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ENT 219

Bio-Metallic Material

Lecturer: Mrs Normahira Mamat @ Mohamad Nor


Update: 13/10/2014
1.0 Introduction
◼ Metals and its alloys widely used as
biomaterial because:
◼ Strong material
◼ Ductile : Relatively easily formed into complex shape
◼ High modulus and yield point : make them suitable for
bearing large load without leading to a large deformations
and permanent dimensional change.

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1.0 Introduction

◼ Metallic material usually used in


◼ Prostheses: serve to replace a portion of body such as
joint, long bones and skull plates.

◼ Fixation devices: used to stabilize broken bones and other


tissue while the normal healing proceed. E.g. bone plates,
rods, intramedullary nails, screw and sutures.

◼ In dental applications, metal are used for


◼ Filler material for decayed teeth
◼ Screws for dental implant support
◼ Dental material replacement

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Metal used in Biomedical

◼ Metals commonly used in Biomedical Application


Metals Applications
Cobalt-chromium alloys Artificial heart valves, dental prosthesis,
orthopedic fixation plates, artificial joint
components, vascular stents

Gold and platinum Dental fillings, electrodes for cochlear


implants
Silver-tin-copper alloys Dental amalgams

Stainless steel Dental prosthesis, orthopedic fixation


devices (such as plates and screw),
vascular stents
Titanium alloys Artificial heart valves, dental implants,
artificial joint components, orthopedic
screws, pacemaker cases, vascular
stents
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Biometals
◼ Specific characteristic for application in the
human body
◼ Biocompatibility
◼ Chemical stability, corrosion resistance, non
carcinogenic & nontoxic when used in the human body.

◼ Able to endure large & variable (cyclic)


stress in the highly corrosive environment
of the human body
◼ Strong, fatigue & wear resistance in a highly corrosive
environment
Applications of biometal in
human body

bone fixation plate intramedullary nail1


Applications of biometal in
human body

Knee replacement
2.0 List of metals
◼ Stainless steel
◼ Cobalt-chromium alloys
◼ Titanium alloys
◼ Gold and platinum
◼ Silver-tin-copper alloys

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3.0 Stainless Steels
◼ Predominant implant alloy.

◼ In 1926-The first stainless steel (18Cr-8Ni) was


utilized for implant fabrication, which is stronger
and more resistant to corrosion than the vanadium
steel.

◼ In 1943, type 302 stainless steel had been


recommended to U.S Army and navy for bone
fixation.

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3.0 Stainless Steels (cont)
◼ Later 18-8sMo stainless steel or known as 316 stainless steel,
which contains a small percentage of molybdenum to improve
corrosion in chloride solution (salt water) was introduced.
◼ In the 1950s – 316L stainless steel was developed by
reduction of maximum carbon content from 0.08% to 0.03%
for better corrosion reduction especially to physiological saline
in human body.

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3.0 Stainless Steels (cont)
◼ Chromium content of stainless steel should be at least 11%
to enable them resist corrosion.
◼ Chromium oxide on the surface of steel provide excellent
corrosion resistance.

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3.0 Stainless Steels (cont)

◼ Most widely used for implant fabrication:


◼ Austenitic stainless steel
◼ 316 stainless steel
◼ 316L stainless steel
◼ 316L stainless steel is also easier to machine compared to 316
stainless steel due its lower carbon content.

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3.0 Stainless Steels
(cont)

Strengthens the alloy Weakens the alloys (low


mechanical strength)
Cold working ( material is exposed Annealing (material is exposed to high
at low temperature relative to the temperatures for long period in order to
melting point, This leads to an increase ductility and toughness of the
increase in the yield strength of the material.
material and a subsequent decrease
in ductility. 13
3.1 Stainless steel alloy
application
◼ Stainless steel alloy application
Devices Stainless steel type
Orthopedic Fixation Devices:
Jewitt Hip nails and plates 316L
Intramedullary pins 316L
Mandibular staple bone plates 316L
Schwartz clips (neurosurgery) 420
Implant prostheses
Cardiac pacemaker electrodes 304
Heart valves 316
Stent 316L (new: nickel free
stainless steel) 14
3.1 Stainless steel alloy application Jewitt
Hip nails and plates

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3.1 Stainless steel alloy
application

Mandibular staple
Schwartz clips (neurosurgery)
bone plates

Cardiac pacemaker electrodes

Intramedullary
pin
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4.0 Cobalt-Chromium Alloys

◼ The ASTM list four types of CoCr alloys which are


recommended for surgical implant application:
◼ cast CoCrMo alloy (F75)
◼ Wrought CoCrWNi alloy (F90)
◼ Wrought CoNiCrMo alloy (F562)
◼ Wrought CONiCrMoWFe alloy (F563)

