the material in his passivity domain.
a. Passivation phenomenon
Passivation corresponds to the transformation of an active surface which is corroding
to a quasi inactive surface, by formation of a passivation layer. The first stage of the
formation of this layer is the adsorption of OH- ions. It leads to a compound which quickly
evolves either quickly (Al, Ti, Zr, Nb, Ta) or slowly (Cr, Fe, Co, Ni) to an oxide.
If we admit that the passivation layer is an oxide, the Pourbaix diagrams can define the
possible domains of passivity. However, this oxide is often considered different from a stable
compound and thus E-pH diagrams can not be considered as rigorous; nevertheless they allow
giving a general overview of metals passivity and corrosion properties.
b. TiNi alloys
The titanium-nickel alloys show unusual properties i.e.: if it is deformed below the
transformation temperature, it reverts back to its original shape as the temperature is raised.
This phenomenon is called “shape memory shape”, which can be related to a diffusionless
martensitic phase transformation, which is also thermoelastic in nature, the thermoelasticity
being attributed to the ordering in the parent and martensitic phases. A widely known NiTi
alloy is 55-Nitinol. This alloy is composed by 55 weight % or 50 atomic % of Ni, Ti and
small amounts of Co, Cr, Mn and Fe. Some possible applications of shape memory alloys are
orthodontic dental archwire, intracranial aneurysm clip, contractile artificial muscle for an
artificial heart, vascular stent, catheter guide wire and orthopedic staple. 55-Nitinol exhibits
also others good properties as low temperature ductility, good fatigue properties, direct
conversion of heat energy into mechanical energy, good biocompatibility and corrosion
resistance in vivo. The mechanical properties of NiTi alloys are especially sensitive to the
stoichiometry of composition and the individual thermal and mechanical history.
All these properties make titanium very used biomaterial and we will develop all these
properties in next chapter, where we will focus more our study on its applications.
2.6. Conclusion
We can conclude, according to the summary table of the principal properties bellow,
that mechanical properties and corrosion resistance of Ti alloys and CoCr alloys are quite
similar and are the best among all metallic biomaterials. However, the density is the important
parameter which difference them, and which explain why Ti may be more appreciated for
some applications. As a matter of fact its lightness is appreciated for orthopaedic implants…
That is why we will focus our study on titanium and titanium alloys.
- 8 35-65 25-30 25 -
(g/cm3)
Density
poor in highly
excellent excellent excellent excellent good
stressed
and O2 depleted
region
3.1. Background
Titanium and some of its alloys are used as biomaterials for dental and orthopaedic
applications. The most common grades used are commercially pure titanium and the Ti6Al4V
alloy, derived from aerospace applications.
a. Physiological Behaviour
These materials are classified as biologically inert biomaterials or bio inert. As such,
they remain essentially unchanged when implanted into human bodies. This is no doubt a
result of their excellent corrosion resistance. Titanium is a base metal in the context of the
electrochemical series; however, it forms a robust passivation layer and remains passive under
physiological conditions. Corrosion currents in normal saline are very low: 10-8 A.cm-2.
Titanium implants remain virtually unchanged in appearance. Ti offers superior corrosion
resistance but is not as stiff or strong as steels or Co-Cr alloys.
Passivation layer
Titanium derives its resistance to corrosion by the formation of a solid oxide layer to a
depth of 10 nm. Under in vivo conditions the oxide, TiO2 is the only stable reaction product.
The titanium implant surface consists so of a thin layer and the biological fluid of water
molecules dissolved ions, and biomolecules (proteins with surrounding water shell). The
microarchitecture (microgeometry, roughness…), of the surface and its chemical composition
are important due to the following reasons:
- Physical nature of the surface either at the atomic, molecular, or higher level relative
to the dimensions of the biological units may cause different contact areas with
biomolecules, cells, etc.
- Chemical composition of the surface may produce different types of bonding to the
biomolecules, which may then also affect their properties and functions.
The surface-tissue interaction is dynamic rather than static, i.e. it will develop into new
stages as time passes, especially during the initial period after implantation. The composition
of biofluid will then change continuously. Depending on the type of initial interaction, the
final results may be fibrous capsule formation or tissue integration.
There are more than 10000 artificial hip joint clinical applications a year. However,
because hip joints are sometimes damaged, broken and so on, there are many cases to be
operated again. Today, it is a subject for future improvement of its dependability.
Figure 5 : SEM photographs for the pressed specimens under 17 Mpa at 750°C for 10 min.
Hydroxyapatite-titanium alloy
composites permit then a better mechanical
fixation facilitating the joint between the
prostheses and bones, because the
hydroxyapatite provides a bioactive
surface, i.e. it actively participates in bone
bonding. It involves an increase in the
long-term stability in the implant.
Titanium and its alloys possess suitable mechanical properties such as strength, bend
strength and fatigue resistance to be used in orthopaedics and dental applications. This is part
of the reason why they have been employed in load-bearing biomedical applications in stead
of materials such as hydroxyapatite, which displays bioactive behaviour.
Other specific properties that make it a desirable biomaterial are density and elastic
modulus. In terms of density, it has a significantly lower density (table 3) than other metallic
biomaterials, meaning that the implants will be lighter than similar items fabricated out of
stainless steel or cobalt chrome alloys.
