Metallic Biomaterials
Metallische Biomaterialien
The improvement of medical health care during the past years
has led to an increased use of implants. The requirements placed
on implant materials are determined by medical progresses and
biological demands. Metallic biomaterials are the dominating
group of materials for use as highly tension loaded implants.
Among the metals, titanium and specially developed titanium al-
loys have an outstanding position due to their combination of
strength, elasticity and biocompatibility. In addition it is possible
to develop ªtailored materialsº by functional coating the metals
or by the production of composite materials.
1 Introduction
The properties of an implant or medical device are deter-
mined by the specific product properties such as processabil-
ity, availability or appearance as well as by the material prop-
erties such as the mechanical, physical, chemical or biological
properties. Metals designed for the application as a biomate-
rial have to fulfill certain additional requirements. First of all
the metal or alloy requires a good corrosion resistance in order
to avoid degradation in the biological environment. A good
biocompatibility implies that no toxic or allergic reaction oc-
curs. In the case of endosseous implants a high bioadhesion,
i. e. a high adhesion strength of the osteoblasts to the implant
is required. Adequate mechanical properties such as high fa-
tigue strength or a Young's Modulus similar to that of the
human bone (ªisoelastic implantº) are very important. In or-
der to achieve a cost-saving price a sufficient processability
like casting, deformation, machinability, welding or brazing
is necessary. Last but not least the availability is an important
factor for the production and acceptance of a medical device
or implant. Table 1 gives examples of material properties and
their relevance to biomaterials [1]. In general, the physical
properties play an important role only in the case of special
functional applications as in heart peacemaker electrodes.
Good chemical and biological properties are a prerequisite
for application as a biomaterial as mentioned above. The
most important mechanical properties for highly loaded im-
plants such as hip endoprostheses are fatigue strength and
Young's Modulus, which leads to the definition of the biofunc-
tionality BF as the ratio of the fatigue strength rf to Young's
Modulus E:
rf
BF ˆ 1†
E
A comparison of the applicability of various material
groups to the most important mechanical requirements of bio-
Mat.-wiss. u. Werkstofftech. 32, 137±141 (2001)
Ó WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001
V. Biehl and J. Breme
Die zunehmende Verbesserung der medizinischen Versorgung
der letzten Jahre hat auch zu einer Zunahme des Einsatzes von Im-
plantaten gefuÈhrt. Die Anforderungen an den dabei verwendeten
Werkstoff werden durch die medizinischen Fortschritte bzw. biolo-
gischen Vorgaben bestimmt. Im Bereich der hoch mit Zugspannun-
gen belasteten Implantate sind die metallischen Biomaterialien auf-
grund ihrer Festigkeitseigenschaften die dominierende Werkstoff-
gruppe. Unter den Metallen besitzen insbesondere das Titan und
speziell entwickelte Titanlegierungen aufgrund der herausragen-
den Kombination von Festigkeit, ElastizitaÈt und BiokompatibilitaÈt
eine besondere Stellung. DaruÈber hinaus besitzen metallische Bio-
materialien, neben der MoÈglichkeit die mechanischen Eigenschaf-
ten z. B. durch Legieren gezielt einzustellen, auch den Vorteil, daû
maûgeschneiderte Eigenschaften durch funktionelle Beschichtung
oder Herstellung von Verbundwerkstoffen erzeugt werden koÈnnen.
materials shows the prominent role of the metallic biomate-
rials (Table 2).
The specific requirements placed upon biomaterials such as
corrosion resistance and biocompatibility restrict the metals or
alloys which can be used to the four following groups:
l stainless steels (e. g. DIN/ISO 5832-1 or AISI 316L)
l CoCr-alloys (cast DIN/ISO 5832-4 or wrought DIN/
ISO 5832-6, ªVitalliumº)
l cp-titanium (DIN/ISO 5832-2) or titanium alloys such as
Ti6Al4V (DIN/ISO 5832-3)
l cp-niobium or cp-tantalum
2 Properties of metallic biomaterials
2.1 Mechanical properties
Table 3 summarizes the ranges of mechanical properties
including the biofunctionality for the four groups of metallic
biomaterials. High ultimate tensile and fatigue strength com-
bined with sufficient elongation at fracture can be seen for the
CoCr-alloys as well as for titanium alloys. Stainless steels
show reduced tensile and fatigue strength but higher duc-
tility. The pure metals titanium, tantalum and niobium have
reduced strength properties but high values for elongation
at fracture. A comparison of the biofunctionality of various
alloys shows the exceptional properties of titanium and tita-
nium alloys due to their low Young's Modulus (Fig. 1).
From the biomechanical point of view, it is desirable to
have a Young's Modulus comparable to that of the cortical
bone in order to achieve a good load transfer from the implant
into the bone, leading to a continuous stimulation of new bone
formation (ªisoelastic materialº) [3]. A further reduction of
Young's modulus of titanium alloys can be achieved by alloy-
ing with b-stabilizing elements. For example, the alloy Ti30Ta
which belongs to the group of near b-titanium alloys shows a
0933-5137/01/0202-0137$17.50 ‡ .50/0 137
Table 1. Specific requirements for metallic biomaterials [1]
Tabelle 1. Spezifische Anforderungen an metallische Biomaterialien [1]

