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GOOD MORNING
IMPLANT biomaterials
CONTENTS
• Introduction
• Terminologies
• History
• Classification of biomaterials
• Biocompatibility
• Biofunctionability
• Individual materials
– Metals and alloys
– Ceramics and carbon
– Polymers and composite polymers
• Surface modifications
• Conclusion
• References
• For many years, implants of varied
types have been used in dentistry to
augment or replace hard and soft tissue
components of the jaws. Currently,
implant materials include grade 2
commercially pure titanium, titanium
6% aluminium 4% vanadium, surgical-
grade cobalt-chromium-molybdenum,
aluminium oxide in single crystal or
polycrystalline form, hydroxyapatite,
tricalcium phosphate and calcium
aluminate.
• Biocompatibility – (Dorlands illustrated medical dictionary)
Being harmonious with life and not having toxic or injurious
effects on biofunction.
• Biomaterial – Any substance other than drug that can be
used for any period as a part of a system that treats,
augments or replaces any tissue, organ or function of the
body.
• Biotolerant – Material that is not necessairly rejected but are
surrounded by fibrous layer in the form of a capsule .
TERMINOLOGIES:
• Bio inert – Material that allow close apposition of bone on their
surface
• Bioactive - Materials that allow formation of new bone on their
surface and ion exchange with host tissue
• Osteoconductive – the materials that forms scaffolding that allows
the formation of bone
• Osteoinductive – materials that have capacity to induce bone
formation.
• 2500 BC - Ancient
Egyptians - gold ligature
• 500 BC - Etruscan
population - gold bands
incorporating pontics
• 500 BC - Phoenician
population - gold wire
• 300 BC - Phoenician
population - Carved
Ivory teeth
• 600 AD - Mayan
population -
implantation of pieces of
shell
• 18 th century Pierre
Fauchard and John
Hunter - transplanting
the teeth
1913 - Greenfield –
24 gauge iridium platinum
wire meshwork forming
“basket” implant soldered
with 24 carat gold
•1940 - Formiggini - spiral
implant - stainless steel
wire
• 1937 – Venable et al-
vitallium screw to
provide anchorage for
replacement
1943 - Dahl -Subperiosteal
type of implant
1948 - Goldberg and
Gershkoff - Extension of
frame work
• Early 1960s - Chercheve
- Double helical Spiral
implant of Cobalt
Chromium
• Early 1970s - Grenoble -
Vitreous Carbon
implants
• 1970 and 1980 - Weiss
and Judy - Titanium
Mushroom shaped
projection (INPLANT)
After 1980s –hollow basket Core vent implant
Screw vent implant
Screw vent implant with hydroxyapatite coating
implant with titanum plasma spray
Biological
biocompatibility
Chemical composition
Metals Ceramics Polymers
Biotolerant Gold Polyethylene
Cobalt-chromium
alloys
Polyamide
Stainless steel Polymethylmethacrylate
Zirconium Polytetrafluoroethylene
Niobium Polyurethane
Tantalum
Bioinert Commercially
pure titanium
Aluminium
oxide
Titanium alloy (Ti-
6Al-4V)
Zirconium oxide
BioactiveBioactive HydroxyapatiteHydroxyapatite
TricalciumTricalcium
phosphatephosphate
CalciumCalcium
pyrophosphatepyrophosphate
FluorapatiteFluorapatite
Carbon silicon
BioglassBioglass
Classification based on implant design:
1. Sub periosteial
1. Unilateral
2. Bilateral
2. Transosteal (or) Staple bone implant (or) Mandibular staple
implant (or) Trans mandibular implant
3. Endosteal implant
1. Cylindrical cones (or) thin plates
2. Blade implant
3. Ramus frame implant
4. Root form implant
4. Epithelial implant (or) Sub dermal implant (or) intra mucosal
implant.
BIOCOMPATIBILITY
 Corrosion resistance
 Cytotoxicity of corrosion products
 Metal contamination
Corrosion – It is defined as loss of metallic ions from the
surface of the metal to the surrounding environment
Types of corrosion :
General Galvanic
Pitting Fretting
Crevice Stress corrosion cracking
Williams DF
Williams suggested that three types of corrosion were most
relevant to dental implants:
• Stress corrosion cracking
• Galvanic corrosion
• Fretting corrosion
Stress corrosion cracking (SCC)
The combination of high magnitudes
of applied mechanical stress plus
simultaneous exposure to a corrosive
environment can result in the failure
of metal materials by cracking, where
neither condition alone would cause
the failure.
William presented this phenomenon of
SCC in multicomponent orthopedic
implants.
Lemons et al
Hypothesized that it may be
responsible for some implant
failures in view of high
concentrations of forces in the area
of the abutment-to-implant body
interface.
Most traditional implant body
designs under three-dimensional
finite element stress analysis
show a concentration of stresses
at the crest of the bone support
and cervical one-third of the
implant.
• This tends to support
potential SCC at the implant
interface area (i.e. a
transition zone for altered
chemical and mechanical
environmental conditions).
• This has also been described
in terms of corrosion fatigue
(i.e., cyclic load cycle
failures accelerated by
locally aggressive medium).
Stress Corrosion Cracking
Galvanic corrosion (GC)
GC occurs when two
dissimilar metallic
materials are in contact
and are within an common
electrolyte medium,
resulting in current to flow
between the two.
The metallic materials with the
dissimilar potentials can have
their corrosion currents altered,
thereby resulting in a greater
corrosion rate..
Galvanic Corrosion
Fretting corrosion (FC)
FC occurs when there
is a micromotion and
rubbing contact within a
corrosive environment
such as the perforation of
the passive layers and
shear-directed loading
along adjacent contact
surface.
Normally, the passive oxide layers on metallic
substrates dissolve at such slower rates that the resultant
loss of mass is of no mechanical consequence to the
implants.
A more critical problem is
irreversible local perforation
of the passive layer that is
often caused by chloride
ions, which may result in
localized pitting corrosion.
Pitting Corrosion
PROTECTION AGAINST CORROSION
•Passivation
•Increasing the noble metal content
•Polishing the surface
•Avoid dissimilar metal contact
CYTOTOXICITY OF CORROSION PRODUCTS
The material should undergo only minimal amount of
biochemical changes during service.
The material should have minimal reaction with the surrounding
bone and the soft tissue
Ideally the corrosion products should not produce any toxicity
to the local and systemic environment.
