SAVIGNY Pascale & GIROUD Elodie

3rd December 2002

Metallic Biomaterials

Corrosion – Titanium, Stainless steels, Chromium Cobalt alloys, Amalgam –

Orthopaedic & Dental Applications

Functional materials 4H1609

Course PM Version 1
Rolf Sandström

Metallic Biomaterials – december 2002 page 1

 Summary

Introduction Page 3

1. Corrosion Page 5

1.1. Corrosion of metallic implant Page 5

1.2. Electrochemical aspects - mechanism Page 5
1.3. Pourbaix diagram Page 6
1.4. Rate of polarisation and polarization curves Page 7
1.5. Types of corrosion Page 7
1.6. Protection methods Page 9
1.7. Passivation of metallic materials Page 9
1.8. Conclusion on corrosion Page 10

2. Properties and applications of the most used metallic biomaterials Page 11

2.1. Stainless steels Page 11

2.2. CoCr Alloys Page 12
2.3. Ti Alloys Page 13
2.4. Dental metals Page 14
2.5. Other metals Page 14
2.6. Conclusion Page 15

3. Titanium and Ti alloys as Biomaterials Page 17

3.1. Background Page 17

3.2. Applications Page 21

References Page 26

Metallic Biomaterials – december 2002 page 2

 Introduction

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

Metallic Biomaterials – december 2002 page 3

strengths; low reactivity and good ductility to the stems of hip implant devices. Their
properties depend on the processing method and purity of the metal, however, and the
selection of the material must be made appropriate to its intended use.

Metallic biomaterials are normally considered to be highly corrosion resistance due to

the presence of an extremely thin passive oxide film that spontaneously forms on their
surfaces.
These films serve as a barrier to corrosion processes in alloy systems that would otherwise
experience very high corrosion rates. That is, in the absence of passive films, the driving force
for corrosion for typical implant alloys (e.g., titanium-based, cobalt chromium (CoCr)–based,
and stainless-steel alloys) is very high, and corrosion rates would also be high. The properties
of these passive oxide films depend to a large extent on their structure and chemistry, which
are themselves dependent on the substrate's prior thermal, mechanical, and electrochemical
history.

Metallic Biomaterials – december 2002 page 4

1. Corrosion

1.1. Corrosion of metallic implant

Corrosion is the unwanted chemical reaction of a metal with its environment, resulting
in its continued degradation to oxides, hydroxides or other compounds. Biological fluids in
the human body contains water, salt, dissolved oxygen, bacteria, proteins, and various ions
such as chloride and hydroxide. As a result, the human body is a very aggressive environment
for metals if we want to use them as biomaterials. Corrosion resistance of a metallic implant
material is consequently an important aspect of its biocompatibility.

1.2. Electrochemical aspects - mechanism

Corrosion occurs when a metal atom becomes ionized and goes into solution, or
combine with oxygen or other species in solution to form a compound which flakes off or
dissolves. The body environment is very aggressive in terms of corrosion since it contains
chloride ions and proteins and many chemical
V
reactions can occur. The electrolyte, which
anode cathode
contains ions in solution, serves to complete the + -
electrical circuit. Anions are negative ions that
 anions
migrate toward the anode, and cations are positive cations 
ions that migrate toward the cathode. At the
electrolyte
anode, or positive electrode, the metal oxidizes by
losing valence electrons as in the following: M 
Mn+ + ne-. So the anode is always the one which Figure 1 : Electrochemical cell
corrodes and thus has to be protected.
The tendency of metals to corrosion is based on the Standard Electrochemical Series
of Nernst potentials, shown in the table 1, which are the potentials associated with the
ionization of metal when one electrode is the standard hydrogen electrode.

Reaction ∆ E0 (volts) Reaction ∆ E0 (volts)

+ 2+
LiLi -3,05 CuCu -0,34
+ 2+
NaNa -2,71 CoCo -0,28
3+ 2+
AlAl -1,66 NiNi -0,23
TiTi3+ -1,63 H22H+ 0
2+ +
CrCr -0,56 AgAg +0,80
2+ +
FeFe -0,44 AuAu +1,68
Table 1 : Standard Electrochemical Series

Metallic Biomaterials – december 2002 page 5

1.3. Pourbaix diagram
The Pourbaix diagram is a plot of regions of corrosion, passivity and immunity as they
depend on electrode potential and pH. The Pourbaix diagrams are derivated from the Nernst
equation and from the solubility of the
RT concentrat ion of reactants
degradation products and the equilibrium E = E0 ln ∏
nF concentrat ion of products
constants of the reaction.
Nernst equation

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

Metallic Biomaterials – december 2002 page 6

2H3O+ + 2e- H2 + 2H2O. Aqueous corrosion occurs in the region between these diagonal
lines. In the human body, urine, bile, the lower gastrointestinal tract, and the secretions of
ductless glands, occupy a region somewhat above the hydrogen line.
Different parts of the body have different pH values and oxygen concentrations.
Consequently, a metal which performs well in one part of the body may suffer an
unacceptable amount of corrosion in another part.