Material Properties Important for application

Mechanical Properties
ultimate tensile strength, tensile yield strength elongation at endosseous implants like orthopedic implants, dental
fracture, reduction in area fracture toughness implants, nails, plates, screws
Young's modulus
fatigue strength
wear resistance
Physical Properties
density
acoustic properties ultrasonic examinations
electrical resistance heart pacemaker electrodes
magnetism NMR-examinations
thermal expansion composite materials
Chemical Properties
oxidation prerequisite for all biomaterials
corrosion, degradation
fretting corrosion

Biological Properties
bioadhesion (osseoconductivity, osseointegration) prerequisite for all biomaterials
immune reaction (allergic, toxic, mutogenic, carcinogenic)

Table 2. Applicability of biomaterials to different types of loads [1]

Tabelle 2. Eignung der Biomaterialien fuÈr verschiedener Belastungsarten [1]

Type of Load Metal Ceramics Polymers

Static load
tension q Q R
compression q q R
bending q Q R
torsion q Q R

Dynamic load
tension-compression q Q R
tension q Q R
compression q q R
bending q Q R
Impact load q Q R
legend: q ± suitable, Q ± not suitable, R ± suitable under low stresses

Table 3. Mechanical properties of metallic biomaterials [1, 2]

Tabelle 3. Mechanische Eigenschaften metallischer Biomaterialien [1, 2]

Material ultimate tensile fatigue strength* elongation at BF

strength [MPa] [MPa] fracture [%] [*10ÿ3]
Metals
CrNi-steels 490 ± 690 200 ± 250 > 40 1 ± 1.2
CoCr-alloys 800 ± 1200 550 ± 650 8 ± 40 1.5 ± 2.3
cp-Ti 390 ± 540 150 ± 200 22 ± 30 1.4 ± 1.9
Ti6Al4V 930 ± 1140 350 ± 650 8 ± 15 3.0 ± 5.6
* ± rotating bending fatigue

reduction of Young's Modulus of 80 % as compared to cp.- sintered implants are required. The reduction of Young's Mod-
titanium. In addition, by quenching the alloy from high tem- ulus as a function of the porosity can be calculated by means
peratures a martensitic structure can be achieved which has a of equation (2) [4]:
Young's Modulus of only 63 GPa. In order to provide a Mod-
ulus comparable to that of compact bone (10 ± 15 GPa) porous Ep ˆ E0 1-1:21 * p2=3 † 2†

138 V. Biehl and J. Breme Mat.-wiss. u. Werkstofftech. 32, 137±141 (2001)

 Table 4. Biofunctionality (BF) of metallic biomaterials [1, 2]
Tabelle 4. BiofunktionalitaÈt (BF) metallischer Biomaterialien
[1, 2]