◼ At present only two are used extensively in implant


fabrication, which are cast CoCrMo alloy and
wrought CoNiCrMo alloy

ASTM= The American Society for Testing and Materials 17


4.0 Cobalt-Chromium Alloys
(cont)
◼ Molybdenum is added to produce finer grains =
results in higher strengths.
◼ Chromium = enhance corrosion resistance.
◼ Advantages of CoNiCrMo
◼ Highly corrosion resistance to seawater
(containing chloride ions) under stress.
◼ Has a superior fatigue and ultimate tensile
strength than CoCrMo → suitable for application
which require long service life such as stems of
the hip joint prosthesis

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Femoral
component of hip
joint prosthesis

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4.0 Cobalt-Chromium Alloys
(cont)

This table adapted from Biomaterials, Sujata V.Bhat

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4.0 Cobalt-Chromium Alloys
(cont)
◼ Problems with CoCr alloys:
◼ Particulate Co is toxic to human osteoblast and inhibits
synthesis of type I collagen.
◼ Advantages of CoCr alloys:
◼ Low wear
◼ Hard
◼ Tough
◼ High corrosion resistance
◼ Application: Artificial heart valves, dental prosthesis,
orthopedic fixation plates, artificial joint components, vascular
stents

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5.0 Titanium alloys
◼ Titanium is a light metal.
◼ Density = 4.505 g/cm3 at 26oC
Alloys Density (g/cm3)

Ti and its alloys 4.5


316 stainless steel 7.9
CoCrMo 8.3
CoNiCrMo 9.2
NiTi 6.7

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5.0 Titanium alloys
(cont)

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5.0 Titanium alloys (cont)

◼ Ti6Al4V is widely used to manufacture implant.


◼ Has approximately the same fatigue strength
(550MPa) with CoCr alloy.
◼ That’s why it has same application as CoCr alloy.
◼ However it more preferable because it has low
density.

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5.0 Titanium alloys (cont)

◼ Advantages:
◼ Resistance to corrosion by the formation of solid oxide layer
to a depth of 10nm.
◼ Under in vivo conditions the oxide (TiO 2) is the only stable
reaction product.
◼ Limitation:
◼ Has poor sheer strength → less desirable for bone fixation
devices e.g. bone screw and plates.
◼ Tends to gall when in sliding contact with itself or another
metal.

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5.0 Titanium alloys (cont)

◼ However, micro motion at the cement-prosthesis


and cement-bone are inevitable, consequently
titanium oxide and titanium alloy particles are
released into the extra cellular fluid and can cause
toxicity or triggers giant cell response around the
implant.

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5.0 Titanium alloys (cont)

◼ Biomedical application:
◼ Artificial heart valves,
◼ dental implants,
◼ artificial joint components,
◼ orthopedic screws (less desirable),
◼ pacemaker cases,
◼ vascular stents

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6.0 Silver-tin-copper
alloys (Amalgam)
◼ Amalgam is an alloy made of liquid mercury and
other solid metal particulate alloys made of silver,
tin, copper, etc.
◼ Dental amalgam typically contain:
◼ 45 to 55% mercury
◼ 35 to 45% silver
◼ 15% tin

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6.0 Silver-tin-copper
alloys (Amalgam)
◼ Mechanical properties of dental amalgams
Amalgam Compressive Tensile strength
strength (MPa) (MPa)
Lower Copper 343 60
Admix 431 48
Single 510 64
composition

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6.0 Silver-tin-copper
alloys (Amalgam)
◼ Advantages over other restorative material
◼ It is inexpensive
◼ relatively easy to use and manipulate during
placement
◼ it remains soft for a short time so it can be
packed to fill any irregular volume, and then
forms a hard compound.
◼ Amalgam possesses greater longevity than other
direct restorative materials, such as composite.
◼ On average, serve for 10 to 12 years, whereas resin-
based composites serve for about half that time.

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6.0 Silver-tin-copper
alloys (Amalgam)
◼ Has bacteriostatic effects
◼ Can interfere the bacterial protein
production, DNA replication, or other
aspects of bacterial cellular metabolism

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6.0 Silver-tin-copper
alloys (Amalgam)
◼ Its main disadvantages are:
◼ poor aesthetics on anterior teeth
◼ the known toxicity of mercury.
◼ Concerns about possible harmful health effects from the
low levels of mercury released from amalgam have
resulted in a decline in the routine use of amalgam in
recent years.

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Other metals
◼ Tantalum
◼ Found to be highly compatible
◼ high density (16.6g/cm3)
◼ poor mechanical properties
◼ Application restricted to a few applications such
as wire sutures for plastic and neurosurgery and
a radioisotope for bladder tumour.

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Other metals

◼ Platinum
◼ Extremely corrosion resistant
◼ Poor mechanical properties
◼ Mainly used as alloys for electrodes in neuromuscular
stimulation devices such as cardiac pacemaker.
◼ Because of their high resistance to corrosion
◼ Low threshold potential for electrical conductivity.