1.4. Rate of polarisation and polarization curves

The regions in the Pourbaix
diagram specify whether corrosion will
take place, but they do not determine the
rate. The rate, expressed as an electric
current density, depends upon electrode
potential which can be seen in potential
current curves (figure 4). From those
curves, it is possible to calculate the
number of ions per unit time liberated
Figure 4 : Potential current curves for different metals
in the tissue, as well as the depth of
metal removed by corrosion in a given time. An alternative experiment is one in which the
weight loss of a specimen of metal due to corrosion is measured as a function of time.
The rate of corrosion also depends on the other factors such as mechanical stresses that are
applied on the material. The stressed alloy failures occur due to the propagation of cracks in
corrosive environments.
But the main idea is to remind that the corrosion rate depends largely on the pH.

1.5. Types of corrosion

We need distinguish two types of corrosion: endogenous (produced or growing from
within the material) and exogenous (developed from outside of the body, which means that
there is an external origin).

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:

Metallic Biomaterials – december 2002 page 7

 - Crevice corrosion: a form of localized corrosion in which concentration gradients
around the pre-existing crevices in the material drive corrosion processes. Oxygen is
consumed at the surface, the pH decreases, which causes the passive film to break
down and then corrosion is even stronger.
- Pitting corrosion: a form of localized corrosion in which pits form on the metal
surface. The passivity is locally broken by the chlorides.
- Intergranular: It’s a local depassivation on the stainless steels grain boundaries
because chromium carbide precipitation has occurred and the Cr content can be locally
lower that a minimum value (9%) to be passive. It frequently occurs in the heat-
affected zone during welding, and the resultant corrosion is called weld decay.

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.

Metallic Biomaterials – december 2002 page 8

1.6. Protection methods
Every attempt to fight against corrosion should start by knowing and classifying the
causes of corrosion, and then try to minimize the external causes; which means to be more
careful with the surface treatment and the fabrication methods.

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.

1.7. Passivation of metallic materials

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.

Metallic Biomaterials – december 2002 page 9

To bring a metal in his passivation domain, we can impose a suitable value of potential to the
metal.

b. Stability of the passivation layers

Stability of the passivation layers and their auto-reparation possibility are the main
problems. They depend on pH, oxidant force in the milieu, presence of some ions (Cl -,Br-…),
etc.

1.8. Conclusion on corrosion

Corrosion of an implant in the clinical setting can result in symptoms such as local
pain and swelling in the region of the implant, with no evidence of infection; only cracking or
flaking of the implant (seen on x-rays films), and excretion of excess metal ions. At surgery,
grey or black discoloration of the surrounding tissues may be seen and flakes of metals may
be found in the tissue. Corrosion also plays a role in the mechanical failures of orthopaedic
implants. Most of these failures are due to fatigue, and the presence of a saline environment
certainly exacerbates fatigue. The extent to which corrosion influences fatigue in the body is
not precisely known.
When an implant is subjected to stress, the corrosion process could be accelerated due
to the mechanical energy. If the mechanical stress is repeated then fatigue stress corrosion
takes place as in the femoral stem of the hip joint and hip nails made of stainless steel.
However, other mechanisms of corrosion such as fretting may also be involved at point of
contact such as in the counter-sink of the hip nail or bone fracture for the screws.
Different parts of the body undergo different type and rate of corrosion. Wounds and
infections can significantly change pH. Corrosion and fatigue added together can have a very
bad effect on the organ. The general concern is now to assure that metals in screws and in the
plates are identical. The surgeons must be careful not to scratch metals or to leave them in
tissues.

Metallic Biomaterials – december 2002 page 10

2. Properties and applications of the most used metallic biomaterials

Because all biomaterials have to be biocompatible, the difference in corrosion

resistance and in mechanical properties permits to aim them toward different applications. We
can classify the metallic biomaterials into 4 main groups: stainless steels, CoCr alloys, Ti
alloys, dental metals and the others.

