Bioceramics

Materials in medical Science

lecture 7

Types of Bioceramics

Comparative mechanical properties

Natural Ceramic materials

Bioactivity
Vs.Biocompatibility

Relatively Bioinert Ceramics

Relatively bioinert ceramics maintain their physical
and mechanical properties while in the host.
They resist corrosion and wear.
Examples of relatively bioinert ceramics are dense
and porous aluminium oxides, zirconia ceramics,
and single phase calcium aluminates
Relatively bioinert ceramics are typically used as
structural-support implants. Some of these are
bone plates, bone screws, and femoral heads
.Examples of non-structural support uses are
ventilation tubes, sterilization devices and drug
delivery devices

Uses of Bioinert Ceramics

Alumina(Al203)
The main source of high purity alumina
(aluminium oxide) is bauxite and native
corundum.
The commonly available alumina (alpha,) can
be prepared by calcining alumina trihydrate
The American Society for Testing and
Materials (ASTM) species that alumina for
implant use should contain99.5% pure alumina
and less than 0.1% combined SiO2 and alkali
oxides (mostly Na2O)

Characteristics of Alumina

Characteristics of Alumina
The strength of polycrystalline alumina depends
on its grain size and porosity. Generally, the
smaller the grains, the lower the porosity and
the higher the strength .
The ASTM standards (F603-78) requires a
exural strength greater than 400 MPa and
elastic modulus of 380 Gpa.

NB: Exists as single crystal and polycrystalline

material. Natural single crystals are
Ruby/Sapphire.

Gems
Diamond=Carbon
Ruby: Alumina with chromium
impurity
Sapphire: Alumina
Emerald:Be3Al2(SiO3)6,
Diamond

Emerald

Ruby

Blue Sapphire

Alumina
Both polycrystalline and single crystal alumina have been
used clinically. The high hardness is accompanied by low
friction and wear and inertness to the in vivo environment.
These properties make alumina an ideal material for use
in joint replacements. One of the most popular uses for
aluminium oxide is in total hip prostheses.
Aluminium oxide hip prostheses with an ultra-high
molecular weight polyethylene (UHMWPE) socket have
been claimed to be a better device than a metal prostheses
with a UHMWPE socket [Oonishi, 1992].
However, the key for success of any implant, besides
the correct surgical implantation, is the highest possible
quality control during fabrication of the material and the
production of the implant

Zirconia(ZrO2)
Pure zirconia can be obtained from chemical conversion of
zircon (ZrSiO4), which is an abundant mineral deposit [Park
and Lakes, 1992]. Zirconia has a high melting temperature
(Tm = 2953 K) and chemical stability.
It undergoes a large volume change during phase changes
at high temperature in pure form; therefore, a dopant oxide
such as Y2O3 is used to stabilize the high temperature
(cubic) phase.
Zirconia produced in this manner is referred to as partially
stabilized zirconia. However, the physical properties of
zirconia are somewhat inferior to that of alumina Zirconia has
shown excellent biocompatibility and good wear and friction
when combined with ultra-high molecular weight
polyethylene .

Other uses of Zirconia

Although low-quality zirconia is used as an abrasive in huge
quantities, tough, wear resistant, refractory zirconia
ceramics are used to manufacture parts operating in
aggressive environments, like extrusion dyes, valves and
port liners for combustion engines, low corrosion, thermal
shock resistant refractory liners or valve parts in foundries.
Zirconia blades are used to cut Kevlar, magnetic tapes. High
temperature ionic conductivity makes zirconia ceramics
suitable as solid electrolytes in fuel cells and in oxygen
sensors. Good chemical and dimensional stability,
mechanical strength and toughness, coupled with a Youngs
modulus in the same order of magnitude of stainless steel
alloys was the origin of the interest in using zirconia as a
ceramic biomaterial.

Partially Stabilized Zirconia

Zirconia is a well-known polymorph that occurs in three forms: monoclinic
(M), cubic (C) and tetragonal (T).Pure zirconia is monoclinic at room
temperature. This phase is stable up to 1170C. Above this temperature it
transforms into tetragonal and then into cubic phase at 2370C. During
cooling, a TM transformation takes place in a temperature range of
about 100C below 1070C. The phase transformation taking place while
cooling is associated with a volume expansion of approximately 34%.
Stresses generated by the expansion originate cracks in pure zirconia
ceramics that, after sintering in the range 15001700C, break into
pieces at room temperature. It was in 1929 that Ru and coworkers showed
the feasibility of the stabilisation of C-phase to room temperature by
adding to zirconia small amounts of CaO.
The addition of stabilising oxides, like CaO, MgO,CeO2, Y2O3 , to pure
zirconia allows to generate multiphase materials known as Partially
Stabilized Zirconia (PSZ) whose microstructure at room temperature
generally consists of cubic zirconia as the major phase( Except Y2O3:
which are mainly tetragonal zirconia polycrystals).