METAL CONTAMINATION
Two different metals in the saline solutions or body fluids may result
in a localized difference of electrochemical potential and cause
galvanic corrosion. So the instruments that contact titanium implant
during insertion procedures either be solid titanium, titanium tipped
or treated to prevent metallic transfer.
During storage, sterilization and surgical set up no other type of
metal should contact the implant surface.
PHYSICAL AND MECHANICAL PROPERTIES
• The macroscopic distribution of mechanical stress and strain is
predominantly controlled by the shape and form of the implant.
• The microscopic distribution is controlled by the basic properties of
biomaterials as -Surface chemistry, Microtopography, Modulus of
elasticity and Surface attachment to the adjacent tissue.
• Basic problem lies due to the difference in mechanical
strength and deformability of the material and the
recipient bone.
• The metals can be modified to achieve the required
properties by work hardening or alloying.
• Higher the applied load higher the mechanical
stress greater the possibility of exceeding the fatigue
limit of the material..
MODULUS OF ELASTICITY
• the forces applied on the implant leads to stresses within the bone.
• When the applied forces are equal to stresses it acquires the state of
static equilibrium.
• Forces > , it leads to deformation.
• The physiologic importance of modulus of elasticity of biomaterial
is related to the modulus of elasticity of the bone.
• The degree of relative movement at the interface determines the
health or pathologic state of interface.
• The modulus of elasticity of titanium is very near to
bone compared to any other material used. It is almost 6
times more stiff than dense cortical bone.
• The carbon implants has compatible stiffness with bone
but fail to have adequate strength to withstand
physiologic load leading to microcracks and finally the
failure of implant.
• On the other hand the aluminum oxide ceramic implant
has high ultimate strength but the stiffness is 33 times
greater than the stiffness of the bone which results in
apparent stress shielding of interfacial bone
•The modulus of elasticity in
subperiosteal implants not an important
consideration. The envelopment of the
implant in the outer layer of periosteum
during healing provides a stable
biomechanical situation.
•For unilateral subperiosteal implant the
effect of relative movement of metal is
minimal.
•For bilateral/total subperiosteal implant
may cause excessive relative movement
due to its rigidity. So cutting these at the
midline or providing individual abutment
can increase flexibility.
METALS
Most of the materials used for implants are constructed from metals
and their alloys. These includes Titanium, Tantalum, Aluminum,
Vanadium, Cobalt, Chromium, Nickel and Molybdenum. These
are selected on the basis of their over all strength. Less frequently
used are precious metals as Gold and Platinum.
TITANIUM AND TITANIUM ALLOYS
• In 1791 Wilheim Gregor – Discovered in Black Magnetic Sand at
Cornwall.
• In 1925 Van Arkel.– Refined into pure form with desirable
properties.
• It is extremely reactive and forms tenacious oxide layer that
contribute to its elctrochemical passivity
Uses:
• Pigment industries
• Titanium tennis rackets
• Eyeglass frames
• Largely used in jet engines,
• Fracture site fixation
• Deep well drilling
• Nuclear waste management
• Dental and maxillofacial implants
 Titanium alloys can be classified as alpha, beta, and alpha beta
alloys.
Alpha alloy
 Highest strength, best corrosion resistance, pure titanium, small
amounts of nitrogen and oxygen (CpT1). Aluminium is
stabilizer
Beta alloy
 Difficult to manufacture (vanadium + aluminium) not used for
implant. Vanadium act as stabilizer
Alpha beta alloys
Most common alloys consisting of 6% of aluminium 4% of
vanadium (T1 & Al64Va)
 Good Corrosion resistance
properties
 Material of choice because of inert, bio compatible nature with
excellent resistant corrosion.
 Density 4.5 gm/cm2  40 % lighter than steel
 High heat resistance
 High strength compatible with S.S
 Able to maintain fine balance between sufficient strength to
resist # under occlusal forces and lower modulus of elasticity
for a more uniform stress distribution across the bone implant
interface.
 Titanium – more ductility than titanium alloy
 High dielectric property osseointegration.
Disadvantages
• Its high cost (although the cost has been reduced over the
past few years).
• Titanium is difficult and dangerous to cast. The metal
forms oxides so rapidly that an explosive reaction may
occur.
(So it is used either in machined or plastic form)
Ti Ore (Carbon and Chlorine)
Heated
TiCl
Reduced in presence
of molten Na
Ti Sponge
Fused under Vacuum
Ti Ingots
PRODUCTION
MACHINING &
AUTOCLAVING
Oxide Coatings
• The biocompatibilty of the Ti and Ti alloy is attributed to the ability
of formation of passive tenacious surface oxide.
• Minimum of 85 to 95% of pure titanium is required to maintain
passivity.
• The pure titanium theoretically may form several oxides as TiO, Ti
O2,Ti2O3
• Within a millisecond 10Å thick oxide layer will be formed.
In a minute the layer will become 100Å thick.
• The repair of the oxide layer is instantaneous if any
damage occurs during insertion of Implant.
• Rate of dissolution is extremely low compared to any
implant metals.
Original Branemark
fixture
Titanium screw
Cp Ti screw
implant
Cobalt Chromium Molybdenum Alloy
• These alloys are most often
used in cast-and-annealed
metallurgic condition.
• This clears that the alloy is
used for fabrication of
implants as custom designs
such as subperiosteal
implants.
The various constituents of alloy with their function-
• 63% Co- provides the continuous phase for basic
properties
• C- provides strength, surface abrasion resistance,
controls mechanical properties.
• 30% Cr- provides corrosion resistance through the
oxide surface
• 5% Mo- provides strength & bulk corrosion
resistance.
• Ni- found in traces.
• High modulus (stiffness) and Low ductility.
• Outstanding resistance to corrosion
• Excellent biocompatibility
Precautions
As cast cobalt alloys are the least ductile of the alloy systems
used for dental surgical implants, and bending of finished
implants should be avoided.
Iron – Chromium – Nickel based Alloys
• Surface is passivated to increase biocorrosion resistance.
• High strength and ductility.
• Used in wrought and heat treated condition.
Composition (Surgical austenitic steel)
– 18% chromium – for corrosion resistance.
– 8% nickel – to stabilize austentic structure.
– 0.5% carbon – as hardner.
Precautions
• Contraindicated in patients sensitive to nickel.
• Most susceptible to crevice and pitting corrosion, so care to be
taken to preserve passivated surface.
• Has galvanic potential, so avoid contact with dissimilar metal.
