BIOMATERIALS

Biomedical Engineering
Sem-III

Prof. Arunkumar Ram

Module 5: Properties and

Applications of Polymeric
Biomaterials

POLYMERIC BIOMATERIALS-OVERVIEW
Introduction
Classification
Polyurethanes
PTFE
Polyethylene
Polypropylene
Polyacrylates
PMMA
Hydrogel, Silicone Rubber
Biopolymer
Thermoplastic and Thermosetting Plastics

Drug
Delivery
Devices

Polymers

Skin/cartilag
e
Ocular
implants
Bone
replacements

Orthopedic
screws/fixatio
n

Metals

Dental
Implants

Synthetic
BIOMATERIALS

Semiconductor
Materials
Implantable
Microelectro
des

Ceramics

Dental
Implants
Biosensors

Heart
valves

INTRODUCTION

Polymeric biomaterials are widely used in clinical

applications such as dentistry, ophthalmology,
orthopedics,

cardiology,

drug

delivery,

sutures, plastic and reconstructive surgery,

and tissue engineering.

Polymeric biomaterials are chosen for different

applications depending on their properties. They

act as substitutes for soft and hard tissues in
the body.

INTRODUCTION
Natural Polymers
Polymers derived from living creatures
Scaffolds grow cells to replace damaged tissue

Desirable properties:
Biodegradable
Non-toxic
Mechanically similar to the replaced tissue
Capable of attachment with other molecules

Natural polymers used as biomaterials

Collagen, Chitosan and Alginate

COLLAGEN
Consist of three intertwined protein
chains, helical structure
Collagen can be desorbed into the
body, non-toxic , minimal immune
response
Can be processed into a variety
formats

Porous sponges, Gels, and Sheets

Applications

Surgery, Drug delivery, Prosthetic

implants and tissue-engineering of
multiple organs

CHITOSAN
Derived from chitin, present in hard exoskeletons
of shellfish like shrimp and crab
Chitosan desirable properties

Minimal foreign body reaction

Mild processing conditions
Controllable mechanical/biodegradation properties

Applications
In the engineering of cartilage, nerve, and liver
tissue,
wound dressing and drug delivery devices

ALGINATE
A polysaccharide derived from brown seaweed
Can be processed easily in water, non-toxic,
biodegradable, controllable porosity
Forms a solid gel under mild processing

Has been explored for use in:

Liver, nerve, heart, cartilage & tissue-engineering

Mechanical weakness: low strength & poor cell

adhesion

Can be overcome by enhancing with other

materials

SYNTHETIC POLYMERS

Advantages of Synthetic Polymers

Ease of manufacturability, process ability and

reasonable cost

The Required Properties

Biocompatibility
Sterilizability
Physical Property
Manufacturability

Applications

Medical
disposable
materials,
Dental
dressings, polymeric
engineering products

supplies,
Prosthetic
materials,
implants,
drug delivery, tissue

WHAT IS POLYMER
Polymers

(poly=many
and mer-units)
A long molecule made
up from lots of small
molecules
called
monomers.
Covalent Binding

ALL THE SAME MONOMER

Monomers

all same

type (A)
A+A+A+A
-A-A-A-A eg poly(ethene)
polychloroethene
PVC

DIFFERENT MONOMERS
Monomers of two different types A + B
A+B+A+B
-A-B-A-B eg polyamides
polyesters

POLYMERIZATION

Process of reacting monomer molecules together

in a chemical reaction to form three-dimensional
networks or polymer chains
Addition Polymerization
Condensation Polymerization

Structural
Modification

Molecular Weight
Cross-linking

Effect of
Temperature

POLYMERIZATION
Polymerization

is a process of
reacting monomer molecules together in
a
chemical
reaction
to
form polymer chains or threedimensional networks.

POLYMERIZATION
Polymers such as PVC are referred to as
"homopolymers" as they consist of repeated long
chains or structures of the same monomer unit,
whereas polymers that consist of more than one
molecule are referred to as copolymers.

