Chapter Three

Classes of Biomaterials

1
 Classes of materials used in medicine

Biomaterials can be divided into four major classes

• Metals
• Ceramics (including carbons, glass ceramics, and glasses)
• Polymers

• Natural materials (including those from both plants and

animals).

2
A comparison of general material
properties

3
METALS

4
 METALS
Metallic biomaterials are used almost exclusively for load bearing applications

• Knee or hip implants, dental implants, fracture fixation

Some are pure metals, but alloys are more common

• Alloys are metals containing 2 or more elements

• Relative to pure metals, they typically have greater corrosion resistance and/or

strength.

– In fact, only copper and the precious metals (gold, silver, platinum, etc…) are

found in nature in their metallic state!

– For example, alumnium is found mainly in minerals such as bauxite

(AlOx(OH)3–2x)
5
 An overview of metals – bonding
characteristics

The lattice structure affords high stiffness (modulus) and strength 6

Strength of pure metals versus alloys
Dislocation occurs especially at grain
Scenario 1: a pure metal boundaries (misaligned planes of
atoms)

lateral force
application

Scenario 2: an alloy

Packing of two different sizes of metal

elements prevents physical dislocation of the
lattice structure

7
 Commonly used metals in medicine

Stainless steel
(alloy of Ni, Fe, Cr, Mn) Cobalt-chromium- Titanium (Ti) or Ti
(316L grade – molybdenum (“COCRMO” alloys (Ti6Al4V is a
better corrosion resistance) or “CMM”) very common variant)
8
 STAINLESS STEEL
• Although several types of stainless steels are available for
implant use in practice the most common is 316L (ASTM
F138, F139), grade 2.

• This steel has less than 0.030% (wt.%) carbon in order to

reduce the possibility of in vivo corrosion.

• The “L” in the designation 316L denotes low carbon content.

9
 STAINLESS STEEL
• The 316L alloy is predominantly iron (60–65%) with significant
alloying additions of chromium (17–20%) and nickel (12–14%),
plus minor amounts of nitrogen, manganese, molybdenum,
phosphorus, silicon, and sulfur.

• The key function of chromium is to permit the development of

corrosion-resistant steel by forming a strongly adherent surface
oxide (Cr2O3).

10
 STAINLESS STEEL
• However, the downside to adding Cr is that it tends to stabilize
the ferritic (BCC, body-centered cubic) phase of iron and steel,
which is weaker than the austenitic (FCC, face-centered cubic)
phase.

• Moreover, molybdenum and silicon are also ferrite stabilizers.

So to counter this tendency to form weaker ferrite, nickel is
added to stabilize the stronger austenitic phase.

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 STAINLESS STEEL
• The main reason for the low carbon content in 316L is to improve
corrosion resistance.

12
 Cobalt-Based Alloys
• The cobalt-base alloys may be generally described as wear resistant, corrosion

resistant, and heat resistant (strong even at high temperatures).

Many of the properties of the alloys arise from the

• The crystallographic nature of cobalt (in particular its response to stress)

• The solid-solution-strengthening effects of chromium, tungsten, and

molybdenum,

• The formation of metal carbides, and the corrosion resistance imparted by

chromium.

13
 Cobalt-Based Alloys

• Many of the commercial cobalt-base alloys are derived from the

cobalt-chromium-tungsten and cobalt-chromium-molybdenum
ternaries.

14
 Titanium-Based Alloys
• Commercially pure (CP) titanium (ASTM F67) and extra low
interstitial (ELI) Ti–6Al–4V alloy (ASTM F136) are the two most
common titanium-based implant biomaterials.
• The F67 CP Ti is 98.9–99.6% Ti.

• The oxygen content of CP Ti (and other interstitial elements such as C

and N) affects its yield and its tensile and fatigue strengths
significantly.

15
 Mechanical properties of metals
Typical shape of a metal’s stress strain curve:

16
 Mechanical properties of metals
versus ceramics and polymers

This is a very general graph; the shapes/magnitudes of stress/strain

can vary greatly within each class of biomaterial (as we will see)
17
Heterogeneity of alloy mechanical
properties

18
 Metallic biomaterials – importance of
surface properties
Almost all interactions between cells/tissues and a metal implant occur at the implant
surface. As such, the surface properties of metals implant materials are of great
importance .