Material fatigue strength* Young's BF

[MPa] Modulus [*10ÿ3]
[GPa]

Metals
CrNi-steels 250 210 1.2
CoCr (as cast) 300 200 1.5
CoNiCr (forged) 500 220 2.3
(a ‡ b)-titanium alloys 550 105 5.2
cp-Ti 200 100 1.8
cp-Ni 150 120 1.3
cp-Ta 200 200 1.3
* ± rotating bending fatigue

Fig. 1. Biofunctionality of metallic Biomaterials [1]
Abb. 1. BiofunktionalitaÈt metallischer Biomaterialien [1]
where Ep is the Young's Modulus of the porous sintered ma-
terial, E0 the modulus of the bulk material and p the porosity.
Figure 2 shows Young's Modulus for different porous sintered
biomaterials as a function of their porosity. It can be seen that
with alumina even with a porosity of 40 % no modulus com-
parable to that of the bone can be achieved. By contrast, ti-
tanium and especially the near b-titanium alloys show a
low Young's Modulus with relatively low values of the po-
rosity, leading to the desirable isoelastic behavior (Table 4).
2.2 Chemical and Biological Properties
In order to understand the chemical and biological require-
ments for metallic biomaterials it is necessary to discuss pos-
Fig. 2. Influence of the porosity on Young's modulus of Biomate-
rials [1]
Abb. 2. Einfluû der PorositaÈt auf den E-Modul von Biomaterialien
[1]
sible reactions of primary corrosion products with the human
body.
If corrosion of an metallic implant in the body occurs, the
flow of the electrons in the metal lead to a flow of ions in the
surrounding tissue, resulting in a disturbation of nerve cells.
The metal ions released due to inorganic corrosion reactions
are transported into internal organs such as the liver or the
kidneys. In the ongoing corrosion process these ions accumu-
late in the internal organs, which leads to diseases if the limit
of toxicity will be exceeded. An organic reaction, i. e. a reac-
tion of the metal with proteins may lead to allergic or inflam-
matory reactions of the surrounding tissue. Inflamed cells pro-
duce hydrogen peroxide and hydroxyl radicals respectively,
resulting in heavy damage of the surrounding tissue such
as deterioration of biomembranes.
The reaction of the human body to implant material can be
classified in three groups:
l toxicity
l encapsulation
l inertness
Figure 3 classifies most important elements and alloys used
as biomaterials according to their polarization resistance as a
measure of its corrosion property, and the type of reaction they
induce in the biological environment. In general, a high po-
larization resistance, i. e. good corrosion properties lead to
inert behavior like with titanium and titanium alloys. Toxic
effects are observed with the elements Co, Cr, Ni and V. In
between are the elements Fe, Mo, Al, Au and Ag which
are encapsulated by the human body. The results for stainless
steel (316L) or the CoCrMoNi alloy show that not only the
corrosion behavior determines the reaction of the biological
system. Despite a high polarization resistance of these al-
loys, they are encapsulated by the surrounding tissue [5]. An-
other reason for the good biological properties of titanium and
titanium alloys is the low electrical conductivity of the dense
surface oxide layer on these alloys which is formed at room
temperature in oxidizing media within milliseconds. These
oxide layers prevent an extensive flow of electrons and
ions in the body fluid or surrounding tissue. This isolating
effect can be described by the dielectric constant of the sur-
face oxide which is given in Table 5 [6]. In addition, the heat of
formation and the solubility (pK value) of some elements are
also given in Table 5. For metallic biomaterials, a low solu-
bility and a high thermodynamic stability are desired in order
to avoid dissolution and transport of primary corrosion pro-
ducts and a reaction of these products with the biological sys-

