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Medical devices range from simple devices, to This chapter will discuss plastics used in the
test equipment, to implants. Plastics are used more construction of medical devices in three sections.
and more in these devices, for weight, cost, and The first section will review the general composi-
performance purposes. Examples of medical devices tion of plastic materials which will include the
include surgical instruments, catheters, coronary materials added to the basic polymers. The second
stents, pacemakers, magnetic resonance imaging section will discuss many factors that contribute to
(MRI) machines, X-ray machines, prosthetic limbs, the plastic selection. The final section will review
artificial hips/knees, surgical gloves, and bandages. the chemistry, the response to sterilization
processes, and the application of most common on the ends. These three polymer structures are
plastic materials in medical products. shown in Figure 3.1.
3.1.1.2 Isomers
Isomers (from Greek isomerès, isos 5 “equal,”
3.1 Plastic Compositions méros 5 “part”) are compounds with the same
The basic components of plastic and elastomer molecular formula but a different arrangement of
materials are polymers. The word polymer is atoms. There are many kinds of isomers and the
derived from the Greek term for “many parts.” properties can differ widely or almost not at all.
Polymers are large molecules comprised of many Structural Isomers
repeat units, called monomers, that have been Structural isomers have the atoms arranged in a
chemically bonded into long chains. There are completely different order as shown in Figure 3.2.
thousands of commercially available polymers that Here both polymer repeating groups have the same
are the basis of plastics. While some plastics are formula, aC4H8a, but the atoms are arranged dif-
neat polymers, more often than not they are formu- ferently. The properties of structural isomers may
lated products containing a blend of ingredients be very different from each other.
each added for a purpose. Often the repeating group in a polymer has
exactly the same formula, but the repeating group
3.1.1 Polymer Properties is flipped over as shown in Figure 3.3. If one views
the repeating group as having a head and a tail,
For any given polymer type, there can be hun- then the different ways to connect neighboring
dreds of grades manufactured by multiple resin repeating units is head tail, head head, and
manufacturers with distinctly different properties. tail tail.
Some of these grades include variations of the basic
polymer: its size or its structure. Other variations Geometric Isomers
are the added ingredients (or additives) which may When there is a carbon carbon double bond in
be incorporated to modify performance, appear- a molecule, there may also be two ways to arrange
ance, or other purposes. Variations in the polymer the groups attached to the double bonds. This is
structure are discussed in the next section.
best seen in side-by-side structures as shown in Polypropylenes (PPs) all have the same simpli-
Figure 3.4. fied structural polymer formula of polypropene as
These structures are called geometric isomers shown in Figure 3.5.
which owe their existence to hindered rotation There are, however, subtle differences in the
about double bonds. If the substituents are on the ways the polypropene structure can be arranged.
same side of the double bond, then the isomer is Figure 3.6 shows a longer structure of polypropene,
referred to as cis- (Latin: on this side). If the substi- one that also shows some three-dimensional struc-
tuents are on the opposite side of the double bond, ture. This structure shows how some bonds (the
these are referred to as trans- (Latin: across). dotted lines) are behind the plane of the paper
while others stick out of the paper (the ones on the
Stereoisomers—Syndiotactic, Isotactic, Atactic ends of the little triangular wedges). In this struc-
Stereoisomerism occurs when two or more mole- ture, some of the aCH3 groups are presented above
cules have identical molecular formula and the the paper plane and others are behind the paper
same structural formula (i.e., the atoms are plane. This is called atactic polypropene.
arranged in the same order). However, they differ Atactic polypropene has at random about 50% of
in their two or three dimensional (spatial) arrange- hydrogen/methyl groups in the front and the back
ments of their bonds. This means distinct spatial of the CaCaC chain viewing plane. This form of
arrangements of the atoms—even though they are polypropene is amorphous (noncrystalline) and has
bonded in the same order. The concept would best an irregular structure due to the random arrange-
be understood by an example. ment of the methyl groups attached to the main
carbon carbon chain. It tends to be softer and
more flexible than the other forms of this polymer
which are described next.
In isotactic polypropene, all the methyl groups
are positioned in front of the CaCaC chain viewing
plane and all of the hydrogen atoms are at back, as
shown in Figure 3.7. This stereoregular structure
maximizes the intermolecular contacts and thus
increases the intermolecular forces as compared to
the atactic form. This regular structure is much
Figure 3.3 Head to tail isomers [2]. stronger (than the atactic form) and is used in sheet
and film form for packaging and carpet fibers.
