Biomedical Metals

Stainless steel
„ Longest history among metallic materials being used
for implants.
„ Highly corrosion resistance due to the dense film of
Cr2O3 (Cr content >11%) on the surface.

Plates & screws for orthopedic fracture fixation.

Microstructure
„ Categorised according to the crystalline phase:

„ Ferritic (BCC)
„ Relatively cheap, less corrosion resistant, less ductile
than Austenitic SS.
„ Austenitic (FCC)
„ High in Ni (FCC) and low C content.
„ Highest corrosion resistance, used for endosseus
implants.
„ Martensitic (BCT)
„ Contain relatively high C content (1%)
„ Formed through rapid cooling
„ High strength, high hardness, used as medical surgery
tools (knives, clips, etc.)
Composition Map of SS

„ Chemical composition (mainly Ni & Cr) determines the

type of Stainless Steels.
Types of SS used in Biomedical

„ The first ever used contained 18%Cr and 8%Ni (SS type 302).
„ Later add small amount of Mo & Si (SS type 316).
„Mo enhances resistance when Cl ion is present (body
fluids).
„ C content is further reduced from 0.08wt% to 0.03wt% (SS
type 316L) in order to further improve corrosion resistance.

Type Fe C Cr Ni Mo Mn
302 bal 0.15 18 9 - 2
304 bal 0.08 19 9 - 2
316 bal 0.08 17 12 2.5 2
316L bal 0.03 17 12 2.5 2
Microstructure of 316L
„ Two main features that affect performance are:
„ Grain size (< 100μm)
„ Shape
„ Equiaxed in annealed condition (isotropic)

„ Elongated in a cold-worked condition (anisotropic)

Equiaxed grains of SS316L in Various implant types made of

annealed condition. SS316L.
Mechanical Properties of 316L
„ Low C content – not heat treatable.
„ Use cold-working to improve strength.

Type Treatment E (GPa) σy (MPa) σtensile Ductility

(MPa) (%)
316L Annealed 190 172 485 40

Cold-worked 190 690 860 12

316 Annealed 190 205 515 40

Cold-worked 190 690 860 12

Cobalt-based Alloy
„ Better corrosion resistance and wear resistance than Stainless
Steel, but heavier.
„ Three types are commonly used for medical implants (C
content = 0.25wt%):
„ CoCrMo (F75 or Stellite 21) (Cast or P/M)
„ CoCrWNi (F90 or Stellite 25) (Wrought)
„ CoNiCrMoTi (F562 or MP35N)
„ Cr increases corrosion resistance and provides solid solution
strengthening.
„ Mo produce finer grains and provide solid solution
strengthening.
„ W & Ni added to improve machinability and fabrication
properties.
Co-Cr Phase Diagram
 Microstructure
„ Varies significantly with processing.
„ Casting
„Co-rich ε-phase with interdendritic carbides.
„ Relatively large grains, low strength.
„ Wrought
„ Obtained through hot forging, improve mechanical properties.

Microstructure of cast CoCrMo Artificial Intervertebral Disc (IVD) with top

(left) and wrought CoCrMo (right). and bottom plates made of CoCrMo
 Mechanical Properties
„ Higher E and σ than SS.
„ Lower ductility.
„ Better wear resistance.

Alloys Treatment E (GPa) σy (MPa) σtensile (MPa) Ductility (%)

CoCrMo Cast 248 450 655 8

CoCrMo Wrought 248 827 1172 12

CoNiCrMo Annealed 228 241-448 793-1000 50

Titanium alloys
„ Increasingly used in medical implants due
to excellent biocompatibilities, corrosion
resistance, and low density.
„ TiO2 form on the surface – excellent
protection from corrosion.

Ti64 is widely used as endosteal implants (elbow – left, shoulder –

centre), as well as artificial limbs (right).
 Polymorphs of Titanium

„ Titanium is polymorphic
„ α-Ti (HCP) at low temp.
„ β-Ti (BCC) at high
temperature.
„ α stabilising elements – Al, O,
N, Ga.
„ β stabilising elements – Mo, V,
W, Ta.
„ At RT, can have 3 different Ti:
„ α single phase, α+β dual
phase, β single phase.
Chemical composition
„ CP Titanium (interstitial elements) is commonly used because
most corrosion resistant.
„ Ti-6Al-4V ELI is also widely used due to its strength.