Having a lower elastic modulus compared to the other metals is desirable as the metal
tends to behave a little bit more like bone itself, which is desirable from a biomechanical
perspective. This property means that the bone hosting the biomaterial is less likely to atrophy
and resorb.
a. Orthopaedic Implants
Figure 7 shows the various components of a total hip replacement. On the left is the
femoral stem made of a titanium alloy. The long round section fits down into the thigh bone
or femur. The white section is a hydroxyapatite coating to encourage bone bonding to the
implant. This section is also macro
textured to provide surface features for
the bone to mechanically interlock with.
The ball on top of the femoral stem is
called the femoral head. It is made of
zirconia ceramic and fits into the hip
joint in the pelvis.
Other orthopaedic applications for titanium-based materials include bone pins, plates and
screws, used for repairing broken bones etc. Figure 8 : Total knee replacement prosthesis
b. Ligament anchorages
Figure 10 : Ti screw
Titanium has been used for dental implants because of its excellent biocompatibility
and corrosion resistance, while application in general dentistry has been limited. Titanium
pins and posts are used to secure dental implants. They use threaded fixtures to secure them
into the jaw.
SMAs have the ability to return to a predetermined shape when there are heated. When
the SMA is below its transition temperature, it has very low yield strength and can be
deformed quite easily into a new shape that it will retain. And when the material is heated
above its transition temperature, it undergoes a change in its crystal structure which makes it
return to its original shape. If the SMA encounters any resistance during its transformation, it
can generate extremely large forces.
The most common SMA is an alloy of nickel and titanium called Nitinol. Ti-Ni alloys
have thus special properties like shape memory effect, super elasticity and high wear
resistance.
Super elastic and thermal shape recovery alloys are used in orthodontic application.
Stainless steels have been employed as corrective measures for misaligned teeth for many
years. Owing to the limited “stretch” and tensile properties of these wires, considerable forces
were applied to the teeth, which caused a great discomfort. When the teeth succumb to the
But now super elastic wires are used for these corrective measures. Owing to their
elastic properties and extensibility, the level of discomfort can be reduced significantly as the
SMA applies a continuous, gentle pressure over a longer period. Visits to the orthodontist are
reduced to perhaps three times per year.
Researchers still want to improve metallic biomaterials, and find the best composition
of an alloy to optimise the biocompatibility, non toxicity and the corrosion resistance, but also
to lower the meting point and therefore to facilitate the manufacture of the material without
loosing the good mechanical properties of course!
In the field of orthopaedics applications, the present researches are about to find some
new alloys especially Vanadium-free Titanium alloys, which must replace the most popular
ones, TI-6Al-4V, because of the cytotoxic Vanadium, or Nickel-free shape memory and ultra-
elastic alloys because Nickel can have adverse physiological affects.
In Japan, the team of Professor Shinichi Nitta, from Tokyo University, has developed
artificial cardiac muscle to be attached on the outside of the heart and sandwiched by with
Shape Memory Alloy plates.
On the other way, conventional metallic porous materials are best suited for use as
coatings on implants since they do not readily have the required mechanical and processing
characteristics which would allow them to be used as bulk structural materials for implants,
bone augmentation, or substitutes for bone graft.
A new porous biomaterial made of tantalum has recently been developed for potential
application in reconstructive orthopaedics. The material has an unusually high and
interconnecting porosity with a very regular pore shape and size. It can be made into complex
shapes and used either as bulk implant or as a surfacing coating. This porous tantalum
biomaterial has then desirable characteristics for bone ingrowth. Further studies are warranted
to ascertain its potential for clinical reconstructive orthopaedics.
[1] Joseph D: BRONZINO, The biomedical engineering handbook, second edition, volume I.
[2] Jean BARRALIS & Gérard MAEDER, Précis de métallurgie, élaboration - structures –
propriétés – normalisation, AFNOR.
[3] www.abe.msstate.edu/classes/abe4523-6523/intro-history-metals-alloys.pdf (metallic
biomaterial)
[4] www.cp.umist.ac.uk/lecturenotes (corrosion)
[5] http://ttb.eng.wayne.edu/~grimm/BME5370/Lect2Out.html (biomaterial)
[6] http://www.materials.drexel.edu/LBTE%20website/biomaterials.html (biomaterial)
[7] http://www.azom.com/Details.asp?ArticleID=1520 (Titanium and titanium alloys as
biomaterials)
[8] http://www.choc.fr/index02.html (ligament anchorage)
[9] http://www.tekes.fi/julkaisut/BiomaterialResearchJapan.pdf (Study in Japan)
[10]http://orthonet.on.ca/emergingtrends/notes/A%20New%20Porous%20Tantalum
%20Biomaterial.htm (Study on Tantalum)
[11] The Biomedical Engineering Handbook – Second Edition – Volume 1 CRC Press
[12] Thin hydroxyapatite surface layers on titanium produced by ion implantation
H. Baumann, K. Bethge, G. Bilger, D. Jones, I. Symietz – 2002, Elsevier Science
[13] Implantation of hydroxyapatite granules into superplastic titanium alloy for biomaterials
T. Nonami, A. Kamiya, K. Naganuma, T. Kameyana - 1998, Elsevier Science
[14] http://www.csa.com/hottopics/bceram/biblio12.html (Silicate glass coating)