ADDITION POLYMERIZATION

An addition polymer is a polymer which is

formed by an addition reaction, where
many
monomers
bond
together
via
rearrangement of bonds without the loss of any
atom or molecule.
Addition Polymerization can be achieved by
rearranging the bonds within each monomer

ADDITION POLYMERIZATION

Addition polymers are usually made

a monomer containing a double bond.

from

We can think of the double bond as "opening out"

in order to participate in two new single bonds in
the following way:

ADDITION POLYMERIZATION
Thus,
if
ethylene
is
heated
at
moderate temperature and pressure in the
presence of an appropriate catalyst, it
polymerizes:

ADDITION POLYMERIZATION
The formation of a polymer by addition
polymerization is an example of a chain reaction.
Once a chain reaction gets started, it is able to
keep itself going.

The three steps of this reaction to focus on are

how the reaction gets started (INITIATION)
how the reaction keeps going (PROPAGATION)
how the reaction stops (TERMINATION)

ADDITION POLYMERIZATION
Mechanism involving Free Radical
Initiation
A peroxide molecule breaks up into two reactive
free radicals. Light or heat can provide the
energy needed for this process.
We can write an equation for this process:

ADDITION POLYMERIZATION
The second part of initiation occurs when the free
radical initiator attacks and attaches to a
monomer molecule.
This forms a new free radical, which is called the
activated monomer.
We can write an equation for this process, too:

ADDITION POLYMERIZATION
Propagation

During a chain reaction, most of the time is

spent in the propagation phase as the polymer
chain grows.
In the propagation phase, the newly-formed
activated monomer attacks and attaches to the
double bond of another monomer molecule.
This addition occurs again and again to make
the long polymer chain.

ADDITION POLYMERIZATION

Once again, we can write an equation for this

reaction:

The "n" stands for any number of monomer molecules,

typically in the thousands.

ADDITION POLYMERIZATION
Termination
This chain reaction cannot go on forever.
The reaction must terminate, but how?
A growing polymer chain joins with another free
radical.
We watched a peroxide break up to form two
radicals. It makes sense that two free radicals
could join to make a stable bond.
The equation representing this step of the chain
reaction can be written simply as:

SOME ADDITION POLYMERS

Monomer

Nonsystematic
Polymer
Name

Some Typical
Uses

Ethylene

Polyethylene

Film for
packaging and
bags, toys,
bottles, coatings

Polypropylene

Milk cartons,
rope, outdoor
carpeting

Polystyrene

Transparent
containers,
plastic glasses,
refrigerators,
styrofoam

Propylene

Styrene

SOME ADDITION POLYMERS

Pipe and tubing,
raincoats,
curtains,
phonograph
records,
luggage, floor
tiles

Vinyl chloride

Polyvinyl
chloride, PVC

Acrylonitrile

Polyacrylonitrile
Textiles, ruga
(Orlon, Acrilan)

Tetrafluoroethyl
Teflon
ene

Nonstick pan
coatings,
bearings,
gaskets

CONDENSATION POLYMERIZATION
Condensation polymers are any kind
of polymers formed through a condensation
reactionwhere molecules join together-losing small molecules as by-products such
as water or methanol

CONDENSATION POLYMERIZATION

During Condensation Polymerization, a small

molecule such as water will be condensed out by
the chemical reaction:

R-NH2 + RCOOH

RCONHR + H2O

(amine) (carboxylic acid)

(amide) (condensation molecule)

CONDENSATION POLYMERIZATION
One

major drawback of condensation

polymerization is tendency for the
reaction to cease before the chain grows to
sufficient length.

This

is due to decreased mobility of the

chains. This results in shorter chains

SOME COMMON CONDENSATION POLYMER

Polyester
Polyamide
Polyurea
Polyurethane
Polysiloxane
Protein
Cellulose

BONE CEMENT: PMMA

PMMA: Polymethyl methacrylate

Used for Fixation of joint prosthesis for hip and

knee joints.

Bone cement is made up of PMMA Powder and

monomer methyl methacrylate liquid.

