BIOMATERIALS

ENT 219

Lecture 10
Polymeric Biomaterials
 1.0 Introduction
◼ Application of synthetic polymers
◼ medical disposable supply
◼ prosthetic materials,
◼ dental materials
◼ implants
◼ dressings
◼ extracorporeal devices
◼ encapsulants
◼ polymeric drug delivery systems
◼ tissue engineered products
◼ orthodosis

2
 1.0 Introduction

Main Advantages
◼ Ease of manufacturability to produce various shapes
◼ Ease of secondary processability
◼ Reasonable cost
◼ Availability with desired mechanical and physical
properties.

3
1.0 Introduction

4
 2.0 Basic Structure
◼ Polymers have very long chain molecules which are
formed by covalent bonding along the backbone
chain.

◼ The long chains are held together by:

◼ primary covalent bonding forces thru crosslinks between
chains
◼ 2ndary bonding forces such as van derWaals & hydrogen
bonds

◼ Each chain can have side groups, branches &

copolymeric, chains or blocks
5
 2.0 Basic Structure
◼ As the molecular chains become longer, their relative
mobility decreases
◼ The higher the molecular weight, the less the mobility
of chains which results in higher strength & greater
thermal stability
◼ Polymer chains can be arranged in 4 ways:
◼ Linear
◼ Branched,
◼ Cross-linked
◼ Three-dimensional network

6
2.0 Basic Structure

7
 3.0 Crystal & Amorphous
Structure in Biopolymer
◼ Crystallization is easier for polymer with shorter
chain
◼ Branched polymer in which side chains are attached
to the main backbone chain at positions will not
crystallize easily
◼ Linear polymers are much easier to crystallize
◼ Partially crystallized structure (semicrystalline) is
commonly occur in linear polymers
◼ The cross-linked or 3-D network polymers cannot
be crystallized at all & they become amorphous
polymers.

8
 3.0 Crystal & Amorphous
Structure in Biopolymer
◼ Polymer with small side group are easy to
crystallize
◼ Isotactic & syndiotactic polymers usually crystallize
even when the side groups are larger
◼ Copolymerization always disrupts the regularity of
polymer chains thus it is more amorphous
◼ Plasticizers can prevent crystallization by keeping
the chains separated from one another

9
 3.0 Crystal & Amorphous
Structure in Biopolymer

Classical “fringed-micelle” model which shows the

amorphous and crystalline regions coexist
10
 4.0 Biopolymers Properties

◼ Thermoplastic Polymers
◼ Usually have linear & branched structures, they
soften when heated & harden when cooled.
◼ The process reversible & can be repeated
◼ The reheating and reforming process did not
have significant change on the polymer
properties
◼ Mostly consist of a very long main chain of
carbon atoms covalently bonded together

11
 4.0 Biopolymers Properties

◼ Thermoplastic Polymers

12
 4.0 Biopolymers Properties

◼ Thermosetting Polymers

◼ The term implies that heat is required to

permanently set the plastic
◼ Thermosets polymer, once having hardened, will
not soften upon heating, their structures are
cross-linked & network.
◼ They could be degrade or decompose if heated
at very high temperature
◼ Thermoset polymers are harder & stronger than
thermoplastics

13
 4.0 Biopolymers Properties
◼ Thermosetting Polymers

14
15
 5.0 Polymeric Biomaterials

◼ Only ten to twenty polymers are mainly

used in medical device fabrications from
disposable to long-term implants

16
 5.0 Polymeric Biomaterials
Polyethylene (PE)
◼ Available commercially as
◼ high density (HDPE)
◼ low density (LDPE)
◼ linear low density (LLDPE)
◼ very low density (VLDPE)
◼ ultra high molecular weight (UHMWPE)

◼ Clear to whitish translucent thermoplastic

17
 5.0 Polymeric Biomaterials
Polyethylene (PE)…(continue)

• Low
density

• High
Density

• Linear low
density

18
 5.0 Polymeric Biomaterials
Polyethylene (PE)…(continue)

19
 5.0 Polymeric Biomaterials
Polyethylene (PE)…(continue)

◼ HDPE -pharmaceutical bottles, nonwoven fabrics, &

caps
◼ LDPE - flexible container applications, nonwoven-
disposable & laminated (or coextruded with paper) foil
& polymers for packaging.
◼ LLDPE - pouches & bags due to its excellent puncture
resistance
◼ VLDPE - extruded tubes.