Syndiotactic polypropene has a regular alterna-
tion of 50% of hydrogen/methyl groups in front/
Figure 3.4 cis- and trans-isomers. Figure 3.5 The structure of polypropene.
back of the CaCaC chain viewing plane as shown Molecular weight of the polymers that are used
in Figure 3.8. Its properties are similar to isotactic in medical plastics affects a number of their proper-
polypropene rather than the atactic form, i.e., the ties. While it is not always possible to quantify the
regular polymer structure produces stronger inter- molecular weights of plastics, as mentioned previ-
molecular forces and a more crystalline form than ously, higher flowing plastics of a given series of
the atactic polypropene. products generally have lower molecular weights.
relatively expensive polymer used which reduces terms of the coefficient of friction (COF). Plastic
the overall cost. films with high COF tend to stick together instead
Platelet additives may impart color and luster, of sliding over one another. Sticking makes the
metallic appearance, or a pearlescent effect, but handling, use, and conversion of films difficult. To
they also can strongly affect permeation properties. overcome sticking, slip agents are added.
Most of these additives have little or no permeation Slip additives are divided into two migrating and
through themselves, so when a film contains partic- non-migrating types. Migrating slip additives are
ulate additives, the permeating molecule must fol- the most common class and they are used above
low a path around the particulate additive as shown their solubility limit in the polymer. These types of
in Figure 3.11. This is called a tortuous path effect. additives are molecules comprised of two distinct
parts, typically pictured as a head and tail as shown
3.1.3.2 Release Agents in Figure 3.12. One part of the molecule, usually
the head, is designed to be soluble in the polymer
External release agents are lubricants, liquids, or
(particularly when it is molten during processing)
powders, which coat a mold cavity to facilitate part
making up the plastic. The other part, the tail, is
removal. Internal release agents, which are part of the
insoluble. As the plastic cools and solidifies from
plastic formulation, can accomplish the same purpose.
its molten state, these molecules migrate to the sur-
The identities of the release agents are rarely disclosed,
face, where the insoluble end “sticks out” reducing
but frequently they are fine fluoropolymer powders
the COF. This process is shown in Figure 3.12.
(called micropowders), silicone resins, or waxes.
These additives are typically fatty acid amides.
Some common non-migrating slip additives are
3.1.3.3 Slip Additives/Internal dusted on plastic surfaces. These include:
Lubricants
When polymeric films slide over each other, • PTFE (polytetrafluoroethylene) in micropowder
they encounter a resistance that is quantified in form imparts the lowest COF of any internal
3: PLASTICS USED IN MEDICAL DEVICES 27
Figure 3.11 Tortuous path of permeant molecule through a particulate containing film.
Insoluble tall
Soluble head
• conductive filler (bulk and surface effect); Hip and bone implants
it must be light enough to handle precisely. The absorption, lubricity, and wear resistance. Important
design engineer must consider the loads, stresses, mechanical properties are tensile strength, tensile
and impact that the product might see during its use. elongation, tensile modulus, impact resistance (all
Other physical properties can be important including for toughness), and flexural modulus. Details on the
transparency/opacity, color (some items might use importance of these properties and their measure-
color to aid in identification), aesthetics, water ment are available in the literature [8].
3: PLASTICS USED IN MEDICAL DEVICES 31
130
PC 1— Low molecular weight
Notched izod impact strength (% retention)
120 PC 2
PC 3
110
PC 4— High molecular weight
100
90
80
70
60
50
40
30
20
10
0
0 1 2 3 4 5 6 7 8 9 10 11
Number of cycles
Figure 3.13 The effect of steam sterilization on the impact strength of PCs [10].
32 HANDBOOK OF POLYMER APPLICATIONS IN MEDICINE AND MEDICAL DEVICES
300000
250000
200000
Molecular weight
150000
100000
50000
0
0 10 20 30 40 50 60 70 80
Radiation dose (kGy)
Figure 3.14 The effect of electron beam sterilization on the molecular weight of polylactic acid (PLA).