“The XPS analysis showed that dental implants surfaces

consisted of oxidized titanium (mainly TiO2), carbon,
oxygen, and…contaminants like N, P and Si…Some
authors have reported that surface findings vary
according to each manufacturer procedure technique…”

Scanning electron microscopy (SEM)

image of a Ti dental implant
19
Corrosion of metal implant materials

•The physiological environment contains dissolved gases, electrolytes, cells and

proteins at 37°C.

•In this environment, immersion of metals can lead to corrosion.

Corrosion – the deterioration and removal of the metal by chemical

reactions

•Implants with “rough” surfaces as in the previous slide are especially susceptible!

•Ions released from the implant:

Are potentially cytotoxic

Can reduce the biocompatiblity of the implant and jeopardize its function

20
 Rust formation on metallic surfaces

• A simple form of metallic corrosion that occurs naturally

is rust formation.

• A very thin oxide film forms on the metal surface.

• For most metals/alloys, occurs naturally in air as long as

some water vapor is present.
21
 Metallic biomaterials – surface
passivation
•Though rust formation is often undesired for
aesthetic reasons (e.g., on bridges and other types
of public infrastructure), how might it be useful
for metal implant materials?

•Surface passivation is purposely applied to metal

implants to provide a “shielding layer” to prevent
further corrosion! Often is accomplished by
immersion in acidic solution (for the oxidation
step)

22
Metallic biomaterials – surface passivation

• The resulting oxide surface is an electrical and thermal insulator.

• Alloys are generally more corrosion resistant after implantation

because of the increased stability of the oxides formed through

passivation (relative to pure metals)

23
CERAMICS AND GLASSES

24
 An overview of ceramic biomaterials
•Ceramics are materials composed of metallic and nonmetallic
elements held together by ionic and/or covalent bonds.

The oxides described earlier for metals are actually ceramics!

•Like metals, have a long-range 3D crystal structure
Some common material properties:
• Usually inorganic (not containing carbon)
• Highly inert (non-chemically reactive)
• Hard and brittle
• High compressive strength
Applications
• Orthopaedic implants
• Dental applications
25
Mechanical properties of ceramics
Ceramics exhibit good compressive strength (UCS; below), but lower tensile
strength (UTS) compared to those of metals

26
 Nature features ceramic composites
Natural hard tissues are ceramic-polymer
composites e.g., bones and teeth

Tissue constituents
• Organic polymer fibers
• Cells
• Mineral component

HA found in the dentin of teeth (indicated

Mineral component (ceramic) by the gray arrow above)
• hydroxyapatite (HA) –
Ca5(PO4)3OH
• Gives teeth and bones their hardness!
27
 Hydroxyapatite
•HA is a mineral with structure Ca5(PO4)3OH
•More generally, an apatite is of the form Ca5(PO4)3X
•The X ion can also be fluoride (F), chloride (Cl) or carbonate
(CO32-)

HA crystal structure Bone HA (SEM)

28
HA-like materials for bone/dental implants
•Tricalcium phoshate (TCP) – Ca3(PO4)2 – is a commonly used
ceramic material.
•Very commonly, materials marketed under this name are actually
powdered HA!

β-TCP (SEM)

29
 Degradation of ceramic biomaterials
•Unlike corrosion (the passivation of a metal surface), degradation, which refers to the
chemical breakdown of the bulk material, occurs for ceramics.
• However, even this statement requires a caveat – what we are referring to mostly for
ceramics is dissolution, not true degradation:

“patches” of solid crystal lattice – break-up of

these bonds would be true degradation (not
what We see with ceramics!)

Instead, pieces of the solid break apart from each

other at the grain boundaries where the crystal
patches meet (also is why ceramics are much
stronger in compression than tension)

30
 Degradation of ceramic biomaterials

• However, osteoclasts (bone-resorbing cells) mediate true

degradation of the ceramic component of bone

• For this reason, ceramics such as TCP can undergo

degradation upon implantation into the body.

