CERAMIC BIOMATERIALS

Ceramics
Ceramics are refractory polycrystalline compounds;
 Inorganic
 Hard and brittle
 High compressive strength
Applications:
 Orthopaedic load-bearing coatings
 Dental implants
 Bone graft substitutes
 Bone cements
 The class of ceramics used for repair and replacement of diseased and damaged
parts of the musculoskeletal system are usually referred to as bioceramics.
 Ceramics are refractory polycrystalline compounds ;
 Usually inorganic
 Highly inert
 Hard and brittle
 High compressive strength
 Generally good electric and thermal insulators
 Good aesthetic appearance
Advantages and Disadvantges of
Bioceramics
Advantages Disadvantages
 Biocompactible  Low Tensile Strength
 Wear Resistant  Difficult to Fabricate
 Light Weight  Low Toughness
 Not Resilient
Types of Bioceramics

Bioinert
Bioactive/Surface active
Bioresorbable
Ceramics used in Biomedical Application
Carbon

Properties

 Inert ceramic materials

 Carbon has good biocompatibility with one and other tissues

 Carbon does not provoke an inflammatory response in

adjacent tissues and no foreign body reactions

 It has high strength and an elastic modulus Carbonaceous

ceramic material do not suffer from fatigue
 Mechanical Properties of Carbon

Properties Graphite Glassy Pyrolytic

Density (g/ml) 1.5-1.9 1.5 1.5-2.0

Elastic modulus (GPa) 24 24 28

Compressive strength (MPa) 138 172 517

 Graphite:
 Turbo static carbon, there are two types of bonding.

 The type that binds the atom within the hexagonal layers is
predominantly of covalent type.

 The type of bonding is very strong and is responsible for the

high strength of the material.

 The other type of bonding, which binds the parallel layers

together in crystallites of carbon, is basically a Vander Walls
interaction.

 The weak bonding causes low stiffness of carbon

Pyrolytic carbons (PC):

 formed by deposition of the isotropic structure on a substrate

while in fluidized bed at controlled temperature between 1000-
2400ºC.

 Pyrolysis of a hydrocarbon gas (e.g. methane) occurs at a

temperature of less than 1500ºC. They are called low
temperature isotropic carbon (LTI) carbons
Vitreous carbons:

Vitreous carbon gets its name from its glassy

black appearance.

It is polycrystalline solid with a very small

grain size, formed by the controlled
pyrolysis of a polymer such as phenol
formaldehyde resin, rayon and
polyacrylonitrile.
Biomedical applications:
 Carbon coatings find wide applications in heart valves,
blood vessel grafts, percutaneous devices because of
exceptional compatibility with soft tissues and blood.

 Percutaneous carbon devices containing high density

electrical connectors have been used for the chronic
stimulation of the cochlea for artificial hearing and
stimulation of the visual cortex to aid the blind

 LTI carbons deposited on preformed graphite substrates or

metal implants is used in restorative dentistry
Alumina (Al2O3)

 The main source of high purity of alumina is bauxite.

 The commonly available alumina (α-alumina) can be
prepared by calcining alumina trihydrate.
 As per ASTM specification, alumina for implant use
should contain 99.05% pure alumina and less than 0.1%
combined SiO2 and alkali oxides (Na2O).
 Alpha alumina has a rhombohedral structure. Natural
alumina is known as sapphire or ruby (based on
impurities)
Alumina
 Single crystal alumina can be made by feeding fine
alumina powders on to the surface of a seed crystal
which is slowly withdrawn from an electric arc as the
fused powder build up.

 The strength of polycrystalline alumina depends on its

grain size and porosity. The smaller the grains lower the
porosity and the higher the strength.

