Biomaterials - Endoprostethics

HIP ARTHROPLASTY
 Metallic Implant Materials
• 40% of annual 3.6 million
orthopaedic operations

• $6 billion market

• 5 out of 100 Americans carry a piece

of metal in them!
2
 Metallic Implant Materials
• Reduction of fracture, internal
fixation

• Replacement of hip, knee and

shoulder

• Oral and maxillofacial surgery

3
 Types of Metallic Implants
• Stainless steel
• Cobalt Based Alloys
• Titanium Alloys

Composition? Properties?
Manufacturing?
4
 Stainless Steels
• The most
common
stainless steel:
316L
– Fe 60-65 wt%
– Cr 17-19 wt %
– Ni 12-14 wt%
5
 Stainless Steels
• Carbon content reduced to 0.03 wt%:
– better resistance to in vivo corrosion.

• Why reduce carbon?

– reduce carbide (Cr23C6) formation at grain
boundary
– carbide impairs formation of surface
oxide
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 Corrosion at the Grain Boundary

High risk of corrosion when

Cr drops down to less then
C 9% at the boundary

Cr Cr
Cr
Cr23C6

C
C

7
 Stainless Steels
• Why add chromium?
– corrosion resistance by formation of
surface oxide

• Why add nickel?

– improve strength by increasing face
centered cubic phase (austenite)

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 Stainless Steels
• Good stainless steel:
– Austenitic (face centered cubic)
– No ferrite (body centered cubic)
– No carbide
– No sulfide inclusions
– Grain size less then 100m
– Uniform grain size

9
 Stainless Steels
• Improved
mechanical
properties by cold
working (a.k.a.
strain hardening)

• How? excessive
number of
dislocations are
induced prior to in-
vivo use, newer
dislocations will be
harder to induce
10
 Stainless Steels
• How to cold
work: load
plastically.
• Pros: increased
yield strength,
ultimate strength
and fatigue
strength
• Cons: reduced
ductility
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 Cobalt Based Alloys
• Common types for surgical
applications:
– ASTM F75
– ASTM F799
– ASTM F790
– ASTM F 562

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 Cobalt Alloys: ASTM F75
• Co-Cr-Mo Cofield Humeral Stems;
• Surface oxide; thus Intermediate Length Humeral Stem
Components Chromium Cobalt
corrosion resistant (ASTM F75
• Wax models from
molds of implants
• Wax model coated
with ceramic and wax
melted away                                   
• Alloy melted at 1400
C and cast into
ceramic molds.

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 Cobalt Alloys: ASTM F75
• Three caveats:
– Carbide formation  corrosion.
Solution: anneal at 1225 C for one
hour.
– Large grain size  reduced mechanical
strength (WHY?)
– Casting defects  stress concentration,
propensity to fatigue failure
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The enemy within: Casting defect

Polished-etched view of a cast In vivo fracture initiated from a

ASTM F75 femoral hip stem. an inclusion formed during the
Note dendrites and large grains casting process 15
 Cobalt Alloys: ASTM F799
• Modified form of F75: hot forged after
casting
• Mechanical deformation induces a shear
induced transformation of FCC structure to
HCP.
• Fatigue, yield and ultimate properties are
twice of F75.

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 Cobalt Alloys: ASTM F90
• W and Ni are added to improve
machinability and fabrication

• Mechanical properties similar to F75

• Mechanical properties double F75 if

cold worked
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 Titanium Based Alloys
• Lighter

• Good mechanical
properties

• Good corrosion
resistance due to
TiO2 solid oxide
layer
18
 Titanium Based Alloys
• Ti-6% wt Al-4% wt V (ASTM F136) is
widely used

• Contains impurities such as N, O, Fe,

H, C

• Impurities increase strength and

reduce ductility
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 Titanium Alloys: ASTM F136
• HCP structure
transforms to BCC for
temperatures greater
than 882 C.
• Addition of Al
stabilizes HCP phase
by increasing
transformation
temperature
• V has the inverse
effect
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Yield Strength of Metals

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 Dental Metals
• Amalgam:
– Solid alloy
• silver, tin, copper, zinc and
mercury
– deformable mixture packed in
cavity
– cures over time
• 25% of total strength in 1 hour
• full strength in a day
• Gold:
– Durable, stable, corrosion
resistant as fillings

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 Dental Metals: Nitinol
• NIckel-TItanium-Naval Ordinance Lab

• Shape memory alloy (SMA): ability to return to a predetermined shape

when heated

23
 Dental Metals: Nitinol

Orthodontic applications

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 Corrosion
• Corrosion is the degradation of metals to oxide,
hydroxide or other compounds through chemical
reactions.
• Human body is an aggressive environment:
– water
– dissolved oxygen
– proteins
– chloride
– hydroxide
– pH (after surgery pH around 5.3-5.6)
– flow rate
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 Corrosion: Basic Reactions
• Ionization: formation of metallic cations
under acidic or reducing (i.e. oxygen poor)
conditions
M  M++e-

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 Corrosion: Basic Reactions
• Oxidation: reaction of metal with oxygen

M + O2  MO2

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 Corrosion: Basic Reactions
•Hydroxylation: reaction of water under alkaline
(i.e. basic) or oxidizing conditions
– yields a hydroxide or hydrated oxide

2M + O2 (aq) + 2H2O  2M(OH)2

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 Corrosion: Basic Reactions
• Reaction: combination with other cations
and anions