OTHER METALS AND ALLOYS
• Early spirals and cages included tantalum,
platinum, iridium, gold, palladium, and
alloys of these metals.
• More recently, devices made from
zirconium, hafnium, tungsten and sapphire
have been evaluated.
Ceramics and Carbon as implant
Materials
CERAMICS – these are non organic, non metallic, non polymeric
materials manufactured by compacting and sintering at elevated
temperatures.
• Have low ductility and inherent brittleness are their limitations
can be Classified into
Bio active – Ca3(PO4), Hydroxyapatite, tri calcium phosphate
Bio nonreactive – Aluminum Titanium Zirconium oxides
Aluminum Titanium Zirconium Oxides
• Used for endosteal root form, plate form
implants
• Have clear white cream or light grey
color so used for anterior root form
• Minimal biodegradation
• High modulus of elasticity
• Low fracture resistance
• Exhibit direct interface with bone
THE TÜBINGEN IMPLANT OF ALUMINUM OXIDE HAS
SPECIFIC MICRO-IRREGULARITIES ON THE SURFACE,
CLAIMED TO ALLOW BONE INGROWTH.
DISADVANTAGES
• Exposure to steam sterilization results in measurable
decrease in strength of some ceramics
• So dry heat sterilization is recommended
• Scratches or notches may induce fracture initiating sites
• Although initial testing showed adequate mechanical
strengths long term clinical results clearly demonstrate a
functional design and material related limitations.
Bioactive and Biodegradable Ceramics
Calcium Phosphate Ceramics
• The compositions was relatively similar to bone Ca5(PO4)3OH
• Color similar to bone
• Shows good bonding with bone so it can be used when structural support is
required under high magnitude loading
• It is used as a coating over the metallic implants
• Modulus of elasticity is very near to bone
DISADVANTAGES
• Low mechanical tensile and shear strengths under fatigue
loading
• Low attachment strength on some substrates
• Variable solubility depending on the product and their
clinical applications
HYDROXYAPATITE
• When the calcium and phosphorus in the ratio of 1.5 to 1.7 are
sintered in water containing atmosphere at 1200ºC to 1300ºC a
crystallographic end product will be obtained that is
Hydroxyapatite.
• This has osseoconductive effect when comes in contact with
bone.
• Hydroxyapatite is non porous with angular or spherical shape
particles that are examples of crystalline high pure
hydroxyapatite.
• Their compressive strength is 500 Mpa and tensile strength is 50-
70 Mpa.
PROPERTIES OF BIOACTIVE CERAMICS
Forms, Microstructure and Mechanical Properties
• Dense polycrystalline ceramics with small crystallites have higher
mechanical strength
• These ceramics are widely used as coatings on metallic implant
substrates
• Calcium phosphate ceramics have become a routine use by plasma
spray technique
• This technique increases the surface area which in turn increases the
osseointegration.
Density, Conductivity and Solubility
• Density of the material increases as the percentage of crystallinity
increases
• As the density / crystallinity increases the solubility decreases
• The solubility also depends on the surface area
• The amorphous products are more slouble because they have less
organized atomic structure
• These are susceptible to enzyme or cell mediated breakdown in the
same way of that of living bone.
• Thse are non conductors of heat and elecctricity.
• The Ceramic implant surface responds to the local Ph changes by
releasing Na,Ca,P&Si ions in exchange for H2 ions.
• Si reacts with O2 to form Silica gel
• As the concentration of phosphorus and calcium increases at the
surface they combine to form calcium phosphate rich layer and the
collagen fibers become incorporated into it.
• This way the functional integration with bone occurs with the help
of natural bone cementing substance so the bond formed is strong.
TISSUE RESPONSE
CARBON AND CARBON SILICON
COMPOUNDS
• Extensive applications for
cardiovascular devices.
• Excellent Biocompatibility
profiles and Moduli of
elasticity close to that of bone.
ADVANTAGES
• Tissue attachment
• Thermal and electrical insulation
• Color control.
• Provides opportunities for attachment of active
biomolecules
LIMITATIONS
• Poor Mechanical strength.
• Time dependent changes in the physical characteristics.
• Biodegradation could adversely affect Stability.
• Minimal resistance to scratching or scraping.
POLYMERS AND COMPOSITES
• These can be designed to match tissue properties and can be
fabricated at relatively low cost.
• These include polytetraflouroethylene (PTFE),
polyethyleneterephthalate (PET), polymethylmethacrylate
(PMMA), polypropylene (PP), polysulfone (PSF), silicon
rubber (SR)
Properties
• Polymers have low strengths and elastic moduli and higher
elongation to fracture compared with other class of
biomaterials.
• Thermal and electric insulators
• Relatively resistant to biodegradation compared to bone
• Most uses have been for internal force distribution
connectors intended to better simulate biomechanical
conditions for normal tooth functions
• Some are porous where as others are constituted as solid
structural forms
DISADVANTAGES
• Sensitive to sterilization and handling techniques.
• Electrostatic surface properties and tend to gather dust or other
particulate if exposed to semiclean oral environments
• Cleaning the contaminated porous polymers is not possible
without a laboratory environment
• So the talc on the gloves or contact with towel or gauze pad or
any such contamination must be avoided.
Types of Surface Roughness
1) Macrosurface Roughness.
SURFACE TOPOGRAPHY
Surface topography relates to the degree of roughness of
the surface and the orientation of surface irregularities.
Screw
Hollow basket
Core vent
2) Microsurface Roughness.
a) Abraded
TiO2
Al203
b) Acid Etched
HCl
H2SO4
c) Coating
TPS
HA
ADVANTAGES OF INCREASED
SURFACE ROUGHNESS
1) Increased surface areas of the implant adjacent to bone.
2) Improved cell attachment to the bone.
3) Increased bone present at implant surface.
4) Increased biomechanical interaction of the implant with bone.
Blasting with particles of various diameters is one of
the frequently used method of surface alteration.
In this approach, the implant surface is bombarded
with particles of aluminum oxide (Al2O3) or titanium oxide
(TiO2), and by abrasion, a rough surface is produced with
irregular pits and depressions.
BLASTING
Roughness depends on
particle size, time of blasting,
pressure, and distance from the
source of particles to the implant
surface.
Blasting a smooth Ti surface
with Al2 O3 particles of 25 µm, 75
µm, or 250 µm produces surfaces
with roughness values of 1.16 to
1.20, 1.43, and 1.94 to 2.20,
respectively.