 The implant devices are prepared from purified alumina

powder by isostatic pressing and subsequent firing at
1500-1700ºC.
Properties of Alumina
 It has wear corrosion and wear resistance
 Good biocompatibility
 Reasonable strength
 Not cytotoxic
 Do not show inflammatory or progressive fibrotic reaction

Types
 Calcined alumina: calcination of aluminium trihydrate

 Tabular alumina: massive low shrinkage form that has been

sintered without adding permanent binders
Applications
 High density alumina is used in load bearing hip
prosthesis and dental implants because of its
combination of excellent corrosion resistance, good
biocompatibility, high wear resistance and reasonable
strength.
 Orthopedic uses of alumina consist of hip and knee
joints, tibial plate, femur shaft, shoulders, vertebra, leg
lengthening spacer and ankle joint prosthesis
 Alumina finds applications in dentistry as well as in a
reconstructive maxillofacial surgery to cover bone
defects
Zirconia (ZrO2)
 Pure zirconia can be obtained from of zircon (ZrSiO4)

 At room temperature zirconia maintains crystal structure.

Upon heating, it transforms to a tetragonal phase at
1000-1100ºC and cubic phase around 2000ºC.

 Yttria oxide stabilizes the tetragonal phase so that upon

cooling the tetragonal crystals made of ZrO2-Yr2O3, can
be maintained

 Zirconia has high melting temperature (Tm=2953K),

harder than alumina
Zirconia

Applications

 Improved mechanical properties of Yttria stabilized

zirconia combined excellent biocompatibility and wear
properties make this suitable for orthopedic prosthesis
design

 Hydroxyapatite coated zirconia dental implants are also

in use.
 Bioactive /surface reactive ceramics
 The main objective of this type of ceramics is to achieve a controlled surface
reactivity that will induce a direct chemical bond between the implant and
the surrounding tissues. Examples of surface reactive ceramics are
nonporous glasses, bioglass and ceravital.
 One of their many uses is the coating of metal prosthesis.

Uses of surface reactive bioceramics

 For coating of metal prosthesis
 In reconstruction of dental defects
 For correcting periodontal defects
 In replacing subperiosteal defects
 As replacement of middle ear ossicles
 For filling space vacated by bone screws, donor bone, excised tumours
 Glass ceramics
 Glass ceramics are polycrystalline ceramics made by controlled crystallization of glasses

 Glass ceramics are manufactured by controlled nucleation and growth of crystals of

small (<1µm diameter) size. It is estimated that about 1012-1015 nuclei/cc are required to
achieve such small crystals

 In addition to the metals of Pt groups, metal oxides such as TiO2, ZrO2 and P2O5 are widely
used for nucleation

 The nucleation of glass is carried out at temperature much lower than the melting
temperature.
 The mixture is melted in a platinum crucible at 1500ºC for 3 hours, annealed and cooled.
The nucleation and crystallization temperatures are 680 and 750ºC respectively each of
24hours

 The crystallization is usually more than 90% complete when grain sizes are between 0.1
and 1µm.
 The glass ceramics developed for implantation are SiO2-CaO-Na2O-P2O5 system
Ceravital

 The composition of ceravital is similar to that of Bioglass

in SiO2 but differ somewhat in other components

 In order to control the dissolution rate Al2O3, TiO2 and

Ta2O5 re added in ceravital glass ceramics
Biodegradable or resorbable ceramics
 Resorbable ceramics degrade upon implantation in the host.
 The rate of degradation varies from material to material.
 Almost all bioresorbable ceramics except biocoral and plaster
of paris (calcium sulphate dehydrate) are variations of calcium
phosphate.

Use of bio-resorbable ceramics

 As drug delivery device
 For repairing bone damage due to disease or trauma
 For filling space vacated by one screws, donor bone, excised
tumors and diseased bone loss
 For repairing maxillofacial and dental defects
Calcium phosphate
 Used in the form of artificial bone. This can be synthesized and can be used for
manufacturing various forms of implants as well as solid or porous coating on other
materials
 Calcium phosphate can be crystallized into salts such as hydroxyapatite and β-
whitelockite depending on the Ca: P ratio, presence of water, impurities and
temperature.