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7.0 Corrosion of Metallic
Implant
◼ Corrosion is the unwanted chemical reaction of metals with its
environment.
◼ Tissue fluids in the human body contains water, dissolved
oxygen, proteins and various ions such as chloride and
hydroxide.
◼ As a result the human body presents a very aggressive
environment for metals used for implantation.

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7.0 Corrosion of Metallic
Implant
◼ Fundamental of corrosion
◼ Corrosion is an electrochemical process that
involves transfer of electrons from one substance
to another.

◼ Coupling of two reaction:


◼ Oxidation (generates electrons)
◼ Reduction (consumes electron)

◼ Corrosion occurs when metal atoms become


ionized and go into solution to form a compound
which flakes off or dissolves.
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7.1 Where does corrosion
occur?
◼ In region where two dissimilar metals in contact
◼ Implantation of dissimilar metals (mixed metals) is to be avoided,
because:
◼ Galvanic corrosion may occur
◼ One which is most negative in the galvanic series will become
anode, and the other one will become cathode.

◼ Region where there are variations in material


homogeneity.
◼ Occur within a single material
◼ Grain boundaries are anodic with respect to the grain
interior.
◼ Crack in material- matrix will become cathode, crack will
become anode.

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7.2 Types of corrosion
◼ CORROSION DUE TO DEFECTS DURING
FABRICATION.
◼ Crevice corrosion
◼ Pitting Corrosion
◼ Intergranular corrosion

◼ CORROSION DUE TO EFFECTS OF MECHANICAL


ENVIROMENT
◼ Stress and Galvanic corrosion
◼ Stress corrosion cracking
◼ Fatigue corrosion
◼ Fretting corrosion
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CORROSION DUE TO DEFECTS
DURING FABRICATION.

◼ Crevice Corrosion
◼ Corrosion occurring in spaces to which the access of the
working fluid from the environment is limited.
◼ These spaces are generally called crevice which is narrow,
deep crack.
◼ Example: In between the screw and plate of a bone fixation
device.
◼ Usually exhibit in stainless steel orthopaedic applications.

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CORROSION DUE TO DEFECTS
DURING FABRICATION.

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CORROSION DUE TO DEFECTS
DURING FABRICATION.

◼ Pitting corrosion
◼ Caused by same mechanism as crevice corrosion.
◼ Small defects on the surface of the material (e.g scratch).
◼ Passivation layer on the surface is disrupted.
◼ Leading to the formation of a relatively small anode and a
large cathode.
◼ The anodic region undergo significant dissolution.
◼ This is dangerous type of corrosion because it can be
undetected until device failure due to the small overall
material loss.

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7.2 Types of corrosion
◼ Intergranular Corrosion
◼ Devices fabricated by casting often have multiple grains
◼ Thus susceptible to intergranular corrosion.
◼ Grain boundaries will become anodic regions of the
material.
◼ Grain will become cathode.

Grain
(cathode)

Boundaries
(anode) 51
CORROSION DUE TO EFFECTS
OF MECHANICAL ENVIROMENT

◼ Galvanic corrosion
◼ Occur when two dissimilar metals in contact.
◼ One which is most negative in the galvanic series will
become anode, and the other one will become cathode.
◼ Bending of metal rod or plate will cause:
◼ Tensile side → anode
◼ Compression side → cathode

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Galvanic or two-metal
corrosion
◼ Occurs when two metals or alloys
having different compositions are
electrically coupled while exposed to an
electrolyte.
◼ Examples:
◼ Galvanized steel, steel coated with
Zn; Zn is sacrificed to protect steel
◼ Tin can (food container), steel
coated with Sn; Sn is sacrificed to
protect steel

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CORROSION DUE TO EFFECTS
OF MECHANICAL ENVIROMENT

◼ Stress corrosion cracking


◼ Occurs to a metal that is both under tension and
subjected to a corrosive environment.
◼ Results in small crack that form perpendicular to
the direction of applied stress.
◼ Crack propagate due to anodic dissolution at
crack tip.
◼ This lead to brittle fracture.

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CORROSION DUE TO EFFECTS
OF MECHANICAL ENVIROMENT

◼ Fatigue corrosion
◼ Continued bending, loading or motion around the implant
may disrupt the passivating film formed on the metal and
exposed the underlying surface, leading to corrosion of this
area.
◼ This type of corrosion may significantly shorten the fatigue
life of the implant
◼ Results in premature device failure.

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CORROSION DUE TO EFFECTS
OF MECHANICAL ENVIROMENT

◼ Fretting corrosion
◼ Not related to loading.
◼ Dependent on motion near the implant (abrasion, friction).
◼ Involves removal of the metal’s passivating layer by
mechanical means.
◼ Can be seen around connection between fixation plates and
bone screws.

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