SAND BLASTED IMPLANT
SAND BLASTED AND ACID
ETCHED IMPLANT
Laser Induced Surface Roughening
Eximer laser – “Used to create roughness”
Regularly oriented surface roughness configuration
compared to TPS coating and sandblasting
SEM x 300
SEM x 300SEM x 70
Chemical etching is another process by which surface
roughness can be increased.
The metallic implant is immersed into an acidic solution,
which erodes its surface, creating pits of specific dimensions and
shape.
Concentration of the acidic solution, time, and
temperature are factors determining the result of chemical attack
and microstructure of the surface.
CHEMICAL ETCHING
IRREGULAR SURFACE MORPHOLOGIES
Sandblasted specimen Specimen acid etched for 1
minute.
Specimen acid etched for 5
minutes.
Specimen acid etched for 10
minutes.
Recently, a new surface was introduced that was sandblasted
with large grit and acid-etched (SLA, Straumann).
This surface is produced by a large grit (250 to 500 µm)
blasting process, followed by etching with hydrochloric-sulfuric
acid.
The average ra for the acid-etched surface is 1.3 µm, and the
sandblasted and acid-etched surface, ra=2.0 µm.
SANDBLASTED AND ACID ETCHED
(SLA)
Sand blasting Acid etch
The objective
Sand blasting – surface roughness
(substractive method)
Acid etching – cleaning
SEM 1000X SEM 7000X
Lima YG et al (2000), Orsini Z et al
(2000).
- Acid etching with NaOH, Aq.
Nitric acid, hydrofluoric acid.
Decrease in contact angle by 100
–
better cell attachment.
increase in osseointegration by
removal of aluminium particles
(cleaning).
Wennerberg et al 1996. superior bone fixation and bone adaptation
Porous sintered surfaces are produced when spherical
powders of metallic or ceramic material becomes a coherent mass
with the metallic core of the implant body.
Lack of sharp edges is what distinguishes these from rough
surfaces.
Porous surfaces are characterized by pore size, pore shape,
pore volume, and pore depth, which are affected by the size of
spherical particles and the temperature and pressure conditions of the
sintering chamber.
POROUS
POROUS SURFACE: ADVANTAGES
1. A secure, 3-D interlocking interface with bone.
2. Predictable and minimal crestal bone remodelling.
3. Greater surgical options with shorter implant lengths.
4. Shorter initial healing times and
5. Porous coating implants provide the space, volume for cell
migration and attachment, thus support contact osteogenesis.
SURFACE OF A POROUS
TITANIUM ALLOY IMPLANT
FIBROBLASTS CULTURED
FOR 24 HOURS ON THE
SURFACE OF A POROUS
TITANIUM ALLOY
IMPLANT.
TITANIUM PLASMA SPRAYED
Titanium Plasma Sprayed Coating (TPS)
 Steinemann 1988,
Tetsch 1991- 6-10
times increase surface
area.
Roughness Depth profile of about 15µm
SURFACE OF A TITANIUM PLASMA-SPRAYED
IMPLANT. (SEM, MAGNIFICATION 5,000 X).
HYDROXYAPATITE COATINGS
HA coated implant bioactive
surface structure – more rapid
osseous healing comparison
with smooth surface implant.
↓
Increased initial stability
Can be Indicated
- Greater bone to implant
contact area
- Fresh extraction sites
- Newly grafted sites
SEM 100X
• Hydroxyapatite([Ca10(PO4)6OH]2) coating was
brought to the dental profession by DeGroot
ADVANTAGES OF HA-COATINGS
1. HA coating can lower the corrosion rate of the same substrate
alloys.
2. HA coatings has been credited with enabling to obtain improved
bone to implant attachment compared with machined surface.
3. The bone adjacent to the implant has been reported to be better
organized than with other implant materials and with a higher
degree of mineralization.
CERAMIC AND CERAMIC COATED
IMPLANTS
Ceramic materials are used to coat metallic implants to
produce an ionic ceramic surface, which is thermodynamically
stable and hydrophilic, thereby producing a high strength
attachment to bone and surrounding tissues.
These ceramic can either be plasma sprayed or coated on
to the metal implant to produce bio-active surface.
Aluminum oxide (Al2O3) is
used as the gold standard for ceramic
implants because of its inertness with
no evidence of ion release or immune
reaction in vivo.
Zirconia (Zro2) has also demonstrated a high
degree of inertness.
THE TÜBINGEN IMPLANT OF ALUMINUM OXIDE HAS
SPECIFIC MICRO-IRREGULARITIES ON THE SURFACE,
CLAIMED TO ALLOW BONE INGROWTH.
OTHER SURFACE MODIFICATIONS
Surface modification methods include controlled chemical
reactions with nitrogen or other elements or surface ion implantation
procedures.
The reaction of nitrogen with "titanium alloys at elevated
temperatures results in titanium nitride compounds being formed along
the surface.
Electrochemically, the titanium nitrides are similar to the
oxides (TiO2), and no adverse electrochemical behavior has been noted
if the nitride is lost regionally.
The titanium substrate reoxidizes when the surface layer of
nitride is removed.
Doped surfaces that contain various types of bone growth factors
or other bone-stimulating agents may prove advantageous in
compromised bone beds. However, at present clinical
documentation of the efficacy of such surfaces is lacking : BMP =
Bone morphogenetic protein.
DOPED SURFACES
•The biomaterials discipline has evolved
significantly over the past decades, and
synthetic biomaterials are now constituted,
fabricated, and provided to health care
professionals as mechanically and chemically
clean devices that have a high predictability
of success when used appropriately within
the surgical disciplines
List of referencs
• Implant Dentistry -Carl E Misch.
• Principles and practice of implant dentistry -Charls M
Weiss, Adam Weiss.
• J Dent Edu 1988; 52: 815-820.
• Atlas of Oral implantology - A Norman Cranin.
• Sciences of dental materials - Anusavise.
• The BRANEMARK system of oral reconstruction - A
clinical atlas.
• DCNA 1986 ; 30 (1) 25-47
• IJOMI 2000 ;(15) 675-690
• D.C.N.A., 1992 ; 36, 1-17
• JPD, 1983 ; 50 : 108-113.
• JPD, 1983; 50:832-37.
• IJP, 1990 ; 3 : 30-41
implant  biomaterial

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implant biomaterial

  • 3. CONTENTS • Introduction • Terminologies • History • Classification of biomaterials • Biocompatibility • Biofunctionability • Individual materials – Metals and alloys – Ceramics and carbon – Polymers and composite polymers • Surface modifications • Conclusion • References
  • 4.
