Effect of Sterilization

Techniques on Polymers

Contents of Presentation

Introduction to Polymers
Properties and Stability of Polymers
Affect of Ionising Radiation and Ethylene Oxide on Polymers
The need to test for effects

Applied Sterilisation Technologies

 Introduction to Polymers

Applied Sterilisation Technologies

Health Care Products made from Polymers

Catheters
Artificial limbs (legs, feet, arms)
Dental fillings and bridges
Disposable process equipment
Disposable surgical clothes and instruments
Plasters - some
Eyeglass frames and lenses
Wound dressings 5 year shelf live
Metered Dose Inhalers (MDI)
Medical implants (e.g. Hip joint replacements,
cranial and spinal implants)

Applied Sterilisation Technologies

 What are Polymers?
Polymers are high molecular weight molecules, which form long molecular
chains built up by repetition of low molecular weight, simple chemical
species (monomers)

- Poly (from the Greek) many

- Meros (from the Greek) - parts
Polymers are.. many chemical links chained together

Monomer

Polymer
Applied Sterilisation Technologies

The Structure of Polymers

The basic makeup of many polymers is carbon and

hydrogen
Other elements can also be involved
- Oxygen, chorine, fluorine, nitrogen, silicon, phosphorous, and sulphur are
other elements found in the molecular makeup of polymers.
Polyvinyl chloride (PVC) contains chlorine
Nylon (polyamide) contains nitrogen
Teflon (PTFE) contains fluorine
Polyester and polycarbonates contain oxygen

Applied Sterilisation Technologies

 Basics of Polymer Structure
The simplest polymer structure is polyethylene (thermoplastic)

The repeat units (monomers) join chemically (polymerisation) end-on- end to

produce linear chain-like polymer molecules

n(CH2=CH2) CH3(CH2-CH2)n-1CH3
ethylene monomer polyethylene polymer

Typically n = 1,000 to 10,000

High molecular weights 28,000 to 280,000

Applied Sterilisation Technologies

General Classes of Polymers

Thermoplastics
- Can be repeatedly melted upon the application of heat recyclable because of this
- Can be amorphous or semi-crystalline

Thermosets
- Rigid materials that can withstand higher temperatures than elastomers and plastics -
they do not melt
- Often filled and reinforced with fibrous or particulate fillers

Rubbers
- Usually sulphur or peroxide cross- linked

- Materials that can stretch many times their original length

- Do not melt upon application of heat

Applied Sterilisation Technologies

 Structure of Thermoplastics

Thermoplastics have primary chemical bonds (covalent) between

atoms in chain, and weaker secondary bonds between chains which
break down on heating causing softening

Thermoplastics tend to be flexible

Applied Sterilisation Technologies

Structure of Thermosets

Thermoset plastics have strong primary bonds within and between

(cross links) chains which do not break down on heating, hence no
softening. Thermoset plastics tend to be rigid

Applied Sterilisation Technologies

 Examples of Thermoplastics, Thermosets and Rubbers
Thermoplastics
POM- Acetal , PA - Polyamides , LDPE, HDPE, PP etc. Polyolefins
PEEK- Polyetheretherketone , PPS- Polyphenylenesulphide

Thermosets
PF - phenolic resins, UF - urea resins, MF - melamine resins, Epoxy resins
PU polyurethanes, PE polyesters

Rubbers
NR - Natural rubber, BR Polybutadiene, IR Polyisoprene,
SBR - Styrene- butadiene rubber, EPDM - Ethylene-propylene-diene terpolymers
NBR - Nitrile rubber, FR Fluoroelastomers
Also blends of rubbers and plastics are possible

Applied Sterilisation Technologies

Effect of Ionising Radiation and Ethylene

Oxide on Polymers

Applied Sterilisation Technologies

Stabilisation of Polymers

Ionising Radiation will generate free radicals in the Polymer, which can cause
degradation due to:
Chain scission
Cross-linking
Stabilisers can be added to the polymer to help protect it during sterilization
and during its service life
Different classes of stabiliser:
Chain breaking antioxidants that react with free radicals, e.g. Phenolic
antioxidants
Compounds that decompose the peroxides/hydroperoxides formed in the
polymer when the radicals react with oxygen, e.g. organo-phosphorous
compounds