140
Tensile stress
120 Tensile strain
Molecular weight
Percent property retention (%)
100
80
60
40
20
0
0.0 0.5 1.0 1.5 2.0
Radiation dose (kGy)
resistance, flexibility, transparency and clarity, sterili- products must be nonirritating, chemically resistant,
zation resistance, toughness, tear and burst strength, and stain resistant.
softness, and no leachables and extractables (dis-
cussed in the next section). End-of-life and disposal
requirements are also important. Endoscopy is one
area that uses a lot of electronics and ancillary pro- 3.2.7 Leachables and Extractables
ducts like cameras, light sources, monitors, and An important criterion for the use of plastics in
recording equipment. Electric, power, and thermal medical device applications is quantifying the type
management is very important, including material and amount and identifying the material that is
durability and toughness. Infection control products leached out or extracted from the plastic when in
and devices include gloves, masks, drapes, and contact with chemicals, reagents, or bodily fluids
gowns. Apart from fit and comfort, materials for these during the end use. Extractables and leachables are
3: PLASTICS USED IN MEDICAL DEVICES 33
compounds that can be extracted from the elasto- 3.2.9 Shelf Life and Aging
meric or plastic components, or coatings. This is
commonly considered for containers and medical Accurate prediction of medical product shelf-life
devices that come into contact with solvents such performance is critical. Fortunately, the majority of
as alcohol at various temperatures of use and stor- medical products are constructed from a limited
age. The difference between extractables and leach- number of polymers that have been well character-
ables is slight; leachables is generally a more ized in terms of change in their properties over
aggressive exposure that is meant to indicate a extended-use periods. A procedure known as the
worst-case scenario. simplified protocol for accelerated aging (also
Both extractables and leachables are affected by called the “10-degree rule”) is used. When applied
the type and amount of additives in the formulation to well-characterized polymer systems over moder-
of the plastic. They include plasticizers, antioxi- ate temperature ranges, the test results obtained can
dants, stabilizers, pigments, lubricants, vulcanizers, be within the required degree of accuracy [11].
catalysts, residual monomers and oligomers, resid-
ual solvents, and contaminants. 3.2.10 Joining and Welding
The extracts or leachants are often used for the
Medical devices may have complex shapes that
further biological tests. Cytotoxicity is the assess-
cannot be molded directly. In these cases, the plastic
ment of the (toxic) effect of chemicals on cells.
parts made need to be separately made and joined
Sensitization tests determine the allergic or hyper-
together with adhesives or by welding. A number of
sensitivity reactions of skin and tissues when
techniques are used for welding, including:
exposed to materials or their extracts for prolonged
periods of time. Irritation tests determine whether
• Hot gas welding
the part, material, or extract causes local irritation
on skin or mucous membranes via exposure • Speed tip welding
through skin, eye, or mucosa. Acute system toxicity • Extrusion welding
testing evaluates whether the extracts cause toxicity • Contact welding
effects on various systems of the body when
injected into the animal. Subchronic toxicity testing • Hot plate welding
is used for all implants. The extract is injected • High-frequency welding
intraperitoneally (in the abdomen walls) or intrave- • Injection welding
nously (in the veins) and evaluated for system tox-
icity effects. Genotoxicity testing evaluates the • Ultrasonic welding
genetic damage caused by the extracts. • Friction welding
Hemocompatibility evaluates the compatibility of • Spin welding
materials and their extracts with blood and blood
• Laser welding
components.
• Solvent welding.
HDPE
3.3 Common Medical Device Density = 094-0.97 g/cm3
Polymers Melt point = 128–136°C
3.3.1 Polyethylene
LDPE
Polyethylene can be made in a number of ways. Density = 0.915-0.935 g/cm3
The way it is produced can affect its physical prop- Melt point = 105–115°C
EtO has no effect on the properties of HDPE. cold temperatures to the compound. This type
Polyethylene will oxidize or cross-link under high- has intermediate stiffness and tensile strength
energy radiation and needs to be stabilized to and is quite cloudy. In general, the more eth-
reduce it. In some cases, UHMWPE is deliberately ylene monomer added, the greater the impact
cross-linked with high-energy radiation to improve resistance with correspondingly lower stiff-
the wear behavior in the knee and hip implants. ness and tensile strength.
Radiation doses of 50 100 kGy are used for cross-
linking and standard doses of 25 40 kGy (in an
inert atmosphere) are used to sterilize the Oriented and multilayered films of PP are also
UHMWPE parts. common.