Min tensile Min yield

% Impurity
strength strength
Materials
Oxygen Fe MPa MPa

Ti grade 1 0.18 0.20 240 170

Ti grade 2 0.25 0.30 345 275

Ti grade 3 0.35 0.30 450 380

Ti grade 4 0.40 0.50 655 485

Ti-6Al-4V ELI 0.10 0.20 890 825

α + β alloys
„ High strength and formability
„ Contain 4-6 wt% of β-stabilisers – substantial amounts of β
retained during quenching from β to α + β phase.
„ Most popular alloy is Ti-6Al-4V
„ Al reduces density, stabilises & strengthens α.
„ V provides a more ductile β phase for hot working.
„ Strength 110GPa, creep resistance at 300OC, fatigue
resistance and castability.

Microstructure of Ti-6Al-4V
Biomedical Polymers
Categories
„ Natural
„ Used because similar structure to human tissues.
„ Biodegradable.
„ E.g.: Collagen, Alginate, Chitin & Chitosan.
„ Synthetic
„ Non-degradable.
„ Used as implants, drug delivery, tissue scaffolds.
„ E.g.: PE, PMMA, Polyester, PC, Polyamides, PU,
Polysulfones, PEEK.
Polyethylene

„ HDPE and UHMWPE are frequently

used.
„ Very inert.
„ Used as bone and cartilage substitute.
„ Minimal inflammatory and foreign body
response.
„ HDPE is used in medical tubing and as
porous scaffolds – tissue ingrowth into Medical tubing (top) and
the implant. porous scaffold (bottom).
„ HDPE also used for Craniofacial
applications – nasal reconstruction, ear
reconstruction.
 UHMWPE
„ Produced as powder and must be
consolidated under elevated
temperatures and pressures due
to its high melt viscosity.
„ Due to UHMW, only compression
moulding can be used for
production (cannot use IM, Extr.,
Blow Moulding). Long entangled chains of UHMWPE
„ Due to its low Thermal (top) and various implants for human
Conductivity, processing time is joints (bottom).
long to ensure uniform heating
and cooling rates.
„ Direct compression moulding has
been used to manufacture
acetabular cup liner, tibial knee
inserts and patellar component.
Properties of UHMWPE
„ High abrasion resistance, Low friction, High impact strength,
excellent toughness, low density, ease of fabrication.
„ Very attractive as bearing surfaces in arthroplasty.
„ Wear is still a problem – cause osetolysis.

Wear of UHMWPE tibial insert.

 PMMA
„ Used primarily as bone cement.
„ Consists of two parts – solid in a packet & liquid in a vial.
„ When the two part mixed, the viscosity of the mixture will increase,
and will become dough in a few minutes.
„ The dough will harden in another few minutes.
 PET
„ Belong to the Polyester family which
have ester linkage connecting the
polymers.

O C Various suturing techniques (top)

and closing of wound via sutures
(bottom).
„ It has very good mechanical
properties.
„ PET fibers are used as sutures,
internal patches, pledglets,
ligamentous prosthesis, artificial
blood vessels, heart valve sewing
cuffs, etc.
 PC
„ Have carbonate linkages in
their polymer chains
O

O C O

„ Used to make components for

oxygenator for open heart
surgery, venous reservoir, arterial
filter.
„ Sterilisable, ease of processing,
clarity.
Oxygenator for Open Heart
Surgery.
 Polyamides
„ Have amide linkages in their
polymer chains.

Nylon sutures (top) and the surgical

C N procedure in the treatment of
glaucoma using sutures (bottom).
„ Have amide linkages in their polymer
chains.
„ Nylon-66 was the first Polyamides
ever synthesized.
„ Nylon-66/Nylon-6 have been used as
surgical sutures.
 Polyurethanes

„ Have urethane linkages in their

polymer chains.

O C N
Schematic of pacemaker system
„ Excellent fatigue resistance. (top) and a pacemaker set
„ Used as blood contacting materials – (bottom).
totally implantable artificial heart, left
Ventricular Assist Devices (VADs),
pacemaker lead insulators.
Biomedical Ceramics
Categories
„ Bioactive
„ Calcium Phosphate.

Calcium phosphate grown in an organic matrix. The sample is highly porous and the walls
between the pores are composed of ~ 50 nm sized subunits.