Applied Sterilisation Technologies

Comparison
Ethylene oxide vs Ionising Radiation
Attributes of Ethylene Oxide (EtO) Sterilization
Can leave toxic residuals or by-products in the polymer
Has limited ability to penetrate into the polymer
Can sterilize almost every plastic
Does not degrade polymers and so can be used for articles that require to
be repeatedly sterilized, e.g. hospital products
Can be used on heat sensitive polymers as alternative to steam
Attributes of Ionising Radiation Sterilization
May degrade some polymers
Has excellent penetration
Does not leave toxic residuals

Applied Sterilisation Technologies

Summary of Potential Affects of Ionising
Radiation and Ethylene Oxide on Polymers
Ionising Radiation
Chain scission reduces overall molecular weight
Cross-linking will increase hardness, modulus, cause flex cracking etc
Free radical reactions can alter the chemical structure of species (polymer
related and additives) within the material
Potential to generate low pH (i.e. acidic) species and non-volatile higher
molecular weight species
Ethylene Oxide
Toxic and highly reactive gas that can leave residuals (see ISO 10993-7)
Ethylene glycol formed upon reaction with water
Less affect on physical properties than ionising radiation
Potential to react with polymer molecules and additives and alter chemistry
change in overall toxicity
Applied Sterilisation Technologies

Potential Undesirable Affects of Irradiation

Change in molecular weight, e.g. reduction due to chain scission

Increase in cross-link density, leading to changes in modulus, hardness etc

Change in colour, e.g. yellowing from oxidation of surface

Generation of an odour due to volatiles formed by reactions with the polymer

molecules and/or additives in the polymer

Applied Sterilisation Technologies

Affect of Ionising Radiation (Gamma and
Electron Beam) on Polymers
Competing chemical reactions result in either :
Chain scission reduction in molecular weight

Cross-linking increase in molecular weight

Of the two - Reduction in molecular weight the least desirable

More severe impairment of mechanical properties
Hence, polymers more prone to chain scission (e.g. PP and PTFE)
are classed as less resistant to ionising radiation that those (e.g. PS
and PE) that tend towards cross-linking
Resistance to ionising radiation varies greatly:
Chemical structure
Presence of fillers, e.g., glass fibres, mineral fillers
Applied Sterilisation Technologies

Analysis and Testing Techniques

Analysis of polymer products before and after sterilization to:

Determine influence on Extractables and Leachables

Effect on physical properties

Strength
Colour
Smell

Applied Sterilisation Technologies

 Critical Gamma Radiation Dose for a
Selection of Common Polymers

Thermosets Critical Plastics Critical Rubbers Critical

Dose (kGy) Dose Dose
(kGy) (kGy)

Polyester + glass 10,000 PET 1000 EPDM 400

Polyurethane 10,000 Polysulphone 700 PU 300

Silicone + mineral 10,000 Polystyrene 600 SBR 300

Epoxy resin 7,000 UPVC 300 NBR 100

Silicone (unfilled) 1,000 Polyamides 300 Hypalon 100

Polyester + mineral 700 Polycarbonate 250 Polysulphide 90

MF resin 40 Polyethylene 100 Butyl 40

Acetal 15 Polypropylene 10 Silicone 40

Polyester (unfilled) 3 PTFE 4 Fluorocarbon 8

Applied Sterilisation Technologies

Conclusions of Presentation

Wide range of polymers and polymer-based materials used in health care

products
Stability of polymers varies according to:
Molecular structure
Presence of stabilizers
Type and levels of other additives present, e.g. Glass fibres
Need to undertake tests to characterise the effect of sterilization on properties
Ionising radiation and Ethylene oxide can both:
Potentially alter the structure and physical properties of polymers
Alter the extractables and leachables profile

Applied Sterilisation Technologies

Thank-you for
listening.
Any questions?