Mat.-wiss. u. Werkstofftech. 32, 137±141 (2001) Metallic Biomaterials 139

 Table 5. Heat of formation, solubility and dielectric constant of
primary corrosion products [6]
Tabelle 5. Standard Bildungsenthalpie, LoÈslichkeitsprodukt und
DielektrizitaÈtskonstante von primaÈren Korrosionsprodukten [6]

Primary Corrosion ÿ DH0298 pk e

Products [kJ/mol]

Ta2O5 2090 > 20 12

Nb2O5 1905 > 20 280
Al2O3 1675 14,6 5 -10
V 2O 3 1560 10,3
Cr2O 1141 18,6 12
Cr(OH)2 988 ÿ 1,8
Al(OH)3 916 32,3
Fig. 3. Tissue reaction of various elements and biomaterials [5] WO3 838 14
Abb. 3. Gewebereaktion auf verschiedene Elemente und Biomate- Fe2O3 822 ÿ 14 100
rialien [5] MoO3 712 3,7
CrO3 595
Fe(OH)2 568 2,3 30 - 38
Ni(OH)2 538 15,8
TiO 518
NbO 486
VO 410
H 2O 273 14 78
FeO 267 ÿ 13,3
NiO 240 ÿ 12,2
CoO 239 ÿ 12,6
Cu2O 168 > 14
CuO 162
Ag2O 32 7,7
TiO2
Anatas 935 48
Brookite 18 78
Rutil 943 110

Fig. 4. Survival rate of L132 cells cultivated with metal powders of

different concentrations [7]
Abb. 4. U È berlebensrate von L132 Zellen, die mit Metallpulvern in
unterschiedlicher Konzentration kultiviert wurden [7]
tem. These requirements are fulfilled by titanium and titanium
alloys, making them the metallic biomaterials of preference.
In-vitro cell tests where the concentration of metallic pow-
ders mixed with cell culture medium leads to the LC50-value
(mortality of 50 % of the cells) confirm the good biocompat-
ibility of titanium as compared with other materials. Figure 4
gives the survival rate of L132-cells as a function of the con-
centration of the metal powder in the culture medium. It can
be clearly seen that titanium has nearly no effect on the cells,
i. e. no LC50 rate can be determined. By contrast, a reduced
survival rate of the cells cultured with CoNiCr-alloy or stain-
less steel is observed. Ni seems to be one important factor for
this behavior as it reduces the survival rate of the cells even
with very low concentrations in the culture medium [7].
the oxide layer lead to a good adhesion of cells. For the ap-
plication of titanium or titanium alloys as electrodes for heart
pacemaker leads the oxide layer has to be replaced by a highly
conducting surface coating in order to avoid high battery loss.
Possible layers and their specific electrical resistivities are
given in Table 6. In order to increase the contact surface of
the electrode and the myocardium, which produces a good
signal transmission and low consumption of power, porous
sintered electrodes, which in addition due to their increased
surface possess a high capacity, coated with high conductive
surface coatings were developed. Impedance measurements
showed good results for porous sintered electrodes coated
with TiN or TiB2 and lowest values of impedance for Ir
coated electrodes [8].
Table 6. Specific electrical resistivity of metals and coatings [8]
Tabelle 6. Spezifischer elektrischer Widerstand von Metallen und
Beschichtungen [8]

3 Examples of tailored biomaterials and Material specific electrical resistivity q [lWcm]

their application TiO2 1016
IrO2 49
3.1 Porous sintered heart pacemaker leads Ti 41,8
TiN 25
TiB2 14,4
As mentioned above, titanium and titanium alloys possess a Ir 5,3
dense oxide layer on the surface. The isolating properties of