31
Ceramics for implant applications

• Tensile and compressive strength of ceramics still below that of

metals, both initially and particularly upon their more rapid
bulk degradation.
• Thus, HA and certain other ceramics typically used for non-load
bearing applications:
 Bone fillers
 Coatings on orthopaedic or dental metallic biomaterial implants

The underlying metal carries the load, while the surrounding bone bonds
strongly to the HA – “osteointegration”

32
 Ceramic biomaterials for bone
regeneration?
• Rather than using metal as a “placeholder” for the bone,
another approach is to regenerate it! (still primarily in
vitro)

• The goal is to create “tunnels” within a ceramic

biomaterial into which cells can invade and lay down new
bone matrix while degrading the scaffold.

33
 Ceramic biomaterials for bone
regeneration?
…leaching techniques used to create macroporous ceramic scaffolds:

Water
(contains TCP Ethanol
slurry, paraffin
(solubilizes
non-soluble)
paraffin
at high
temps)

34
POLYMERS

35
 polymers
• The word polymer comes from the Greek words “poly,”
meaning “many”, and “meres,” meaning “parts” or “repeating
units”
• Widely used in biomedical devices that include orthopedic,
dental, soft tissue, and cardiovascular implants.
• They represent the largest class of biomaterials.

36
 polymers
• Polymers may be derived from natural sources, or from
synthetic organic processes.
Synthetic polymers: nylon, poly-ethylene, poly-styrene
Biological polymers: DNA, proteins, carbohydrates
• Both natural and synthetic polymers are long-chain.

37
 polymers
• In synthetic polymers, the chemistry of the repeat units differs
from the small molecules (monomers) that were used in the
original synthesis procedures.

• Polymers are large molecules made by concatenation of many

small units.
• Building blocks are monomers.

38
 polymers
• A polymer may contain thousands of monomers and have a
molar mass of hundreds of thousands

– Homopolymer – the monomers are identical

– Copolymer – the monomers are different (2 or more)

39
 polymers

• Polymer chains are flexible, and usually “clump”

together into a smaller shape.
• This enables the individual chains to interact and
become entangled.
• This helps to give a polymer its strength and
flexibility.

40
 polymers
• Synthetic polymeric biomaterials range from:

– Hydrophobic: non-water-absorbing materials such as silicone rubber (SR),

polyethylene (PE), polypropylene (PP), poly(ethylene terephthalate) (PET),
polytetrafluoroethylene (PTFE), and poly(methyl methacrylate) (PMMA)

– polar materials: such as poly(vinyl chloride) (PVC), copoly(lactic–glycolic acid)

(PLGA), and nylons.

– water swelling materials:such as poly(hydroxyethyl methacrylate) (PHEMA)

– water-soluble materials: such as poly(ethylene glycol) (PEG or PEO)

 Some are hydrolytically unstable and degrade in the body while others remain mostly
unchanged for the lifetime of the patient. 41
 Requirements for Biomedical Polymers

• Biocompatibility - Noncarcinogenesis, nonpyrogenicity,

nontoxicity, and nonallergic response
• Sterilizability- Autoclave, dry heating, ethylenoxide gas, and
radiation
• Physical property - Strength, elasticity, and durability
• Manufacturability - Machining, molding, extruding, and
fiber forming

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 Monomer

• A monomer must be capable of forming two bonds to

generate a chain.
• A double bond meets that requirement.