  • 5. • For many years, implants of varied types have been used in dentistry to augment or replace hard and soft tissue components of the jaws. Currently, implant materials include grade 2 commercially pure titanium, titanium 6% aluminium 4% vanadium, surgical- grade cobalt-chromium-molybdenum, aluminium oxide in single crystal or polycrystalline form, hydroxyapatite, tricalcium phosphate and calcium aluminate.
  • 6. • Biocompatibility – (Dorlands illustrated medical dictionary) Being harmonious with life and not having toxic or injurious effects on biofunction. • Biomaterial – Any substance other than drug that can be used for any period as a part of a system that treats, augments or replaces any tissue, organ or function of the body. • Biotolerant – Material that is not necessairly rejected but are surrounded by fibrous layer in the form of a capsule . TERMINOLOGIES:
  • 7. • Bio inert – Material that allow close apposition of bone on their surface • Bioactive - Materials that allow formation of new bone on their surface and ion exchange with host tissue • Osteoconductive – the materials that forms scaffolding that allows the formation of bone • Osteoinductive – materials that have capacity to induce bone formation.
  • 8.
  • 9. • 2500 BC - Ancient Egyptians - gold ligature • 500 BC - Etruscan population - gold bands incorporating pontics
  • 10. • 500 BC - Phoenician population - gold wire • 300 BC - Phoenician population - Carved Ivory teeth
  • 11. • 600 AD - Mayan population - implantation of pieces of shell • 18 th century Pierre Fauchard and John Hunter - transplanting the teeth
  • 12. 1913 - Greenfield – 24 gauge iridium platinum wire meshwork forming “basket” implant soldered with 24 carat gold •1940 - Formiggini - spiral implant - stainless steel wire
  • 13. • 1937 – Venable et al- vitallium screw to provide anchorage for replacement
  • 14. 1943 - Dahl -Subperiosteal type of implant 1948 - Goldberg and Gershkoff - Extension of frame work
  • 15. • Early 1960s - Chercheve - Double helical Spiral implant of Cobalt Chromium • Early 1970s - Grenoble - Vitreous Carbon implants
  • 16. • 1970 and 1980 - Weiss and Judy - Titanium Mushroom shaped projection (INPLANT)
  • 17. After 1980s –hollow basket Core vent implant Screw vent implant Screw vent implant with hydroxyapatite coating implant with titanum plasma spray
  • 18.
  • 19. Biological biocompatibility Chemical composition Metals Ceramics Polymers Biotolerant Gold Polyethylene Cobalt-chromium alloys Polyamide Stainless steel Polymethylmethacrylate Zirconium Polytetrafluoroethylene Niobium Polyurethane Tantalum Bioinert Commercially pure titanium Aluminium oxide Titanium alloy (Ti- 6Al-4V) Zirconium oxide BioactiveBioactive HydroxyapatiteHydroxyapatite TricalciumTricalcium phosphatephosphate CalciumCalcium pyrophosphatepyrophosphate FluorapatiteFluorapatite Carbon silicon BioglassBioglass
  • 20. Classification based on implant design: 1. Sub periosteial 1. Unilateral 2. Bilateral 2. Transosteal (or) Staple bone implant (or) Mandibular staple implant (or) Trans mandibular implant 3. Endosteal implant 1. Cylindrical cones (or) thin plates 2. Blade implant 3. Ramus frame implant 4. Root form implant 4. Epithelial implant (or) Sub dermal implant (or) intra mucosal implant.
  • 21.
  • 22.
  • 23. BIOCOMPATIBILITY  Corrosion resistance  Cytotoxicity of corrosion products  Metal contamination Corrosion – It is defined as loss of metallic ions from the surface of the metal to the surrounding environment Types of corrosion : General Galvanic Pitting Fretting Crevice Stress corrosion cracking
  • 24. Williams DF Williams suggested that three types of corrosion were most relevant to dental implants: • Stress corrosion cracking • Galvanic corrosion • Fretting corrosion
  • 25. Stress corrosion cracking (SCC) The combination of high magnitudes of applied mechanical stress plus simultaneous exposure to a corrosive environment can result in the failure of metal materials by cracking, where neither condition alone would cause the failure. William presented this phenomenon of SCC in multicomponent orthopedic implants.
  • 26. Lemons et al Hypothesized that it may be responsible for some implant failures in view of high concentrations of forces in the area of the abutment-to-implant body interface.
  • 27. Most traditional implant body designs under three-dimensional finite element stress analysis show a concentration of stresses at the crest of the bone support and cervical one-third of the implant.
  • 28. • This tends to support potential SCC at the implant interface area (i.e. a transition zone for altered chemical and mechanical environmental conditions). • This has also been described in terms of corrosion fatigue (i.e., cyclic load cycle failures accelerated by locally aggressive medium). Stress Corrosion Cracking
  • 29. Galvanic corrosion (GC) GC occurs when two dissimilar metallic materials are in contact and are within an common electrolyte medium, resulting in current to flow between the two.
  • 30. The metallic materials with the dissimilar potentials can have their corrosion currents altered, thereby resulting in a greater corrosion rate.. Galvanic Corrosion
  • 31. Fretting corrosion (FC) FC occurs when there is a micromotion and rubbing contact within a corrosive environment such as the perforation of the passive layers and shear-directed loading along adjacent contact surface.
  • 32. Normally, the passive oxide layers on metallic substrates dissolve at such slower rates that the resultant loss of mass is of no mechanical consequence to the implants.
  • 33. A more critical problem is irreversible local perforation of the passive layer that is often caused by chloride ions, which may result in localized pitting corrosion. Pitting Corrosion
  • 34. PROTECTION AGAINST CORROSION •Passivation •Increasing the noble metal content •Polishing the surface •Avoid dissimilar metal contact
  • 35. CYTOTOXICITY OF CORROSION PRODUCTS The material should undergo only minimal amount of biochemical changes during service. The material should have minimal reaction with the surrounding bone and the soft tissue Ideally the corrosion products should not produce any toxicity to the local and systemic environment.
  • 36. METAL CONTAMINATION Two different metals in the saline solutions or body fluids may result in a localized difference of electrochemical potential and cause galvanic corrosion. So the instruments that contact titanium implant during insertion procedures either be solid titanium, titanium tipped or treated to prevent metallic transfer. During storage, sterilization and surgical set up no other type of metal should contact the implant surface.