2.1. Stainless steels

Vanadium steel’s corrosion resistance in vivo being not enough high, the first stainless
steel utilized for implant fabrication was the 18-8 (302 in modern classification). Later some
Mo has been added to it to improve the corrosion resistance. It was called 18-8Mo and
became later the type 316 stainless steel. In the 1950s the carbon content of 316 stainless
steels was reduced from 0,08 to an amount of 0,03% in weight, to more increase the corrosion
resistance and to minimize the sensitisation. This stainless steel is known today as 316L
stainless steel and contains, more than carbon, 2% of manganese, 17-20% of chromium, 12-
14% of nickel, 2-4% of molybdenum and small amount of phosphorus, sulfur and silicon.
Stainless steels contain enough chromium to confer corrosion resistance by passivity. The
passive layer is not as robust as in the case of titanium or the cobalt chromium alloys. Only
the most corrosion resistant of the stainless steels are suitable for implants, even these types of
stainless steels are vulnerable to pitting and to crevice corrosion around screws.
The 316 and 316L stainless steels are austenitic and this phase can be influenced by
the amount of Ni and Cr, but enhances the corrosion resistance. They can be hardened by
cold-working. We can obtain by this way a wide range of properties as yield and ultimate
tensile strength or elongation. These two steels are widely used for implant fabrication but
because of their poor corrosion resistance in the highly stressed and oxygen-depleted regions,
there are suitable to use in temporary implant devices such as fracture plates, screws and hip
nails.
For the manufacturing of stainless steels, heat treatments are necessary before cold-
working. But it is also the occasion: to cause corrosion by the formation of chromium carbide
in the grain boundaries, to produce distortion of components that can be solved a perfect
control of the uniformity of heating, involve the formation of surface oxide scales which have
to be removed. After the scales are removed, the surface of the component is polished,
cleaned and passivated in nitric acid.

Metallic Biomaterials – december 2002 page 11

2.2. CoCr Alloys
There are two CoCr alloys extensively used in implant fabrications such as artificial
joints, or stems of prostheses for heavily loaded joints such as knee and hip: the castable
CoCrMo alloy and the CoNiCrMo alloy which is usually wrought by (hot) forging. The
castable CoCrMo has been used also for many decades in dentistry.
The two basic elements of the CoCr alloys form a sold solution of up 65% Co. The
molybdenum is added to produce finer grains, which results in higher strengths after casting
or forging. The chromium enhances the corrosion resistance as well as solid solution
strengthening of the alloy.
The abrasive wear properties of the wrought CoNiCrMo are similar to he cast
CoCrMo alloy (about 0,14 mm/year in joint simulation tests PEHD acetabular cup); however,
the former is not recommended for the bearing surfaces of joint prosthesis because of its poor
frictional properties with itself or other materials. The superior fatigue and ultimate tensile
strength of the wrought CoNiCrMo alloy make it suitable for the applications which require
long service life without fracture or stress fatigue, such in the case of stems of the hip joint
prostheses. As with the other alloys, the increased strength is accompanied by decreased
ductility. Both the cast and wrought alloys have excellent corrosion resistance. As a matter of
fact, cobalt chromium alloys are passive in the human body. They are widely used in
orthopaedic applications. They do not exhibit pitting corrosion. However the metallic
products released from the prosthesis because of wear, corrosion and fretting may impair
organs and local tissues, and moreover some alloys with certain amount of Co can be toxic in
the body. Low wear has been recognized as an advantage of metal-on-metal hip articulations
because of its hardness and toughness.
The CoCrMo alloy is particularly susceptible to work-hardening so the normal
fabrication procedure used with other metals cannot be employed. The fabrication method
consists of making a wax pattern of the desired element. The pattern is coated with a
refractory material, first by a thin coating with a slurry (suspension of silica in ethyl silicate
solution) followed by complete investing after drying:
- wax melted in furnace (100-150°C)
- mould heated at high temperature burning out any traces of wax
- molten alloy poured with gravitational or centrifugal force
- mould broken after cooled.