BONE CEMENT: PMMA

Liquid Component (20ml)

Solid Powder(40g)

Methyl Methacrylate(monomer) 97.4

vol%

Polymethyl methacrylate 15.0 wt%

N,N Dimethyl-p-toluidine 2.6 vol%

Methyl methacrylate co-polymer

75.0 wt%

Hydroquinone 7515 ppm

Barium Sulfate 10.0 wt%

Dibenazoyl peroxide

BONE CEMENT: PROCESS

Hydroquinone is added to prevent premature
polymerization, which may occur under exposure
to light, or elevated temperature.
N,N dimethyl-p-toluidine is added to promote
curing of the finished product.
The solid component is a finely grounded .
When the powder and liquid are mixed together ,
the monomer liquid is polymerized by free radical
polymerization.
Dibenzoyl peroxide mixed with the powder, will
react to form monomer to form monomer radical.
Finally dimer radical

BONE CEMENT: PROCESS

The process continues until long chain polymers
are formed.
The monomer liquid wets the polymer powder
particles and links them together after
polymerization
Polymerization during curing increases the degre
of polymerization. i.e molecular weight.

BONE CEMENT: CONCERN

Porosity development during the curing process.
Large pores of about millimeters diameters are
observed in clinical situations.
Monomer vapors and air trapped during the
mixing process is the main reason for porosity
development.
One can reduce these porosity by using vacuum
and centrifugation technique during mixing of
monomer and powder.
But
this may result in depletion of
monomer, segregation of constituents by
centrifuging etc.

FACTORS AFFECTING BONE CEMENT

PROPERTIES

Intrinsic Factors

Composition of monomer and powder.

Powder particle size, shape and distribution :
degree of polymerization.
Liquid/Powder ratio

Extrinsic Factors
Mixing environment, temperature, humidity,
type of container.
Mixing Technique: Rate and number of beating
with spatula.
Curing environment: temperature, pressure,
contacting surface (tissue, air, water etc)

FLUOROCARBON POLYMERS

The

best

known

fluorocarbon

is

polytetrafluoroethylene (PTFE) commonly

know as TEFLON

Other polymers containing fluorine are:

Polytrifluorochloroethylene

Polyvinylfluoride

Fluorinated ethylene propylene

POLYTETRAFLUOROETHYLENE:PTFE

PTFE is made from tetrafluoroethylene under

pressure with peroxide catalyst in the presence
of excess water for removal of heat.

PTFE: PROPERTIES

This polymer is highly crystalline (94% above)

Molecular weight . g/mol.

The polymer has very high density: 2.15-2.2

/

Low modulus of elasticity (0.5GPa)

Low tensile strength(14 MPa).

Very

low

surface

coefficient(0.1)

tension

and

friction

PTFE: PROPERTIES

PTFE has an unusual property of expanding in

microscopic scale into a micro porous materials

thus can be used as an external thermal
insulator.

PTFE can not be injection molded or metal

extruded

because

of

its

very

high

melt

viscosity.

So the powders are sintered to above 327degC

under pressure to produce implants.

PTFE: PROPERTIES

Sintering

is

method

for

creating

objects

from powders, including metal and ceramic powders.

It is based on atomic diffusion. Diffusion occurs in
any material above absolute zero, but it occurs much

faster at higher temperatures. In most sintering

processes, the powdered material is held in a mold
and then heated to a temperature below the melting

point

RUBBERS

Silicon, Natural and Synthetic Rubbers

Rubbers as defined by ASTM

A material which at room temperature cab be

stretched repeatedly to at least twice its

original length and upon release of the
stress, returns immediately with force to its
approximate original length

RUBBERS

The amount of cross-linking for natural rubber

controls the flexibility of the rubber: the addition

of 2-3% sulfur results in a flexible rubber, while
adding as much as 30% sulfur makes it a hard

rubber.

Rubbers contains antioxidants to protect them

against

decomposition

by

oxidation,

hence

improving aging properties.

Fillers like Carbon black or silica powder are also

used to improve their physical properties.

RUBBERS

Natural rubber is made from latex of Hevea

brasiliensis tree.

Shows high blood compatibility.

SILICON RUBBERS

Silicon rubber developed by Dow Corning

used for medical use.

The repeating unit is dimethyl siloxane,

which

is

polymerized

polymerization.
unstable
polymers.

and

The

by

condensation

reaction

condenses,

product

resulting

is

into

SILICON RUBBER

SILICON RUBBERS

Silicon rubbers contains silica SiO2 powder

as a filler to improve their mechanical
properties.