Characteristics of Zirconia

Carbon: Pyrolytic
Pyrolytic carbon is a material similar to graphite, but
with some covalent bonding between its graphene
sheets as a result of imperfections in its production.
Pyrolytic carbon is man-made and not found in
nature. Generally it is produced by heating a
hydrocarbon nearly to its decomposition
temperature, and permitting the graphite to
crystallise (pyrolysis). One method is to heat
synthetic bers in a vacuum. Another method is to
place seeds or a plate in the very hot gas to collect
the graphite coating.

Carbon: Pyrolytic
High mechanical strength (fatigue)
and chemical resistance
Applications: Articial joints (rarely
used) and Heart valves (main use)

Glassy Carbon
Glassy carbon, also called vitreous carbon, is an advanced material of pure
carbon combining glassy and ceramic properties with these of graphite. Unlike
graphite, glassy carbon has a fullerene-related microstructure. This leads to a
great variety of unique material properties.

High temperature resistance in inert gas or vacuum up to 3000C

High purity
Extreme corrosion resistance
Impermeability to gas and liquids, no open porosity
No wetting by melts
High hardness and strength
Low density
High surface quality, no particle generation
Low thermal expansion
Extreme resistance to thermal shock
Isotropy of physical and chemical properties
Good electrical conductivity
Biocompatibility

Glassy carbon
Unlike all other ceramic and metallic high
temperature materials, glassy carbon increase in
strength with a rise in temperature up to 2700 K.
Glassy carbon shows at 2700 K compared to room
temperature the double strength. Compared to
ceramic and metallic materials, glassy carbon
shows even at high temperatures no
embrittlement.
Due to the high purity the catalytic action of foreign
elements (reaction centres) concerning oxidation
and corrosion is limited to a minimum.
Mainly electrode and biosensor application

Carbon
Graphite and glassy carbon have a
much lower mechanical strength
than Pyrolytic carbon . However, the
average modulus of elasticity is
almost the same for all carbons

Carbon
Carbons exhibit excellent
compatibility with tissue.
Compatibility of Pyrolytic carboncoated devices with blood have
resulted in extensive use of these
devices for repairing diseased heart
valves and bloodvessels

Distribution of minerals in hard

tissues

Mechanical properties of
Tissues

Biodegradable or Resorbable
Ceramics
Although Plaster of Paris was used in 1892 as a bone
substitute [Peltier, 1961], the concept of using synthetic
resorbable ceramics as bone substitutes was introduced in
1969 [ Hentrich et al., 1969; Graves et al., 1972].
Resorbable ceramics , as the name implies, degrade
upon implantation in the host. The resorbed material is
replaced by endogenous tissues. The rate of degradation
varies from material to material. Almost all Bioresorbable
ceramics except Biocoral and Plaster of Paris (calcium sulfate
dihydrate) are variations of calcium phosphate Examples of
resorbable ceramics are aluminium calcium phosphate,
coralline, Plaster of Paris, hydroxyapatite and tricalcium
phosphate

Calcium Phosphate
Calcium phosphate has been used in the form of articial bone.
This material has been synthesized and used for manufacturing
various forms of implants, as well as for solid or porous
coatings on other implants.
Calcium phosphate can be crystallized into salts such as
hydroxyapatite and -whitlockite depending on the Ca:P ratio,
presence of water, impurities, and temperature. In a wet
environment and at lower temperatures (<900C), it is more
likely that hydroxyl- or hydroxyapatite will form, while in a
dry atmosphere and at a higher temperature, -whitlockite will be
formed [Park and Lakes 1992]. Both forms are very tissue
compatible and are used as bone substitutes in a granular form or
a solid block. The apatite form of calcium phosphate is considered
to be closely related to the mineral phase of bone and teeth.

Calcium Phosphate
The ideal Ca:P ratio of hydroxyapatite is
10:6 and the calculated density is 3.219
g/cm3. Substitution of OH with uoride
gives the apatite greater chemical
stability due to the closer coordination of
uoride (symmetric shape) as compared
to the hydroxyl (asymmetric, two atoms)
by the nearest calcium. This is why
uoridation of drinking water helps in
resisting caries of the teeth.