20
 5.0 Polymeric Biomaterials
Polyethylene (PE)…(continue)
◼ UHMWPE (MW >2×106 g/mol) has been used for orthopedic
implant fabrications.
◼ This orthopedic implant fabrications include load-bearing
applications:

◼ Acetabular cup of total hip

◼ Tibial plateau &
◼ Patellar surfaces of knee joints.

◼ Specific Properties: Low cost, easy to process, excellent electrical

insulator, excellent chemical resistance, tough & flexible even at
low temperature
21
 5.0 Polymeric Biomaterials
Polyvinylchloride (PVC)
◼ PVC is amorphous, does not recrystallize due to the large side
group (Cl, chloride)
◼ It has a high melt viscosity hence it is difficult to process.
◼ PVC homopolymer has high strength (7.5 to 9 psi) & brittle
◼ PVC sheets & films – blood, solution storage bags & surgical
packaging

22
 5.0 Polymeric Biomaterials
Polyvinylchloride (PVC)…continue
◼ PVC tubing-commonly used in intravenous (IV) administration,
dialysis devices, catheters, & cannulae
◼ Specific Properties: Excellent resistance to abrasion, good
dimensional stability, high chemical resistance
Note:
◼ To prevent the thermal degradation of the polymer (HCl could be
released), thermal stabilizers -metallic soaps/salts are
incorporated
◼ Di-2-ethylhexylphthalate (DEHP or DOP) is used in medical PVC
formulation.

23
 Coronary Stent Implant

◼ Percutaneous transluminal
coronary angioplasty (PTCA or
angioplasty)

◼ PTCA means:
Percutaneous – performed
through the skin
Transluminal – through the
inside opening of a vessel
Coronary – relating to arteries or
veins of the heart
Angioplasty – a procedure to
open blood vessels

24
 5.0 Polymeric Biomaterials
Polypropylene (PP)
◼ High melting (165-1770C) & heat deflection temperature
◼ Additives for PP such as antioxidants, light stabilizer, nucleating
agents, lubricants, mold release agents, antiblock, & slip agents
are formulated to improve the physical properties &
processability
◼ PP has an exceptionally high flex life & excellent environment
stress-cracking resistance, hence it had been tried for finger joint
prostheses with an integrally molded hinge design [Park, 1984]

25
 5.0 Polymeric Biomaterials
Polypropylene (PP)…continue
◼ PP is used to make disposable hypothermic syringes, blood
oxygenator membrane, packaging for devices, solutions, and
drugs, suture, artificial vascular grafts, nonwoven fabrics, etc.

◼ Specific Properties: Low density, good chemical resistance,

moisture resistance & heat resistance

◼ Good surface hardness & dimensional stability

26
 5.0 Polymeric Biomaterials
Polymethylmetacrylate (PMMA)
◼ Commercial PMMA-amorphous material with good
resistance to dilute alkalis & other inorganic solutions
◼ Best known for exceptional light transparency (92%
transmission), high refractive index (1.49), good
weathering properties & as one of the most
biocompatible polymers
◼ Used broadly in medical applications:
◼ blood pump & reservoir,
◼ IV system,
◼ membranes for blood dialyzer
◼ in vitro diagnostics.
27
 5.0 Biomedical Applications of
Polymeric Biomaterials
Polymethylmetacrylate (PMMA )…continue
◼ It is also found in contact lenses & implantable ocular lenses due
to excellent optical properties
◼ Dentures, & maxillofacial prostheses due to good physical &
coloring properties
◼ Bone cement for joint prostheses fixation

28
 5.0 Biomedical Applications of
Polymeric Biomaterials
Polystyrene (PS) and Its Copolymers
◼ PS has good transparency, lack of color, ease of
fabrication, thermal stability, low specific gravity &
relatively high modulus
◼ Commonly used in tissue culture flasks, roller bottles,
vacuum canisters & filterware
◼ Acrylonitrile–butadiene–styrene (ABS) copolymers
are produced by 3 monomers: acrylonitrile, butadiene
& styrene
◼ Resistant to common inorganic solutions, have good
surface properties, and dimensional stability
◼ For IV sets, clamps, blood dialyzers, diagnostic test
kits
29
 5.0 Polymeric Biomaterials
Polyesters
◼ Frequently found in medical applications due to their
unique chemical & physical properties
◼ PET (polyethyleneterephthalate) is so far the most
important
◼ Biomedical applications-as artificial vascular graft,
sutures & meshes.
◼ It is highly crystalline with high melting temperature,
hydrophobic & resistant to hydrolysis in dilute acids
◼ Polycaprolactone is crystalline & has a low melting
temperature.
◼ Soft matrix or coating for conventional polyester
fibers. Tissue engineering 30
 Polyamides (Nylon)
◼ Flexibility of carbon chain contributes to molecular flexibility, low
melt viscosity and high lubricity
◼ Nylons are hygroscopic and lose their strength in vivo when
implanted
◼ Poly (p-phenylene terephthalate) commonly known as Kevlar®
◼ Very good mechanical properties, good thermal properties, good
chemical resistance, permeable to gases
◼ Tubes for intracardiac catheters,surgical sutures, dialysis devices
components,heart mitral valves, sutures