Polyurethanes

are

usually

thermosetting

polymers they are widely used to coat

implants.

THERMOPLASTICS

Thermoplastics is a polymer.

It

becomes

moldable

above

specific

temperature and returns to a solid state

upon cooling.

Polymeric

chains

associate

through

intermolecular forces.

Intermolecular interactions increases upon

cooling.

THERMOPLASTICS

Property Change

Above glass transition temperature and below

its melting temperature there is drastic change
in the physical properties of the Thermoplastics.

Examples

Polyacetals

Polysulfones

Polycarbonates

Polyformaldehyde

THERMOPLASTICS

Polyacetals/Polyformaldehyde

both

names

used interchangeably

Sometimes called as POM/Delrin(DuPont)

Poly oxy methylene

Formed by reacting formaldehyde

THERMOPLASTICS

Polyoxymethylene Properties

High abrasion resistance

Low coefficient of friction

High heat resistance

Good Electrical Properties

Low water absorption

Resistance to most chemicals/water

THERMOPLASTICS

Polyoxymethylene Applications

Insulin Pens

Metered Dose Inhalers

Implant Material

THERMOPLASTICS

Polusulfones

Developed by Union Carbide in 1960

Chemical Formula

THERMOPLASTICS

Polyusulfones Properties

High thermal Stability (due to presence of

bulky side groups and rigid main backbone
chain).

Stable to most chemicals.

Applications

Implant Material

Hemodialysis membranes (pore size 40 nm)

THERMOPLASTICS

Polycarbonates

Made by reacting bisphenol A and diphenyl

carbonate.

Best

known

commercial

Lexan(general Electric)

polycarbonate

is

THERMOPLASTICS

Polycarbonates

Made by reacting bisphenol A and diphenyl

carbonate.

Best known commercial polycarbonate is

Lexan(general Electric)

Tough, Amorphous, Transparent.

Excellent mechanical/thermal properties.

THERMOPLASTICS

Polycarbonates Applications

Renal

Dialysis-Polycarbonate

Filter

Cartridge housing membrane.

Cardiac

Surgery

Oxygenators,

Blood

Products-Blood
Reservoirs,

Blood

Filters

Surgical Instruments: Used in minimally

invasive surgery, trocars.

IV Connectors

DIALYZERS

CARDIAC SURGERY PRODUCTS

CARDIAC SURGERY PRODUCTS

THERMOSETS/ THERMOSETTING POLYMERS

Thermoset materials are those materials that

are made by polymers joined together by
chemical bonds, acquiring a highly cross linked
polymer structure.

The highly cross linked structure produced by

chemical

bonds

in

thermoset

materials,

is

directly responsible for the high mechanical and

physical strength.

THERMOSETS/ THERMOSETTING POLYMERS

THERMOSETS/ THERMOSETTING POLYMERS

One

of

characteristic

parameter

of

thermosets

materials are the gel point, which refers to the time

when the material changes from an irreversible
way-viscous liquid state to a solid state during the

curing process.

Once has been transferred the gel point the

material stops flowing and it can not be molded or

processed grid.

One of the negative aspects of thermosets is its no

ability to recycle

THERMOSETS CHARACTERISTICS

Molded-in color (no paint required)

Excellent cosmetic appearance

Antimicrobial properties

Corrosion resistance

High-temperature heat and flame resistance

Dimensional control

Dielectric strength and thermal insulation

X-ray transparency or opaqueness

THERMOSETS APPLICATIONS

Instrumentation covers, bases, and components

Standard and contagious/biohazard trash cans

and receptacles

X-ray film containers

PROPERTIES OF POLYACETOL,
POLYSULFONES AND POLYCARBONATES
Property

Density /3

Polyacetal
(Delrin)

Polysulfones
(Udel)

Polycarbonates
(Lexan)

1.425

1.24

1.20

70

70

63

15-75

50-100

60-100

Tensile Modulus
(GPa)

3.65

2.52

2.45

Water Absorption
(%, 24 hr)

0.25

0.3

0.3

Tensile Strength
(MPa)
Elongation (%)