Calcium Phosphate
Polycrystalline hydroxyapatite has a high
elastic modulus (40 to 117 GPa). Hard tissue
such as bone,dentin, and dental enamel are
natural composites which contain
hydroxyapatite (or a similar mineral),as well
as protein, other organic materials, and water.
Enamel is the stiffest hard tissue, with an
elastic modulus of 74 GPa, and contains the
most mineral. Dentin (E = 21 GPa) and
compact bone (E = 12 to18 GPa) contain
comparatively less mineral.

Among the most important properties of hydroxyapatite as a biomaterial is its

excellent biocomaptibility. Hydroxyapatite appears to form a direct chemical
bond with hard tissues [Piattelli and Trisi, 1994].
On implantation of hydroxyapatite particles or porous blocks in bone,
new lamellar cancellous bone forms within 4 to 8 weeks [Bajpai and Fuchs,
1985]

Whitlockite
Whitlockite is a mineral, an unusual form of calcium phosphate. Its formula is Ca9(MgFe)
(PO4)6PO3OH. It is a relatively rare mineral but is found in granitic pegmatite, phosphate
rock deposits, guano caves and in chondrite meteorites.
Whitlockite can also be found in biological systems and has been implicated in several
human diseases. Whitlockite can be found at many different sites in the human body, but
is particularly concentrated in calcied tissues, such as embryonic and adult bone. The
highest concentrations of whitlockite appear in the weight bearing area of the femoral
head.Traces of whitlockite have also been found in tuberculous lesions, urinary calculi
and even prostatic deposits. Whitlockite can also be found in the oral cavity, where it is a
primary component of dental calculi and salivary stones. Lastly, whitlockite can be found
in aortic media, where it may be involved in arteriosclerosis. The presence of whitlockite
at these different locations has not attracted much attention from biomedical scientists
or clinicians, chiey because whitlockite is not visible with the stains used to routinely
examine microscopic sections of healthy or diseased tissue. However, the presence of
whitlockite does become obvious when X-ray diffraction is used to examine these same
sections. In part, whitlockite occurs commonly in biologic systems because of the high
concentrations of proteolipids and divalent cations in biologic uids. Formation of this
type of whitlockite is magnesium rich, and is preferred at temperatures typical of biologic
systems because of the smaller diameter of the magnesium ion compared to calcium.

Bioactive or Surface-Reactive
Ceramics
Upon implantation in the host, surface
reactive ceramics form strong bonds with
adjacent tissue. Examples of surface
reactive ceramics are dense nonporous
glasses, Bioglass and Ceravital, and
hydroxyapatites. One of their many uses
is the coating of metal prostheses. This
coating provides a stronger bonding to
the adjacent tissues, which is very
important for prostheses.

Glass Ceramics
Glass ceramics are polycrystalline
ceramics made by controlled
crystallization of glasses .
The formation of glass ceramics is
inuenced by the nucleation and growth
of small (<1 m diameter) crystals as well
as the size distribution of these crystals. It
is estimated that about 10 12 to 10 15
nuclei per cubic centimeter are required to
achieve such small crystals.

Glass Ceramics

The glass ceramics developed for implantation are SiO2

-CaO-Na2O-P2O 5 and Li 2O-ZnO-SiO2 systems. The bonding
to bone is related to the simultaneous formation of a
calcium phosphate and SiO 2 -rich lm layer on the surface,
as exhibited by the 46S5.2 type Bioglass.

Glass Ceramics
Glass ceramics have several desirable properties compared to
glasses and ceramics. The thermal coefcient of expansion is
very low, typically 10 7 to 10 5 C 1 , and in some cases it can
even be made negative. Due to the controlled grain size and
improved resistance to surface damage, the tensile strength of these
materials can be increased by at least a factor of two, from about
100 to 200 MPa. The resistance to scratching and abrasion of glass
ceramics is similar to that of sapphire .
A negative characteristic of the glass ceramic is its brittleness. In
addition, limitations on the compositions used for producing a
biocompatibile (or osteoconductive) glass ceramic hinders the
production of a glass ceramic which has substantially higher
mechanical strength. Thus glass ceramics cannot be used for
making major load-bearing implants such as joint implants. However,
they can be used as llers for bone cement, dental restorative
composites, and coating material.