Applications and uses: Containers, packaging Sterilization resistance: The use of PP films in
films, pouches, lidstock, breather patches, and radiation-sterilized applications is somewhat lim-
headers for bags. UHMWPE is used as the wear- ited. The high ratio of film surface area to mass,
bearing surface of hip and knee arthroplasty and combined with the sensitivity of irradiated PP to
total joint replacement. oxygen-promoted degradation, causes them to be
severely embrittled after normal sterilizing doses of
radiation. Even resin formulations which yield
3.3.2 Polypropylene highly radiation-resistant injection molded devices
The three main types of PP are generally are badly degraded after irradiation in thin film
form. Special formulations of medical PP are com-
available:
ing to market specifically to overcome this disad-
vantage. Blends of PP and metallocene-catalyzed,
1. Homopolymers are made in a single reactor
ethylene-based plastomers are particularly suited to
with propylene and catalyst. It is the stiffest
of the three propylene types and has the high- the construction of highly radiation-resistant, thin-
gauge medical device packages.
est tensile strength at yield. In the natural
state (no colorant added), it is translucent and Gamma radiation resistance: Basell offers sev-
eral grades which are specially formulated to mini-
has excellent see-through or contact clarity
with liquids. In comparison to the other two mize the effects after typical radiation sterilization
dosages of up to 5 megarads, as tested by Basell
types, it has less impact resistance, especially
protocol. Catastrophic failures have been reported
below 0°C.
in gamma-sterilized PP materials that experienced
2. Random copolymers (homophasic copolymer) shelf-life storage. This was a result of long-term
are made in a single reactor with a small degradation. “Long-lived free radicals trapped in
amount of ethylene (,5%) added which dis- the crystalline domains migrated toward the crystal-
rupts the crystallinity of the polymer allowing line/amorphous interface combining with available
this type to be the clearest. It is also the most oxygen to form peroxy and hydroperoxy radicals
flexible with the lowest tensile strength of the that initiated degradation near the interface. As
three. It has better room temperature impact enough tie molecules between crystallites were cut
than homopolymer but shares the same rela- through the chain scission process, significant
tively poor impact resistance at low reduction of PP’s elongation could occur which
temperatures. would lead to catastrophic failures” [12].
3. Impact copolymers (heterophasic copolymer), PP materials that are adequately stabilized can
also known as block copolymers, are made in survive the radiation stabilization process with
a two reactor system where the homopolymer enough antioxidant remaining to protect the steril-
matrix is made in the first reactor and then ized product from further degradation. The stability
transferred to the second reactor where ethyl- of sterilized PP depends on the supplier stabilizer
ene and propylene are polymerized to create system, and the stability of a radiation-sterilized PP
ethylene propylene rubber (EPR) in the form can be simply and rapidly determined by oxygen
of microscopic nodules dispersed in the induction testing (OIT) [13].
homopolymer matrix phase. These nodules Autoclave sterilization: PP has a melting temper-
impart impact resistance both at ambient and ature high enough for autoclave application.
36 HANDBOOK OF POLYMER APPLICATIONS IN MEDICINE AND MEDICAL DEVICES
Applications and uses: temperature will cause the parts to warp and disfig-
ure. Polystyrene can be sterilized with EtO.
• Homopolymer: Thermoforming, slit film and EtO resistance: Polystyrene resins retain their
oriented fibers, high clarity, syringes, and clo- properties after exposure to one normal EtO sterili-
sures, sutures, drapes, and gowns. zation cycle. Excessive or multiple exposures to
• Random copolymer: Food, household chemi- EtO sterilization are not recommended because EtO
cals, beauty aid products, clear containers, and can cause embrittlement and stress cracking of the
hot fill applications. polymer [13].
Gamma and electron beam resistance:
• Impact copolymers: Film, sheet, profiles, high- Polystyrene is very stable to gamma radiation and
pressure resistance, medical trays, and thin- electron beam due to its high aromatic content.
wall parts. Color changes are seen after e-beam sterilization
[14].