  • 37. PHYSICAL AND MECHANICAL PROPERTIES • The macroscopic distribution of mechanical stress and strain is predominantly controlled by the shape and form of the implant. • The microscopic distribution is controlled by the basic properties of biomaterials as -Surface chemistry, Microtopography, Modulus of elasticity and Surface attachment to the adjacent tissue.
  • 38. • Basic problem lies due to the difference in mechanical strength and deformability of the material and the recipient bone. • The metals can be modified to achieve the required properties by work hardening or alloying. • Higher the applied load higher the mechanical stress greater the possibility of exceeding the fatigue limit of the material..
  • 39. MODULUS OF ELASTICITY • the forces applied on the implant leads to stresses within the bone. • When the applied forces are equal to stresses it acquires the state of static equilibrium. • Forces > , it leads to deformation. • The physiologic importance of modulus of elasticity of biomaterial is related to the modulus of elasticity of the bone. • The degree of relative movement at the interface determines the health or pathologic state of interface.
  • 40.
  • 41. • The modulus of elasticity of titanium is very near to bone compared to any other material used. It is almost 6 times more stiff than dense cortical bone. • The carbon implants has compatible stiffness with bone but fail to have adequate strength to withstand physiologic load leading to microcracks and finally the failure of implant. • On the other hand the aluminum oxide ceramic implant has high ultimate strength but the stiffness is 33 times greater than the stiffness of the bone which results in apparent stress shielding of interfacial bone
  • 42. •The modulus of elasticity in subperiosteal implants not an important consideration. The envelopment of the implant in the outer layer of periosteum during healing provides a stable biomechanical situation. •For unilateral subperiosteal implant the effect of relative movement of metal is minimal. •For bilateral/total subperiosteal implant may cause excessive relative movement due to its rigidity. So cutting these at the midline or providing individual abutment can increase flexibility.
  • 43.
  • 44. METALS Most of the materials used for implants are constructed from metals and their alloys. These includes Titanium, Tantalum, Aluminum, Vanadium, Cobalt, Chromium, Nickel and Molybdenum. These are selected on the basis of their over all strength. Less frequently used are precious metals as Gold and Platinum.
  • 45. TITANIUM AND TITANIUM ALLOYS • In 1791 Wilheim Gregor – Discovered in Black Magnetic Sand at Cornwall. • In 1925 Van Arkel.– Refined into pure form with desirable properties. • It is extremely reactive and forms tenacious oxide layer that contribute to its elctrochemical passivity
  • 46. Uses: • Pigment industries • Titanium tennis rackets • Eyeglass frames • Largely used in jet engines, • Fracture site fixation • Deep well drilling • Nuclear waste management • Dental and maxillofacial implants
  • 47.  Titanium alloys can be classified as alpha, beta, and alpha beta alloys. Alpha alloy  Highest strength, best corrosion resistance, pure titanium, small amounts of nitrogen and oxygen (CpT1). Aluminium is stabilizer Beta alloy  Difficult to manufacture (vanadium + aluminium) not used for implant. Vanadium act as stabilizer Alpha beta alloys Most common alloys consisting of 6% of aluminium 4% of vanadium (T1 & Al64Va)  Good Corrosion resistance
  • 48. properties  Material of choice because of inert, bio compatible nature with excellent resistant corrosion.  Density 4.5 gm/cm2  40 % lighter than steel  High heat resistance  High strength compatible with S.S  Able to maintain fine balance between sufficient strength to resist # under occlusal forces and lower modulus of elasticity for a more uniform stress distribution across the bone implant interface.  Titanium – more ductility than titanium alloy  High dielectric property osseointegration.
  • 49. Disadvantages • Its high cost (although the cost has been reduced over the past few years). • Titanium is difficult and dangerous to cast. The metal forms oxides so rapidly that an explosive reaction may occur. (So it is used either in machined or plastic form)
  • 50. Ti Ore (Carbon and Chlorine) Heated TiCl Reduced in presence of molten Na Ti Sponge Fused under Vacuum Ti Ingots PRODUCTION MACHINING & AUTOCLAVING
  • 51. Oxide Coatings • The biocompatibilty of the Ti and Ti alloy is attributed to the ability of formation of passive tenacious surface oxide. • Minimum of 85 to 95% of pure titanium is required to maintain passivity. • The pure titanium theoretically may form several oxides as TiO, Ti O2,Ti2O3
  • 52. • Within a millisecond 10Å thick oxide layer will be formed. In a minute the layer will become 100Å thick. • The repair of the oxide layer is instantaneous if any damage occurs during insertion of Implant. • Rate of dissolution is extremely low compared to any implant metals.
  • 54. Cobalt Chromium Molybdenum Alloy • These alloys are most often used in cast-and-annealed metallurgic condition. • This clears that the alloy is used for fabrication of implants as custom designs such as subperiosteal implants.
  • 55. The various constituents of alloy with their function- • 63% Co- provides the continuous phase for basic properties • C- provides strength, surface abrasion resistance, controls mechanical properties. • 30% Cr- provides corrosion resistance through the oxide surface • 5% Mo- provides strength & bulk corrosion resistance. • Ni- found in traces.
  • 56. • High modulus (stiffness) and Low ductility. • Outstanding resistance to corrosion • Excellent biocompatibility Precautions As cast cobalt alloys are the least ductile of the alloy systems used for dental surgical implants, and bending of finished implants should be avoided.
  • 57. Iron – Chromium – Nickel based Alloys • Surface is passivated to increase biocorrosion resistance. • High strength and ductility. • Used in wrought and heat treated condition. Composition (Surgical austenitic steel) – 18% chromium – for corrosion resistance. – 8% nickel – to stabilize austentic structure. – 0.5% carbon – as hardner. Precautions • Contraindicated in patients sensitive to nickel. • Most susceptible to crevice and pitting corrosion, so care to be taken to preserve passivated surface. • Has galvanic potential, so avoid contact with dissimilar metal.
  • 58. OTHER METALS AND ALLOYS • Early spirals and cages included tantalum, platinum, iridium, gold, palladium, and alloys of these metals. • More recently, devices made from zirconium, hafnium, tungsten and sapphire have been evaluated.
  • 59. Ceramics and Carbon as implant Materials CERAMICS – these are non organic, non metallic, non polymeric materials manufactured by compacting and sintering at elevated temperatures.