Metallic Biomaterials – december 2002 page 12

2.3. Ti Alloys

a. Pure Ti and Ti6Al4V

Attempts to use titanium for implant fabrication dates to the late 1930s. Titanium’s
lightness (4,5 g/cm3) and good mechano-chemical properties are salient features for implant
application. There are four grades of unalloyed commercially pure (cp) titanium for surgical
implant applications. The impurity contents separate them: oxygen, iron, and nitrogen should
be controlled carefully. Oxygen in particular has a great influence on the ductility and
strength. These alloys contain also hydrogen and carbon (respectively, 0,015 % and 0,1% in
weight) Titanium alloys can be strengthened and mechanical properties varied by controlled
composition and thermo mechanical processing techniques. Moreover the addition of certain
elements, such as aluminium or vanadium, enables it to have a wide range of properties.
In addition titanium alloys have an excellent corrosion resistance thanks to the formation of
an oxide layer on its surface.
Another kind of titanium alloys is appreciated for its capacity to “have the memory of
its shape”.

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.

Metallic Biomaterials – december 2002 page 13

 Titanium is very reactive at high temperature and burns readily in the presence of
oxygen. Therefore, it requires an inert atmosphere for high temperature processing or is
processed by vacuum melting. Oxygen diffuses readily in titanium and the dissolved oxygen
embrittles the metal. As a result, any hot working or forging operation should be carried out
below 925°C. Machining at room temperature is not the solution to all the problems since the
material also tends to gall or seize the cutting tools. Very sharp tools with slow speeds and
large feeds are used to minimize this effect. Electrochemical machining is an attractive mean.

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.

2.4. Dental metals

Dental amalgam is an alloy made of liquid mercury and other solid metal particulate
alloys made of silver, tin, and copper…The solid alloy is mixed with liquid mercury in a
mechanical vibrating mixer and the resulting material is packed into the prepared cavity. The
final composition of dental amalgams typically contain 45 to 55% mercury, 35 to 45% silver,
and about 15% tin after fully set in about one day.
Amalgam often corrodes and is the most active material used in industry. Furthermore,
the use of mercury is forbidden because of the harmful effects of mercury on the human body.
Gold and gold alloys are useful metals in dentistry as a result of their durability, stability and
immunity to corrosion. Gold is widely used in dental restoration and in that setting it offers
superior performance and longevity. Gold is not, however, used in orthopaedic applications as
a result of its high density, insufficient strength and high cost. Gold alloys are used for cast
restorations, since they have mechanical properties, which are superior to those of pure gold.
Copper or platinum, alloyed with gold, increase its strength, while silver is only added for
compensation for the colour of copper.

2.5. Other metals

Several others metals have been used for a variety of specialized implant applications.
Tantalum has been subjected to animal implant studies and has been shown very
biocompatible. Due to its poor mechanical properties and its high density, it is restricted to
few applications such as wire sutures for plastic surgeons and a radioisotope for bladder
tumors.

Metallic Biomaterials – december 2002 page 14

 Platinum group metals, such as Pt, Pd, Rh, Ir, Ru and Os are extremely corrosion
resistant but have poor mechanical properties. They are mainly used as alloys for electrodes
such as pacemaker tips because of their high resistance to corrosion and low threshold
potentials for electrical conductivity.
Thermoseeds made of 70% Ni and 30% Cu are used to deliver a constant hyperthermic
temperature extra corporally at any time and any duration, by applying an alternative
magnetic field.

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.

Metallic Biomaterials – december 2002 page 15

 Materials
Propertie
316L stainless CoCrMo CoNiCrM Ti6Al4V
s Grades Ti Tantalum
steel alloy o alloy alloy
(Mpa)
strength
Tensile

485-860 655 793-1793 240-550 860 207-517

(Mpa)
(0,2% offset)
Yield strength

172-690 450 240-1585 170-485 795 138-345

(%)
Elongation

12-40 8 8-50 15-24 10 2-30

(%)
of area
Reduction

- 8 35-65 25-30 25 -
(g/cm3)
Density

7,9 8,3 9,2 4,5 4,5 16,6

resistance
Corrosion

poor in highly
excellent excellent excellent excellent good
stressed

and O2 depleted
region

Table 2 : Summary table

Metallic Biomaterials – december 2002 page 16

3. Titanium and Ti alloys as Biomaterials

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.

Metallic Biomaterials – december 2002 page 17

  Hydroxyapatite – Ti alloys composites

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.