31
 Polytetrafluoroethylene
(PTFE)
◼ Commonly known as Teflon®
◼ The polymer is highly crystalline, high density, low modulus of
elasticity & tensile strength
◼ It also has a very low surface tension & friction coefficient (0.1)
◼ Specific Properties: Chemical inertness, exceptional weathering &
heat resistance, nonadhesive, very low coefficient of friction
◼ Application: Vascular & auditory prostheses, catheters, tubes

32
 5.0 Polymeric Biomaterials
Rubbers
◼ Rubbers have been used for the fabrication of
implants
◼ Natural rubber is compatible with blood in pure form
◼ Crosslinking by x-ray & organic peroxides produces
rubber with superior blood compatibility
◼ Silicone rubber developed for medical use
◼ Good thermal stability, resistance to atmospheric &
oxidative agents, physiological inertness
◼ Burn treatment, shunt, mammary prostheses,
maxillofacial implants
33
 5.0 Polymeric Biomaterials
Polyurethanes
◼ Polyurethanes are usually thermosetting polymers: they are
widely used to coat implants
◼ polyurethane rubber is quite strong and has good resistance to
oil and chemicals
◼ Exceptional resistance to abrasion, resistance to breaking, very
high elasticity modulus at compression traction & sheering
remarkable
◼ Adhesives, dental materials, blood pumps, artificial heart & skin

34
 5.0 Polymeric Biomaterials
Polyacetal, Polysulfone & Polycarbonate
◼ Polyacetals & polysulfones are being tested as implant
materials
◼ Polycarbonates have found their applications in the
heart/lung assist devices & food packaging
◼ Polyacetals have reasonably high molecular weight &
excellent mechanical properties
◼ Excellent resistance to most chemicals & to water
over wide temperature ranges
◼ Hard tissue replacement

35
 5.0 Polymeric Biomaterials
Polyacetal, Polysulfone & Polycarbonate
◼ Polysulfones have a high thermal stability due to the
bulky side groups (therefore, they are amorphous) &
rigid main backbone chains
◼ Polycarbonates are tough, amorphous, & transparent
polymers
◼ Excellent mechanical & thermal properties,
hydrophobicity & antioxidative properties

36
 5.0 Polymeric Biomaterials
Biodegradable Polymers
◼ Hydrolysis of PLA yields lactic acid which is a normal
byproduct of anaerobic metabolism in the human body
& is incorporated in the tricarboxylic acid (TCA) cycle to
be finally excreted by the body as CO2 & water
◼ PGA biodegrades by a combination of hydrolytic
scission & enzymatic (esterase) action producing
glycolic acid either enter the TCA cycle or is excreted in
urine and can be eliminated as CO2 & water
◼ PLGA can be controlled from weeks to over a year by
varying the ratio of monomers & the processing
conditions
37
 5.0 Polymeric Biomaterials
Biodegradable Polymers…(continue)
◼ PLA-high tensile strength & low elongation resulting in
a high modulus. Application:bone fracture fixation
◼ PLGA-tissue engineered repair systems where cells are
implanted within PLGA films or scaffolds
◼ PLGA-drug delivery systems in which drugs are loaded
within PLGA microspheres
◼ Other-Poly-p-dioxanon:bioabsorbable polymer which
can be fabricated into flexible monofilament surgical
sutures

38
 5.0 Polymeric Biomaterials

Summary

39
 Biopolymers

◼ Polymers are used in biomedical applications

➢ Cardiovascular, Opthalmic and Orthopaedic
implants
➢ Dental implants, dental cements and
denture bases

• Low density, easily formed

and can be made biocompatible.

Recent development – biodegradable polymers.

40
 Cardiovascular Applications

◼ Heart valves can be stenotic or incompetent

◼ Polymers are used to make artificial heart valves
◼ Leaflets are made from biometals
• Sewing ring made from PTFE or
PET
➢ Connected to heart tissue
• Blood clogging is side effect
• PTFE is used as vascular graft to bypass clogged arteries.
• Blood oxygenators : Hydrophobic polymer membranes
used to oxygenate blood during bypass surgery
➢ Air flows on one side and blood on the other side
and oxygen diffuses into blood.