3.3.3 Polystyrene UV light sterilization resistance: Styron is resis-
tant to sterilization by UV light. This technology is
Polystyrene is the simplest plastic based on sty- based on a short wavelength of 254 nm during
rene. Its structure is shown in Figure 3.18. Pure which the part-to-lamp distance is controlled [15].
solid polystyrene is a colorless, hard plastic with Applications and uses:
limited flexibility. Polystyrene can be transparent
or can be made in various colors. It is economical • General purpose: Diagnostic instruments and
and is used for producing plastic model assembly disposable laboratory ware, Petri dishes, tissue
kits, plastic cutlery, CD “jewel” cases, and many culture components, flasks, and pipettes.
other common objects where a fairly rigid, econom-
ical plastic is desired. There are numerous medical • Oriented: Oriented polystyrene films can be
applications. printed and laminated to foams for food ser-
Three general polystyrene types are: vice plates and trays offering improved
esthetics. The films can also be used as a lami-
1. General purpose or crystal (PS or GPPS) nate to polystyrene sheet for a high-gloss
shine.
2. High impact (HIPS)
• High impact: Laboratory ware and other medi-
3. Syndiotactic (SPS). cal devices.
Sterilization:
Polystyrene is not recommended for steam and 3.3.4 Polyester
autoclave sterilization. Its low heat distortion Polyesters are formed by a condensation reaction
that is very similar to the reaction used to make
polyamide or nylons. A diacid and dialcohol are
reacted to form the polyester with the elimination
of water as shown in Figure 3.19.
While the actual commercial route to making the
polyesters may be more involved, the end result is
the same polymeric structure. The diacid is usually
aromatic. Polyester resins can be formulated to be
Figure 3.18 Chemical structure of polystyrene. brittle and hard, tough and resilient, or soft and
Polyhydroxyalkanoates (PHAs) are naturally pro- EtO sterilization: EtO is chemically highly reactive
duced and include poly-3-hydroxybutyrate (PHB or and acts as a plasticizer for PLA, PGA, and PLGA,
PH3B), polyhydroxyvalerate (PHV), and polyhy- which can lead to changes in the polymer structure.
droxyhexanoate (PHH). A PHA copolymer called EtO sterilization is performed at temperatures of
PHBV (poly(3-hydroxybutyrate-co-3-hydroxyvale- 50 60°C, which can lead to molecular weight loss.
rate)) is less stiff and tougher, and it may be used Therefore, EtO sterilization is not suggested.
as packaging material. Chemical structures of some Radiation sterilization: For the radiation sterili-
of these polymers are shown in Figure 3.22. zation of bioresorbable polymers, temperature and
Sterilization: dose conditions need to be closely controlled to
Autoclave and dry heat is usually performed at avoid significant degradation. Gamma sterilization
temperatures equal to or higher than 121°C. PLA, at dry ice temperatures is preferred.
PGA, and PLGA implants are susceptible to hydro- Applications and uses: Commercially available
lysis and their deformation at higher temperatures biodegradable devices are employed in sutures, ortho-
therefore precludes the use of these sterilization pedic fixation devices, dental implants, ligature clips,
methods. tissue staples, and skin covering devices; stents, dialy-
sis media, and drug-delivery devices. It is also being
evaluated as a material for tissue engineering.
3.3.6 Polycarbonate
PC is a type of polyester but is being discussed
separately. Theoretically, PC is formed from the reac-
tion of bis-phenol A and carbonic acid. The structures
of these two monomers are shown in Figure 3.23.
Commercially, different routes are used (differ-
ent monomers), but the PC polymer of the structure
shown in Figure 3.24 is the result.
PC performance properties include:
Applications and uses: Medical apparatus (steri- • PVC formulations exhibit excellent strength
lizable), reservoirs, high-pressure syringes, artery and toughness.
cannulas, stopcocks, luers, centrifugal force separa- • PVC exhibits very good chemical resistance
tors, blood filter housings, dialyzer housings; glu- and stability and is also biocompatible for
cose meters, pumps, insulin pens; surgical device applications in blood bags and drug delivery.
handles and housings.
• Plasticized PVC maintains its product integrity
under various sterilization environments like
3.3.7 Polyvinyl Chloride steam, radiation, and EtO.
PVC is a flexible or rigid material that is chemi- • PVC can be easily welded to various other
cally nonreactive. Rigid PVC is easily machined, plastics by a wide range of methods.
heat formed, welded, and even solvent cemented.