  • 60. • Have low ductility and inherent brittleness are their limitations can be Classified into Bio active – Ca3(PO4), Hydroxyapatite, tri calcium phosphate Bio nonreactive – Aluminum Titanium Zirconium oxides
  • 61. Aluminum Titanium Zirconium Oxides • Used for endosteal root form, plate form implants • Have clear white cream or light grey color so used for anterior root form • Minimal biodegradation • High modulus of elasticity • Low fracture resistance • Exhibit direct interface with bone THE TÜBINGEN IMPLANT OF ALUMINUM OXIDE HAS SPECIFIC MICRO-IRREGULARITIES ON THE SURFACE, CLAIMED TO ALLOW BONE INGROWTH.
  • 62. DISADVANTAGES • Exposure to steam sterilization results in measurable decrease in strength of some ceramics • So dry heat sterilization is recommended • Scratches or notches may induce fracture initiating sites • Although initial testing showed adequate mechanical strengths long term clinical results clearly demonstrate a functional design and material related limitations.
  • 63. Bioactive and Biodegradable Ceramics Calcium Phosphate Ceramics • The compositions was relatively similar to bone Ca5(PO4)3OH • Color similar to bone • Shows good bonding with bone so it can be used when structural support is required under high magnitude loading • It is used as a coating over the metallic implants • Modulus of elasticity is very near to bone
  • 64. DISADVANTAGES • Low mechanical tensile and shear strengths under fatigue loading • Low attachment strength on some substrates • Variable solubility depending on the product and their clinical applications
  • 65. HYDROXYAPATITE • When the calcium and phosphorus in the ratio of 1.5 to 1.7 are sintered in water containing atmosphere at 1200ºC to 1300ºC a crystallographic end product will be obtained that is Hydroxyapatite. • This has osseoconductive effect when comes in contact with bone. • Hydroxyapatite is non porous with angular or spherical shape particles that are examples of crystalline high pure hydroxyapatite. • Their compressive strength is 500 Mpa and tensile strength is 50- 70 Mpa.
  • 66. PROPERTIES OF BIOACTIVE CERAMICS Forms, Microstructure and Mechanical Properties • Dense polycrystalline ceramics with small crystallites have higher mechanical strength • These ceramics are widely used as coatings on metallic implant substrates • Calcium phosphate ceramics have become a routine use by plasma spray technique • This technique increases the surface area which in turn increases the osseointegration.
  • 67. Density, Conductivity and Solubility • Density of the material increases as the percentage of crystallinity increases • As the density / crystallinity increases the solubility decreases • The solubility also depends on the surface area • The amorphous products are more slouble because they have less organized atomic structure • These are susceptible to enzyme or cell mediated breakdown in the same way of that of living bone. • Thse are non conductors of heat and elecctricity.
  • 68. • The Ceramic implant surface responds to the local Ph changes by releasing Na,Ca,P&Si ions in exchange for H2 ions. • Si reacts with O2 to form Silica gel • As the concentration of phosphorus and calcium increases at the surface they combine to form calcium phosphate rich layer and the collagen fibers become incorporated into it. • This way the functional integration with bone occurs with the help of natural bone cementing substance so the bond formed is strong. TISSUE RESPONSE
  • 69. CARBON AND CARBON SILICON COMPOUNDS • Extensive applications for cardiovascular devices. • Excellent Biocompatibility profiles and Moduli of elasticity close to that of bone.
  • 70. ADVANTAGES • Tissue attachment • Thermal and electrical insulation • Color control. • Provides opportunities for attachment of active biomolecules LIMITATIONS • Poor Mechanical strength. • Time dependent changes in the physical characteristics. • Biodegradation could adversely affect Stability. • Minimal resistance to scratching or scraping.
  • 71. POLYMERS AND COMPOSITES • These can be designed to match tissue properties and can be fabricated at relatively low cost. • These include polytetraflouroethylene (PTFE), polyethyleneterephthalate (PET), polymethylmethacrylate (PMMA), polypropylene (PP), polysulfone (PSF), silicon rubber (SR)
  • 72. Properties • Polymers have low strengths and elastic moduli and higher elongation to fracture compared with other class of biomaterials. • Thermal and electric insulators • Relatively resistant to biodegradation compared to bone • Most uses have been for internal force distribution connectors intended to better simulate biomechanical conditions for normal tooth functions • Some are porous where as others are constituted as solid structural forms
  • 73. DISADVANTAGES • Sensitive to sterilization and handling techniques. • Electrostatic surface properties and tend to gather dust or other particulate if exposed to semiclean oral environments • Cleaning the contaminated porous polymers is not possible without a laboratory environment • So the talc on the gloves or contact with towel or gauze pad or any such contamination must be avoided.
  • 74.
  • 75. Types of Surface Roughness 1) Macrosurface Roughness. SURFACE TOPOGRAPHY Surface topography relates to the degree of roughness of the surface and the orientation of surface irregularities. Screw Hollow basket Core vent 2) Microsurface Roughness. a) Abraded TiO2 Al203 b) Acid Etched HCl H2SO4 c) Coating TPS HA
  • 76. ADVANTAGES OF INCREASED SURFACE ROUGHNESS 1) Increased surface areas of the implant adjacent to bone. 2) Improved cell attachment to the bone. 3) Increased bone present at implant surface. 4) Increased biomechanical interaction of the implant with bone.
  • 77. Blasting with particles of various diameters is one of the frequently used method of surface alteration. In this approach, the implant surface is bombarded with particles of aluminum oxide (Al2O3) or titanium oxide (TiO2), and by abrasion, a rough surface is produced with irregular pits and depressions. BLASTING
  • 78. Roughness depends on particle size, time of blasting, pressure, and distance from the source of particles to the implant surface. Blasting a smooth Ti surface with Al2 O3 particles of 25 µm, 75 µm, or 250 µm produces surfaces with roughness values of 1.16 to 1.20, 1.43, and 1.94 to 2.20, respectively. SAND BLASTED IMPLANT SAND BLASTED AND ACID ETCHED IMPLANT
  • 79. Laser Induced Surface Roughening Eximer laser – “Used to create roughness” Regularly oriented surface roughness configuration compared to TPS coating and sandblasting SEM x 300 SEM x 300SEM x 70
  • 80. Chemical etching is another process by which surface roughness can be increased. The metallic implant is immersed into an acidic solution, which erodes its surface, creating pits of specific dimensions and shape. Concentration of the acidic solution, time, and temperature are factors determining the result of chemical attack and microstructure of the surface. CHEMICAL ETCHING
  • 81. IRREGULAR SURFACE MORPHOLOGIES Sandblasted specimen Specimen acid etched for 1 minute. Specimen acid etched for 5 minutes. Specimen acid etched for 10 minutes.