41
 Extra: Opthalmic
Applications
◼ Eye glasses, contact lenses and Intraocular implants are
made of polymers.
◼ Hydrogel is used to make soft contact lenses
➢ Absorbs water and allows snug fit
➢ Oxygen permeable
➢ Made of poly-HEMA
• Hard lenses made from PMMA
➢ Not oxygen permeable
➢ Mixed with Siloxanylalkyl
Metacrylate and metacrylic
acid to make permeable and hydrophilic.
• Intraocular implants are made of PMMA
• Poly-HEMA-Poly(hydroxyethyl methacrylic) acid

42
 Orthopedic Applications

◼ Bone cement: Fills space between implant and

bone – PMMA
➢ Centrifuging and vacuum techniques
minimize porosity
• Used in joint prosthesis (Knee and Hip
replacements)
• Other applications:
➢ Drug delivery systems: Polymer matrix
with drug implanted inside the body
➢ Struture materials: High tensile and knot
pull strength.
➢ Non-absorbable: Polypropylene, Nylon
➢ Absorbable : Polyglycolic acid.

43
 Tissue Engineering

◼ Polymers can be synthesized and blend to suite the

applications
◼ Biodegradable polymers are used as scaffolding for
generation of new tissues
◼ In future, tissues can be generated in vivo or in
vitro for repair or replacement.

44
 Sterilization of
healthcare products
◼ The objective of sterilization is to prevent the
introduction into the body of pathogenic organisms
not normally present.
◼ Sterilization can be defined as ‘the removal or
destruction of all living organisms, including
resistant forms such as bacterial or fungal spores’.

45
Sterilization method

46
 Dry Heat

◼ Dry heat is not generally regarded as being suitable

for plastics due to the low thermal transmission
properties of plastics and the difficulty of insuring
that all parts of the product have been exposed to
the required temperature for an adequate time.
◼ Most plastics will degrade during prolonged dry heat
sterilization.

47
 Autoclaving

◼ Autoclaving uses saturated steam to allow lower temperatures

and shorter times than in the dry heat process.
◼ Steam will penetrate well into a product, as water vapor is lost
due to condensation.
◼ Allow steam to reach all surfaces and for items to reach the
required temperature for sterilization.
◼ The temperatures and times:lower temperatures must be held
for longer times), but it is common for the temperature to be
around 121oC

48
 Autoclaving
◼ used significantly in hospitals for the sterilization of
repeated use articles.
◼ not the predominant method in the commercial
sterilization of medical devices because of the
difficulties involved with autoclaving packaged
products.

49
 Irradiation
◼ Generated by either gamma rays from a
Cobalt (Co60) source or an electron beam
(E-beam).
◼ The cost of capital equipment is great, but
high throughputs will improve the return on
investment.

50
◼ Dosage for either process is measured in Megarad
(Mrad) and
◼ as a general rule a radiation dose of around 2.5
Mrad will sterilize clean articles in air.
◼ very effective for fully packaged and sealed single-
use items (most plastic films are effectively
transparent to radiation) where only one radiation
dose is required.

51
◼ lead to changes in the tensile strength, elongation
at break and impact strength (depend both on the
basic polymer and any additives used).
◼ Irradiated devices are completely safe to handle
and can be released and used immediately after
sterilization.

52
 Ethylene oxide
◼ Ethylene oxide is a powerful alkylating agent and is
regarded by the EPA as a toxic and possibly
carcinogenic gas (exposure to EtO is regulated by
the EPA and OSHA).
◼ When mixed with air, EtO is not only flammable but
can also be explosive.
◼ The effectiveness of EtO sterilization depends on
many variables such as time, gas concentration,
temperature and relative humidity (necessary to
moisten bacteria to insure effective destruction).
monitoring EtO sterilization difficult and time
consuming
53
◼ Some plastics are relatively permeable to EtO and
the process can then be used to sterilize fully
packaged articles by using thin packaging films,
such as PE.
◼ EtO gas to enter the package and sterilize the
contents. The packaging film must also be
permeable to water vapor and air to be effective.

54
55
 Standards

◼ AAMI and ISO have produced a range of standards for

sterilization such as:
• ISO 11135 - Medical devices - Validation and routine control
of ethylene oxide sterilization.
• ISO 11137 - Medical devices - Validation and routine control
of radiation sterilization.
• ISO 11737 - Sterilization of medical devices - Microbiological
methods.
o Part 1: Estimation of population of microorganisms on
products.
o Part 2: Tests of sterility performed in the validation of a
sterilization process.

56