PVC can also be machined using standard metal • Its relatively lower cost and high-performance
working tools and finished to close tolerances and value maintains its position as the number one
finishes without great difficulty. PVC resins are plastic used in medical devices.
normally mixed with other additives such as impact • PVC has safety and cost advantages for a wide
modifiers and stabilizers, providing hundreds of variety of medical applications, especially for
PVC-based materials with a variety of engineering single-use disposable devices.
properties.
There are three broad classifications for rigid A large number of plasticizers have been used
PVC compounds: Type I, Type II, and CPVC. with PVC to reduce rigidity, the most common fam-
Type II differs from Type I due to greater impact ily being the phthalates, especially, di(2-ethylhexyl)
values, but lower chemical resistance. CPVC has phthalate (DEHP). It is sometimes called dioctyl
greater high temperature resistance. These materials phthalate and abbreviated DOP. These plasticizers
are considered “unplasticized,” because they are are incorporated in amounts ranging from 40%
less flexible than the plasticized formulations. PVC to 65%. There are many other plasticizers used in
has a broad range of applications, from high- medical applications.
volume construction-related products to simple Heat stabilizers are typically used in medical
electric wire insulation and coatings. grade PVC, to protect it against not only the high
PVC is the most widely used plastic resin in temperatures the resin might see during processing,
medical devices. Approximately 25% of all plastic but also the high heat it may encounter in storage
medical products are made of PVC, according to or autoclaving. Barium zinc additives are very
most market estimates. The main reason is the effective heat stabilizers for PVC but are restricted
resin’s low cost, ease of processing, and the ability for medical applications in some countries.
to tailor its properties to a wide range of applica- Alternatives like calcium zinc formulations are
tions. The following is a more thorough list of rea- often used to stabilize medical-grade PVC. Heat
sons for the popularity of PVC in medical devices: stabilizers trap the hydrogen chloride that is gener-
ated when PVC decomposes at high temperatures.
• Used successfully for over 50 years in various This prevents discoloration and degradation. Rigid
medical devices with no known adverse or PVC may contain up to 15% by weight of thermal
toxic effects. stabilizers. Another additive, Tinuvin® P, 2-(2H-
• Plasticized PVC has good clarity and transpar- benzotriazol-2-yl)-p-cresol, is used to provide sta-
ency retention so that tubes and other products bility from exposure to UV light.
allow for continual monitoring of fluid flow. Sterilization:
Gamma radiation resistance: Gamma-ray sterili-
• PVC can be manufactured in a range of flex- zation generally uses an energy dose of about 2.5
ibilities and its resistance to kinking in tubing megarads. Sterilization at excessive dosage rates or
reduces the risk of fluid flow being interrupted. with excessive sterilization times can result in dis-
• PVC can be used in a wide range of tempera- coloration or odor. Rigid PVC suffers more severe
tures, and it retains its flexibility, strength, and adverse effects than flexible PVC when inappropri-
durability at low temperatures. ate procedures of this type are used. Specific
3: PLASTICS USED IN MEDICAL DEVICES 41
The categories are outlined below: Urethanes are a reaction product of a diisocya-
nate and long and short chain polyether, polyester,
1. TPA—polyamide TPE, comprising a block or caprolactone glycols. The polyols and the short
copolymer of alternating hard and soft seg- chain diols react with the diisocyanates to form lin-
ments with amide chemical linkages in the ear polyurethane molecules. This combination of
hard blocks and ether and/or ester linkages in diisocyanate and short chain diol produces the rigid
the soft blocks. or hard segment. The polyols form the flexible or
2. TPC—copolyester TPE, consisting of a block soft segment of the final molecule. Figure 3.30
copolymer of alternating hard segments and shows the molecular structure in schematic form.
soft segments, the chemical linkages in the The properties of the resin depend on the nature
main chain being ester and/or ether. of the raw materials, the reaction conditions, and
the ratio of the starting raw materials. The polyols
3. TPO—olefinic TPE, consisting of a blend of used have a significant influence on certain proper-
a polyolefin and a conventional rubber, the ties of the thermoplastic polyurethane. Polyether
rubber phase in the blend having little or no and polyester polyols are both used to produce
cross-linking. many products.
4. TPS—styrenic TPE, consisting of at least a The polyester-based TPUs have the following
triblock copolymer of styrene and a specific characteristic features:
diene, where the two end blocks (hard blocks)
are polystyrene and the internal block (soft • Good oil/solvent resistance
block or blocks) is a polydiene or hydroge- • Good UV resistance
nated polydiene.