Hydroxyapatite excels in affinity for a living body. Therefore it is expected to be

applied to artificial bones, dental roots and so on. Hydroxyapatite is a calcium phosphate,
whose chemical composition and properties are very closed to bones, and is moreover
biodegradable in the body. However, since the mechanical strength is low, apatite cannot be
used under a heavy load so that its application is
limited. A high strength β -rich α -β titanium
alloy, Ti-4,5Al-3V-2Fe-2Mo as example, has
remarkable superplastic formability at
temperature below 800 °C, more than 100 °C
lower than Ti-6Al-4V. By a superplastic
forming, titanium alloy can be formed easily into
complicated shapes. Then the application for
dental materials, such as dental base, has been
investigated. The method of implanting
hydroxyapatite into superplastic titanium alloy
substrate was examinated. Hydroxyapatite
granules are spread over the surface of titanium
alloy, and are heated at 750 °C in a vacuum.
There are then implanted into the alloy by giving
pressure of about 17 Mpa.

Figure 5 : SEM photographs for the pressed specimens under 17 Mpa at 750°C for 10 min.

Another method exists for the fabrication of these composites. Hydroxyapatite is

simply deposed on the surface of titanium alloy by plasma spraying. This method is besides
actually the only commercially accepted technique for deposing such coating.

Metallic Biomaterials – december 2002 page 18

 Various processes have been used for manufacture hydroxyapatite coated implants for
biomedical applications, such as chemical, electrochemical or pulsed laser deposition sol–gel
technique, magnetron sputtering or ion implantation. The plasma spraying technique has
become the most frequently used technique to fabricate hydroxyapatite coatings.

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.

Figure 6 : REM picture of marrow bone cells on (a) a titanium

surface, (b) on the hydroxyapatite surface layer produced by ion implantation.

Moreover, fabrication of bioactive silica-based glasses – titanium alloys composite has

been reported. As a matter of fact a new family of potentially bioactive glasses displays good
physical compatibility with Ti. In order to fabricate dense coatings, glass powder is painted
over the metal substrates and the assemblies are fired to make the glass flow and adhere to the
metal.

Metallic Biomaterials – december 2002 page 19

 b. Mechanical Suitability

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.

Material Density ρ Elastic Modulus E (GPa) Specific criteria: E / ρ

Cortical Bone ~2.0 g.cm-3 7-30 ~3,5-15
Cobalt-Chrome alloy ~8.5 g.cm-3 230 ~27
316L Stainless Steel 8.0 g.cm-3 200 25
CP Titanium 4.5 g.cm-3 110 24,4
Ti6Al4V 4.4 g.cm-3 106 24

Table 3. Densities of selected biomaterials and cortical bone.

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.

Metallic Biomaterials – december 2002 page 20

3.2. Applications

a. Orthopaedic Implants

Titanium is commonly used in orthopaedic implants such as joint replacements and

bone pins, plates and screws.

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.

The hemispherical item on

Figure 7 : Implant components for a total hip replacement
the right is the acetabular cup, also
made from titanium alloy. It is coated in a porous alumina ceramic, to allow bone ingrowth
for stabilisation. An ultra high molecular weight polyethylene (UHMWPE) liner fits inside
the acetabular cup and provides the articulating surface for the
femoral head.

Figure 8 shows prototype total knee replacement prosthesis,

similar in design to many commercial implants. It consists of
titanium alloy upper and lower structural components. A zirconia
wear surface has been fabricated for the upper section. Similar to the
hip prosthesis, this articulates against a UHMWPE insert on the lower section.

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

Metallic Biomaterials – december 2002 page 21

 Ti is also newly used in the anchorage screws (figure 9) in the knee (1), the shoulder
(2), the hand (3) and the ankle (4). A suture thread is attached to the screw, which is in turn
fixed to the bone. This Ti screw (figure 10) can easily be seen in the body by a radiography
control and it can also be removed from the tissue, if needed.

Figure 9 : Ligament anchorages

Figure 10 : Ti screw

Metallic Biomaterials – december 2002 page 22

 c. Dental Applications

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.

Titanium superstructures are now

being investigated as an alternative
to other metals such as gold for
implants such as polymer based
dentures (figure 11).

Figure 11 : Side view of a super plastically-formed, titanium alloy, cantilevered

superstructure, attached to dental plaster analogues in a plaster model of a
patients jaw.
Shape Memory Alloys (SMAs)

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

Metallic Biomaterials – december 2002 page 23

corrective forces applied, the stainless steel wire had to be re-tensioned and visits to the
orthodontist were maybe needed every three weeks in the beginning of the treatment.

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.

Metallic Biomaterials – december 2002 page 24

 d. Perspectives and conclusion

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.

Metallic Biomaterials – december 2002 page 25

 References

[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)

Metallic Biomaterials – december 2002 page 26