„ Bioinert
„ Al2O3, Si3N4.

Alumina Ball
Calcium-phosphate
„ Only two are stable at body fluid &
temp.: Dental implant
made of Brushite
„ Brushite:
CaHPO.2H2O at pH < 4.2
„ Hydroxyapatite: Ca10(PO4)6(OH)2
> 4.2

„ TCP {Ca3(PO4)2} & TTCP

{Ca4P2O9} formed @ higher
temperatures.

SEM image of TCP

Hydroxyapatite
„ Good biological stability.
„ Form hydroxy-carbonate apatite (HCA) layer on
the surface when implanted.
„ HCA is similar in composition and structure to
the mineral phase of bone.
„ Widely used in powder and bulk forms.
„ Weak in load-bearing applications – used as
coating.

Furlong Hip Stem coated

with HA.
Morphological variant of HA at 10.6x
magnification (left) and 50.6x magnification (right)
Structure & Chemistry of HA
„ Chemically similar to the
mineral component of bone.
„ Excellent biocompatibility
with hard and soft tissues.

Composition of Bone:
Mineral Phase (70%) „ Mineral – HA 95%, Mg, Na,
Organic Phase (20%)
K, Fl, Cl.
Water (10%)
„ Organic – Matrix, Collagen,
Proteins.
„ Water.
Synthesis of HA powder

„ Categorised into two types:

„ Dry Chemical Methods
„ Wet Chemical Methods
„ Morphology, stoichiometry, crystallinity
vary with processing methods.
Dry Chemical Methods
„ Reactions between Ca and P in solid-state:

6CaHPO4 + 4Ca(OH)2 Æ Ca10(PO4)6(OH)2 + 6H2O

or

3Ca3(PO4)2 + Ca(OH)2 Æ Ca10(PO4)6(OH)2 + H2O

„ Raw Ca compound are milled, mixed, compressed,

and sintered above 950OC.
„ Require high temperature and long sintering time.
Wet Chemical Methods

„ Three major types of WCM:

„ Hydrothermal reactions
„ Hydrolysis
„ Precipitation
„ Produce fine particle size and low cost.
Hydrothermal reactions
„ Reaction in the presence of aqueous solvents and mineralisation under
high P and T.

6CaHPO4 + 4CaCO3 Æ Ca10(PO4)6(OH)2 + 6H2O + 4CO2

Hydrolysis
„ Require low T (< 100OC)
„ Hydrolysis of other CaP (DCPD, DCP, TCP, ACP, CaCO3, etc.)
„ Produce Ca deficient HA which is more soluble in bone.
„ Highly non-stoichiometric, hydrolysis at low T require longer time period
(hours, days).

3Ca3(PO4)2 + H2O Æ Ca9(HPO4)(PO4)5OH

 Precipitation
„ Involves the following reactions:

10Ca(OH)2 + 3H3(PO4)2 Æ Ca10(PO4)6(OH)2

Or

10Ca(NO3)2 + 6(NH4)2HPO4 + 2NH4OH Æ

Ca10(PO4)6(OH)2 + 14NH3 + 10H2O + 20NO2.

„ Low processing T (24-94OC)

„ Crystallinity depends on the concentrations of the reactants and pH
of the reaction.
Mechanical Properties
„ Highly dependent on porosity, grain size, and impurities of HA.
„ Properties comparable to hard tissue:
„ E = 35-120GPa
„ σbend = 38-250MPa
„ σcompr = 120-900MPa
„ σtensile = 38-300MPa
„ Not normally used in load bearing applications due to its brittle nature.

Bone cell growing on the surface of HA.

Alumina

„ Bioinert ceramic, high

corrosion and wear
resistance – good for
joint replacement.
„ Properties:
„ σflex = 400MPa
„ E = 380GPa
„ Hardness = 9/10
Moh’s
Processing
„ Bauxite (Al ore) contains large quantities of Al2O3.
„ Bauxite impurities include Fe2O3 and SiO2.
„ Bayer process for purification:
Al2O3 + 3H2O + 2NaOH + heat → 2NaAl(OH)4
Upon cooling, Al(OH)3 precipitates.

2Al(OH)3 + heat → Al2O3 + 3H2O

„ Fe2O3 does not dissolve – remove through filtering.

„ SiO2 dissolves into Si(OH)62-.
Q&A