• Abrasion resistance
5. TPU—urethane TPE, consisting of a block
• Good heat resistance
copolymer of alternating hard and soft seg-
ments with urethane chemical linkages in the • Mechanical properties.
hard blocks and ether, ester or carbonate link-
ages or mixtures of them in the soft blocks. The polyether-based TPUs have the following
characteristic features:
6. TPV—thermoplastic rubber vulcanizate con-
sisting of a blend of a thermoplastic material • Fungus resistance
and a conventional rubber in which the rub-
ber has been cross-linked by the process of
• Low-temperature flexibility
dynamic vulcanization during the blending • Excellent hydrolytic stability
and mixing step. • Acid/base resistance.
7. TPZ—unclassified TPE comprising any
composition or structure other than those In addition to the basic components described
grouped in TPA, TPC, TPO, TPS, TPU, and above, most resin formulations contain additives to
TPV. facilitate production and processability.
The polyether types are slightly more expensive “M” stands for Me3SiO
and have better hydrolytic stability and low- “D” for Me2SiO2
temperature flexibility than the polyester types. “T” for MeSiO3
Gamma radiation resistance: The physical prop- “Q” for SiO4
erties of transparent rigid thermoplastic polyur- “P” for replace Me with phenyl side groups
ethanes are not significantly affected by exposure “V” for replace Me with vinyl side groups (typi-
to a maximum of 10 megarads of gamma radiation. cally ,1%)
Discoloration is dramatic upon exposure to gamma “F” for replace Me with fluorine.
radiation. Yellowness index increases from 6.3 Some common abbreviations for the polymers
before exposure to 77.6 after exposure. The discol- include MQ, VMQ, PMQ, PVMQ, PDMS poly(1-
oration is permanent with minimal bleach-back. trimethylsilyl-1-propyne) or PTMSP.
EtO resistance: Transparent and opaque rigid ther- Because silicones, in general, are temperature
moplastic polyurethanes are compatible with multiple and moisture resistant, they are typically not
cycles of EtO sterilization. They generally retain ten- affected by most sterilization methods. The most
sile strength and Izod impact properties after expo- common sterilization methods used for medical
sure to five cycles of EtO gas. Less than 300 ppm devices that contain silicone include dry heat, steam
residual EtO was present on the first day following autoclaving, EtO, gamma radiation, and electron
exposure with continued degassing over time. beam (e-beam) radiation.
Applications and uses: Catheters, valves, needleless Dry heat or steam autoclaving will most likely
syringes, surgical instruments, wound dressing and have little effect on silicone’s physical properties
tape, shunts, drug patches, medical bags, and tubing. because of its moisture and heat resistance. The
drawback to heat sterilization of silicone materials
3.3.14 Thermoset Elastomers— is that the high heat may cause the silicone to
expand which must be taken into consideration how
Silicone the device is configured and packaged.
One of the most important thermoset elastomers EtO sterilization: Silicones generally have a high
is silicone, also known as siloxane, polyorganosilox- permeability to EtO molecules allowing the EtO to
ane, or polysiloxane. Silicone rubber is a semi- diffuse through the polymer network, inducing ster-
organic synthetic. Its polymer backbone structure ilization throughout the polymer matrix. The only
consists of a chain of silicon and oxygen atoms precaution is to ensure that all of the EtO has been
rather than carbon and hydrogen atoms, as in the removed from the silicone device before it is used,
case with other types of rubber. The molecular struc- which usually takes 24 h.
ture of silicone rubber results in a very flexible—but Gamma and electron beam sterilization:
weak—chain. Silicones are very stable at low and Radiation is known to induce changes in the molec-
high temperatures. Although fillers may improve ular architecture of silicone rubber, increasing its
properties somewhat, tear and tensile strengths molecular weight and decreasing elasticity.
remain relatively low. Figure 3.31 shows four of the Applications and uses: prostheses, artificial
primary groups that make up a typical polysiloxane. organs, facial reconstruction, catheters, artificial
To simplify the discussion of polysiloxane composi- skin, contact lenses, drug-delivery systems, contact
tion, the monomers are identified by letters: lenses.