140 V. Biehl and J. Breme Mat.-wiss. u. Werkstofftech. 32, 137±141 (2001)

3.2 Porous coated hip endoprostheses
Requirements for highly loaded endosseous implants such
as hip endoprostheses include, in addition to sufficient me-
chanical properties, a good load transfer from the implant
into the bone in order to stimulate the formation of new
bone, leading to a good and long term integration. A reduc-
tion of Young's Modulus to a value similar to that of the bone
will provide this isoelastic behavior. This can be achieved by
production of a suitable alloy such as Ti30Ta and/or porous
sintered surfaces [9]. Osseoconductive effects of hydroxyapa-
tite (HA) have long been known and a large number of im-
plants coated with HA in a plasma spray process are avail-
able. Due to the low reaction temperatures and other proces-
sing parameters thick layers without a shear strength between
the substrate and the HA coating are achieved. To provide a
high shear strength of the HA/metal-interface a heat treatment
is necessary, which due to an interdiffusion produces a chem-
ical bonding. In order to avoid cracks during cooling after the
heat treatment process, a suitable alloy with a thermal expan-
sion coefficient comparable to that of HA has to be developed.
In addition, a coating technique which makes it possible to
produce thin HA layers is desirable as thin layers can with-
stand higher tensile stresses compared to thick ceramic layers
[10].
A combination of these requirements was fulfilled by a hip
endoprosthesis made of the biocompatible alloy Ti5Al2.5Fe
as bulk material. This material was coated in a powder metal-
lurgical process (cold isostatic pressing (CIP) ‡ sintering at
800 ± 900 8C) with Ti30Nb or Ti8Mn and subsequently
coated with HA by sol-gel-techniques. In vitro tests con-
firmed a good adhesion strength of the HA ceramic on the
metal substrate due to a diffusion zone at the crack-free cera-
mic/metal interface resulting from the adapted thermal expan-
sion coefficient of the alloys Ti30Nb and Ti8Mn. In addition a
sufficient fatigue strength of the porous coated implant was
achieved by using small sized powders (63 ± 90 lm) which
show a good sintering behavior even at relatively low sinter-
ing temperatures. The use of sintering temperatures below the
(a ‡ b)/b-transus temperature of the Ti5Al2.5Fe alloy
(950 8C) avoids the inadequate basket weave microstructure
with reduced good fatigue properties of the bulk material.
The rotating bending fatigue strength, measured in step
case tests, of the porous coated samples was 554 MPa which
is sufficient for use as highly loaded implants such as hip en-
doprostheses [11, 12].
3.3 Wear resistant composites based on Ti-Fe-B
Due to the low wear resistance of cp.-Ti and its alloys, the
application of uncoated titanium in articulating components
such as balls for hip endoprostheses is limited. Usually TiN
or TiO2 coatings of titanium or titanium alloys are applied
in order to enhance wear properties. A new method of improv-
ing the wear resistance of titanium is the production of a com-
posite material consisting of a metallic matrix with ceramic
particles (cermet). By the use of biocompatible elements
such as Ti, Fe and B alone, the production of a cermet in
an in-situ reaction according to Eq. (3)
2 Ti ‡ FeB ! TiB ‡ TiFe 3†
is possible. By optimizing the relation of the amount of FeB
and Ti a wear resistant Ti-based biocompatible cermet was
Mat.-wiss. u. Werkstofftech. 32, 137±141 (2001)
produced by casting and powder metallurgical methods. Pin
on disc measurements of samples against 100Cr6 as a counter-
part showed that wear decreases towards zero if the amount of
the hard phase TiB in the Ti matrix exceeds 20 vol.% [13].
4 Conclusions
The outstanding properties of titanium and titanium alloys
such as corrosion resistance or mechanical properties makes
them the biomaterials of preference. In addition a coating of
titanium and especially tailored titanium alloys with layers
which induce specific reactions of the biological system
such as an increased healing of the bone in the case of hy-
droxyapatite is possible. With three examples, the wide-range
of possibilities of tailoring titanium and titanium alloys for
special applications was shown.
5 References
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Anschrift: V. Biehl, UniversitaÈt des Saarlandes, Lehrstuhl fuÈr Me-
tallische Werkstoffe, Postfach 15 11 50, 66041 SaarbruÈcken
Received: 10/13/00 [T 316]
Metallic Biomaterials 141