MO22- + HCl  MOCl- + OH-

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 Corrosion
• MECHANISM:
– corroded state is preferred since lowest
energy state
– metal atoms ionize, go into solution and
combine with oxygen
– metal flakes off

• Corrosion of most metallic biomaterials

occur by “gaseous reduction”

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Corrosion: Gaseous Reduction
Oxygen deficient
Electron requirement
location is the for right cell induces
ANODE. Anode ferrous iron formation
oxidizes i.e. rusts! on the left cell (see the
e- flow)

Oxidation: Reaction in
Reaction in which which
electrons are lost electrons are
gained

+ve electrode --ve electrode 32

 Corrosion: Terminology
• Formation of rust:
Water, oxygen and metal
essential
– Oxidation of iron to ferrous
(iron +2) ion
Fe  Fe+2 + 2 e- Overall Reaction 1:
– Oxidation of ferrous ions to
ferric (iron +3) ion 4Fe+2+O2+8H2O  2Fe2O3. H2O (s) + 8H+
Fe+2  Fe+3 + e-
– Reduction of oxygen using RUST
electrons generated by Overall Reaction 2:
oxidation
4Fe+2 + O2 + 2H2O  4Fe+3 + 4OH-
O2 (g) + 2H2O + 4e-  4OH-
4Fe+3 + 12OH-  4Fe(OH)3
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 Corrosion: Terminology
How it happens on the surface?

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 Corrosion:Closer look at the
“gaseous reduction”:

Crevice
Corrosion
• Pitting Corrosion: special case
of crevice corrosion where
corrosion is induced by
handling damage such as
scratches. Surgeons should be
careful about this type of 35
corrosion.
 Corrosion Memorabilia!
• Electron flow direction is FAT CAT (from
anode to cathode)
• Oxidation at the anode, reduction at the
cathode (OAR-CAT !)
• ANO (anode attracts negative ions and
results in oxidation)
• CPR (cathode attracts positive ions and
results in reduction)
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 Galvanic Corrosion
• Occurs when there are two dissimilar
metals
• Much more rapid than corrosion by
gaseous reduction
• Avoid implantation of dissimilar metals

37
Galvanic Corrosion

Conventional
Electrons current

FeFe
2+ 2+

Fe Cu
O2
O2

taken from Bob Cottis

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Corrosion and Protection Centre, UMIST
 Pourbaix Diagram (poor-bay)
• classification of all
possible reactions
between a metallic 1.6
element and water for B oxyg
combinations of pH and 0.8 en
electrical potential

EM (Volts)
difference 0 A
hydr
ogen
• above B oxygen is
released -0.8
• below A hydrogen is -1.6
released
0 4 8 12
• between A and B water is pH
stable

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 •Corrosion: concentration
of the metal is greater than

hydroxides”
Pourbaix Diagram
•Passivation: formation of “oxides and 10-6 [M]
•Metal and the passive
Immunity: Dominant
•Concentration of the metal is less than
1.6 coating is attacked
[10 ] M
reaction is “ionization”.
-6
B resulting in corrosion.
•Reaction
•Concentration0.8 products
of the metalto the
cling
is lessinterface between
than [10 -6
] M the metal and the
solution, reducing further reactions.
EM (Volts)

•At this concentration A

•Thus, the metal 0 is covered with
the reaction
passive coating.is immune
from corrosion
-0.8

-1.6
0 4 8 12
pH
Passivation

Corrosion

Immunity 40
 Pourbaix Diagram
1.6
B
0.8
EM (Volts)

0 A

-0.8

-1.6
0 4 8 12
pH
Chromium in water
Chromium in water + chloride
•Note smaller passivation region.
Greater chance of corrosion.

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•Most physiological solutions in the
corrosion region
 Against Corrosion
• Use appropriate metals
• Avoid implantation of dissimilar metals
• Minimize pits and crevices
• Avoid transfer of metal from tools to the
implant during surgery
• A metal that does not corrode in one part
of the body may corrode somewhere else

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 The Beginning

– 1930 Smith Petersen Surface Cups

were resumed in Boston
– Aufranc 1957 1000 cases of SP cups
of vitallium
– Bierbaum and Scott + Krakow report
statistics tracked over 14 years-had
assembly survival and over 17 years
Sir JOHN CHANLEY 1962
“LOW FRICTION ARTHROPLASTY”

COMPONENTA FEMURALA – CoCr

COMPONENTA ACETABULARA –
UHMWPE

FIXATE CU CIMENT ACRILIC

• However, the current conclusion is that no
progress has been made on Charnley prostheses
- the maximum survival of implants remains at 25
years!!!!
 The Weak Link

• Polyethylene = friend and foe!

 UHMPWE
• Compression casting in layers
• Extruded into bars
• Pour into final shape
 Initial UHMWPE
• Structura
chimica
 Sterilization process…
• Irradiation in
the oxygen
atmosphere
• Unplanted polyethylene cups -
appearance at 14 years
• Irradiated
polyethylene
structure in
depleted
atmosphere /
inert gases
• Osteolize extinse la 15 ani
• Revizii dificile
• Rezultate funcţionale moderate
Surfaces- Interfaces
Cimentarea
Progrese in tehnica cimentarii
Femur:
lavaj pulsatil + periere
păstrare ţesut spongios
introducerea ciment: canal medular
exsanguinat
sub presiune: pistol/retrograd
Cementless?
Cementless?
Cementless?
Hydroxyapatite
 Metal-metal
• Uzura=60-100X mai mica
• Multifactorial
– Design
– Fixare
– Tehnica
• Osteoliza apare!