3.3.15 Poly-p-xylylene (Parylene) responses in Table 3.3). With regard to tensile prop-
erties, Parylene N and C were largely unaffected by
Parylene is the generic name for members of a any of these sterilization techniques. Only steam
series of polymers. The basic member of the series, appears to have had any effect, causing an annealing
called Parylene N, is poly-para-xylylene, a completely impact on samples coated with Parylene C, seen as
linear, highly crystalline material. The structures of an increase in film crystallinity with a slight change
four Parylene types are shown in Figure 3.32. in the tensile properties. Similarly, the tensile modu-
Parylene polymers are not manufactured and lus property of Parylene N exhibited a minor change.
sold directly. They are deposited from the vapor H2O2 plasma sterilization treatment appeared to
phase by a process which in some respects resem- alter dielectric strength, with a minimal change in
bles vacuum metalizing. The Parylenes are formed Parylene C, and no change in Parylene N.
at a pressure of about 0.1 torr from a reactive dimer Applications and uses: Needles, prosthetic
in the gaseous or vapor state. Unlike vacuum metal- devices, implantable components, catheter, elec-
izing, the deposition is not line of sight, and all trodes, stents, epidural probes, cannulae assemblies.
sides of an object to be encapsulated are uniformly
impinged by the gaseous monomer. Due to the
uniqueness of the vapor phase deposition, the 3.3.16 Fluoropolymers
Parylene polymers can be formed as structurally PTFE polymer is an example of a linear fluoro-
continuous films from as thin as a fraction of a polymer. Its structure in simplistic form is shown in
micrometer to as thick as several millimeters. Figure 3.33.
The first step is the vaporization of the solid Formed by the polymerization of tetrafluoroethy-
dimer at approximately 150°C. The second step is lene (TFE), the (aCF2aCF2a) groups repeat many
the quantitative cleavage (pyrolysis) of the dimer thousands of times. The fundamental properties of
vapor at the two methylene methylene bonds at fluoropolymers evolve from the atomic structure of
about 680°C to yield the stable monomeric diradi- fluorine and carbon and their covalent bonding in
cal, para-xylylene. Finally, the monomeric vapor specific chemical structures. The backbone is formed
enters the room temperature deposition chamber of carbon carbon bonds and the pendant groups are
where it spontaneously polymerizes on the sub- carbon fluorine bonds. Both are extremely strong
strate. The substrate temperature never rises more bonds. The basic properties of PTFE stem from these
than a few degrees above ambient. two very strong chemical bonds. The size of the fluo-
Parylene is used as a coating on medical devices rine atom allows the formation of a uniform and con-
ranging from silicone tubes to advanced coronary tinuous covering around the carbon carbon bonds and
stents, synthetic rubber products ranging from protects them from chemical attack, thus imparting
medical grade silicone rubber to EPDM (ethylene chemical resistance and stability to the molecule. PTFE
propylene diene monomer rubber). is rated for use up to (260°C). PTFE does not dissolve
The manufacturer of coating equipment and in any known solvent. The fluorine sheath is also
starting materials is Para Tech Coating, Inc. They responsible for the low surface energy (18 dynes/cm)
also offer coating services. and low COF (0.05 0.8, static) of PTFE. Another
Sterilization: attribute of the uniform fluorine sheath is the
Parylene coatings respond to these sterilization electrical inertness (or non-polarity) of the PTFE mole-
methods in a variety of ways (see summary of cule. Electrical fields impart only slight polarization in
Table 3.3 Effects of Various Sterilization Methods on Parylene [24]
(Continued )
3: PLASTICS USED IN MEDICAL DEVICES 51
(Continued )
52 HANDBOOK OF POLYMER APPLICATIONS IN MEDICINE AND MEDICAL DEVICES
[22] Plexiglas Acrylic Resin from AtoHaas Clearly [25] Ebnesajjad S. Fluoroplastics, volume 1—non-
The Best, supplier marketing literature (PL- melt processible fluoroplastics. William
1700b), AtoHaas, 1993. Andrew Publishing/Plastics Design Library;
[23] McKeen LW. The effect of temperature and 2000.
other factors on plastics. Plastics Design [26] Sastri V. Plastics in medical devices. Elsevier
Library, William Andrew Publishing; 2008. Inc.; 2010.
[24] Wolgemuth L. Assessing the effects of sterili-
zation methods on parylene coatings. Medical
Device & Diagnostic Industry; 2002.