  • 82. Recently, a new surface was introduced that was sandblasted with large grit and acid-etched (SLA, Straumann). This surface is produced by a large grit (250 to 500 µm) blasting process, followed by etching with hydrochloric-sulfuric acid. The average ra for the acid-etched surface is 1.3 µm, and the sandblasted and acid-etched surface, ra=2.0 µm. SANDBLASTED AND ACID ETCHED (SLA)
  • 83. Sand blasting Acid etch The objective Sand blasting – surface roughness (substractive method) Acid etching – cleaning SEM 1000X SEM 7000X Lima YG et al (2000), Orsini Z et al (2000). - Acid etching with NaOH, Aq. Nitric acid, hydrofluoric acid. Decrease in contact angle by 100 – better cell attachment. increase in osseointegration by removal of aluminium particles (cleaning). Wennerberg et al 1996. superior bone fixation and bone adaptation
  • 84. Porous sintered surfaces are produced when spherical powders of metallic or ceramic material becomes a coherent mass with the metallic core of the implant body. Lack of sharp edges is what distinguishes these from rough surfaces. Porous surfaces are characterized by pore size, pore shape, pore volume, and pore depth, which are affected by the size of spherical particles and the temperature and pressure conditions of the sintering chamber. POROUS
  • 85.
  • 86. POROUS SURFACE: ADVANTAGES 1. A secure, 3-D interlocking interface with bone. 2. Predictable and minimal crestal bone remodelling. 3. Greater surgical options with shorter implant lengths. 4. Shorter initial healing times and 5. Porous coating implants provide the space, volume for cell migration and attachment, thus support contact osteogenesis.
  • 87. SURFACE OF A POROUS TITANIUM ALLOY IMPLANT FIBROBLASTS CULTURED FOR 24 HOURS ON THE SURFACE OF A POROUS TITANIUM ALLOY IMPLANT.
  • 89. Titanium Plasma Sprayed Coating (TPS)  Steinemann 1988, Tetsch 1991- 6-10 times increase surface area. Roughness Depth profile of about 15µm
  • 90. SURFACE OF A TITANIUM PLASMA-SPRAYED IMPLANT. (SEM, MAGNIFICATION 5,000 X).
  • 91. HYDROXYAPATITE COATINGS HA coated implant bioactive surface structure – more rapid osseous healing comparison with smooth surface implant. ↓ Increased initial stability Can be Indicated - Greater bone to implant contact area - Fresh extraction sites - Newly grafted sites SEM 100X • Hydroxyapatite([Ca10(PO4)6OH]2) coating was brought to the dental profession by DeGroot
  • 92. ADVANTAGES OF HA-COATINGS 1. HA coating can lower the corrosion rate of the same substrate alloys. 2. HA coatings has been credited with enabling to obtain improved bone to implant attachment compared with machined surface. 3. The bone adjacent to the implant has been reported to be better organized than with other implant materials and with a higher degree of mineralization.
  • 93. CERAMIC AND CERAMIC COATED IMPLANTS Ceramic materials are used to coat metallic implants to produce an ionic ceramic surface, which is thermodynamically stable and hydrophilic, thereby producing a high strength attachment to bone and surrounding tissues. These ceramic can either be plasma sprayed or coated on to the metal implant to produce bio-active surface.
  • 94. Aluminum oxide (Al2O3) is used as the gold standard for ceramic implants because of its inertness with no evidence of ion release or immune reaction in vivo. Zirconia (Zro2) has also demonstrated a high degree of inertness. THE TÜBINGEN IMPLANT OF ALUMINUM OXIDE HAS SPECIFIC MICRO-IRREGULARITIES ON THE SURFACE, CLAIMED TO ALLOW BONE INGROWTH.
  • 95. OTHER SURFACE MODIFICATIONS Surface modification methods include controlled chemical reactions with nitrogen or other elements or surface ion implantation procedures. The reaction of nitrogen with "titanium alloys at elevated temperatures results in titanium nitride compounds being formed along the surface. Electrochemically, the titanium nitrides are similar to the oxides (TiO2), and no adverse electrochemical behavior has been noted if the nitride is lost regionally. The titanium substrate reoxidizes when the surface layer of nitride is removed.
  • 96. Doped surfaces that contain various types of bone growth factors or other bone-stimulating agents may prove advantageous in compromised bone beds. However, at present clinical documentation of the efficacy of such surfaces is lacking : BMP = Bone morphogenetic protein. DOPED SURFACES
  • 97. •The biomaterials discipline has evolved significantly over the past decades, and synthetic biomaterials are now constituted, fabricated, and provided to health care professionals as mechanically and chemically clean devices that have a high predictability of success when used appropriately within the surgical disciplines
  • 98. List of referencs • Implant Dentistry -Carl E Misch. • Principles and practice of implant dentistry -Charls M Weiss, Adam Weiss. • J Dent Edu 1988; 52: 815-820. • Atlas of Oral implantology - A Norman Cranin. • Sciences of dental materials - Anusavise. • The BRANEMARK system of oral reconstruction - A clinical atlas. • DCNA 1986 ; 30 (1) 25-47 • IJOMI 2000 ;(15) 675-690 • D.C.N.A., 1992 ; 36, 1-17 • JPD, 1983 ; 50 : 108-113. • JPD, 1983; 50:832-37. • IJP, 1990 ; 3 : 30-41

Editor's Notes

  1. Vitallium-alloy of co cr mo Also used as orthodontic nails, screws, joints
  2. Finally P I BRANEMARK IN SWEDEN used titanium implants with controlled condition for surgery.
  3. Classification based on material used and biological response:
  4. The ability of the implant to bear the stress decreases as the number of loading cycles increases.
  5. Astm standard values-American standard of testing material Eli-extra low interstitial grade Yield strenghth-amt of stress required to produce predetermine amt of permanent strain
  6. Dielectric-greater vander waal force due to 2 phases of ti
  7. Hunter process modified by kroll Hunter-Na KROLL-Ca,Mg,
  8. Roxolod – binary ti and zr nd titanium foam- ti powder and polymer and foaming agent
  9. Sem-scanning electron microscope