 In wet condition, low temperature (<900ºC) hydroxyapatite will form

 In dry environment, higher temperature  β-whitelockite will form

 Both hydroxyapatite and β-whitelockite are highly tissue compatible and are used as
bone substitutes in granular form or solid block.
 The apatite form of calcium phosphate is considered to be closely related to the
mineral phase of bone and teeth.

 The mineral part of bone and teeth is made of a crystalline form of calcium
phosphate similar to hydroxyapatite (HAP) [Ca10 (PO4)6(OH) 2]
 Hydroxyapatite (HAP)
 HAP has osteoinductive property
 Releases PO4= and Ca2+ ion in vivo
 Amorphous in nature
 Ca:P ratio of HAP is 10:6 and the calculated density 3.219gm/cc
 The mechanical properties of synthetic calcium phosphates vary
considerably. These variations in properties are due to the variation in
structure and manufacturing process.
 Depending on the final firing condition the calcium phosphate can
be hydroxyapatite or β-whitelockite.
 However, in many instances, both types of structure exist in the same
final product.
 Hydroxyapatite appears to form a direct chemical bond with hard
tissue. Upon implantation of hydroxyapatite particles or porous blocks
in bone, new cancellous bone forms within 4-8 weeks.
Manufacturing process (HAP)
Process1/ Chemical synthesis
 0.6M H3PO3 aqueous
solution+1 M Ca(OH)2
aqueous solution
 Sintered at 40ºC
 Gelatinous precipitate
 Rest it for 10days at 40ºC
 Mature grain
 Filtered
 Pasty cake formed –dried at
110ºC and then dehydrated at
250ºC
 Ground to powder
 Calcined at 900ºC
Process3/ Using (NH4) HPO4 and Ca(OH)2 by
microwave heating
 0.24M (NH4)HPO4 + 0.4 M
Ca(OH)2
 Stirred at pH 10
 Suspension formed
 Irradiated in microwave for 20
minutes
 Gel formed
 Calcined at 1100ºC for 1 hours
 Solid mass
 Treated with ball mill to make
fine powder
Process 3/ From mammalian bone:
Cleaned bone
Refluxed with 5% KOH for 16-18 hours
Add dilute HCl
Dried for 1/2 hour
Initially sintered at 800ºC
Sintered at 1100ºC for 5-6 hours
Aluminium calcium phosphate (ALCAP)
ceramics
 ALCAP has dielectric properties but no magnetic or piezoelectric properties.
 ALCAP ceramics are unique because they provide a multipurpose
crystallographic system where one phase of the ceramic on implantation can
be more rapidly resorbed than others.
 ALCAP is prepared from stock powder of aluminium oxide, calcium oxide and
phosphorus pentoxide.
 A ratio 50:30:16 by weight of AlO2:CaO: P2O5 is used to obtain the starting
mixture
 Calcined at 1350ºC in high temperature for 12 hours
 Calcined material is ignored in a ball mill and sieved by an automatic siever to
obtain particles of the desired size.
 The particulate powder is then pressed into solid blocks or hollow cylinders and
sintered at 1400ºC for 36 hours to increase the mechanical strength.
 ALCAP implants have given excellent results in terms of biocompatibility and
gradual replacement of the ceramic materials with endogenous bone.
 Tricalcium phosphate (TCP)
 A multicrystalline porous form of β-tricalcium phosphate [β-Ca3 (PO4)2] has been
used successfully to correct periodontal defects and augment bony contours.
 TCP degrades faster than calcium phosphate

Preparation of β-TCP
 It is prepared by wet precipitation procedure from an aqueous solution of
Ca(NO3)2 and NaH2PO4
 The precipitate is calcined at 1150ºCfor 1 hour, ground and sieved to obtain the
desired particles for use as bone substitutes.
 TCP is usually more soluble than synthetic hydroxyapatite and upon implantation,
allows good bone growth and eventually replaced by endogenous bone.