43
 Synthesis of polymers

• Addition polymerization(chain reaction)

• Simply adding monomers together – synthetic

plastics

• Condensation polymerization(stepwise growth)

• Combination by exclusion of a small molecule

(usually water) – extensively used by nature

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 Addition polymerization has three steps

– Most common form: free radical chain reaction of ethylenes

– C2H4 is stable – does not spontaneously change into polyethylene

– requires severe conditions

1. Initiation – create reactive species by formation of free radical

(unpaired electron)

2. Propagation – As chain grows by addition of C2H4 units, the radical

is preserved

3. Termination – radicals eliminated when they meet

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Addition polymerization

n monomers one polymer molecule

46
Example of addition polymers

47
 Free-Radical Addition
Polymerization of Ethylene
H2C CH2

200 °C O2
2000 atm peroxides

CH2 CH2 CH2 CH2 CH2 CH2 CH2

polyethylene
48
Free-Radical Polymerization
of Propene
H2C CHCH3

CH CH CH CH CH CH CH
CH3 CH3 CH3 CH3 CH3 CH3 CH3

polypropylene
49
 ..
RO • Mechanism
..
H2C CHCH3

50
 ..
RO:
Mechanism
H2C CHCH3
•

51
 ..
RO: Mechanism
H2C CHCH3
•

H2C CHCH3

52
 ..
RO: Mechanism
H2C CHCH3

H2C CHCH3
•

53
 ..
RO: Mechanism
H2C CHCH3

H2C CHCH3
•

H2C CHCH3

54
 ..
RO: Mechanism
H2C CHCH3

H2C CHCH3

H2C CHCH3
•

55
 ..
RO: Mechanism
H2C CHCH3

H2C CHCH3

H2C CHCH3
•

H2C CHCH3

56
 Like wise…….
• H2C=CHCl polyvinyl chloride

• H2C=CHC6H5 polystyrene

• F2C=CF2 Teflon

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Important constitutions for
synthetic polymers

58
 Condensation polymerization

• The polymer grows from monomers by splitting off a

small molecule such as water or carbon dioxide.
Example: formation of amide links and loss of water

Monomers

First unit of polymer + H2O

59
 Condensation polymerization

• Two types of monomer required – each capable of

making two bonds
• Bonding occurs between them by elimination of
components of water
– OH + H = H2O

• Lower temperature process than addition polymerization

60
 Condensation polymerization

• Two monomers react to form a covalent bond, usually with elimination of a

small molecule (e.g. water, hydrochloric acid, methanol, or carbon dioxide)

• R-NH + R’ COOH  R’CONHR + H2O

(amine) (carboxylic acid) (amide) (condensed molecule)

• This particular process is used to make polyamides (nylons).

• Nylon was the first commercial polymer, made in the 1930s.

• Reaction continues until almost all of one reactant is used up.

• E.g. Polyester, nylon, polyurea, polyurethane, polysiloxane, protein

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Condensation polymer products

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 Basic Structure
• Polymers have very long chain molecules which are formed by covalent
bonding along the backbone chain.
• Long chains held by
– Secondary bonding forces: Vander Waals and hydrogen bonds

– Primary covalent bonding: cross-links between chains

• Long chains are very flexible

• Each chain can have side groups, branches, and co-polymeric chains or blocks
• When chains becomes quite long(repeating units several thousands long),
semicrystalline occur- most commonly occurring structure for linear polymers.

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• Paraffin wax has same chemical formula as polyethylene(PE)

[(CH2CH2)n], but crystallize almost completely b/c it is much shorter

chains length.
• The semicrystalline structure is represented by disordered noncrystalline
(amorphous) regions and ordered crystalline regions which may contain
folded chains as shown.

Fringed-micelle model of a linear polymer with semicrystalline structure .

64
 Effect of Temperature on Properties

• The glass transition temperature, Tg, is a boundary between the glassy

region of behaviour in which the polymer is relatively stiff and the rubbery
region in which it is very compliant.
 As the liquid polymer cools a temperature is reached at which all motions
cease

 This is the glass transition temperature (Tg)

 varies from polymer to polymer

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Effect of Temperature on Properties

 Polymers used below their Tg (e.g. PMMA) are hard and glassy, and

polymers used above their Tg (e.g. SR) are rubbery.

 Polymers with any crystallinity (e.g. PET, PP, and nylon) will also have a
melting temperature (Tm)  melting of the crystalline phase

 These polymers are hard and strong below Tg, and tough and strong

above Tg

 All polymers have a Tg, but only polymers with regular chain architecture

can pack well, crystallize, and exhibit a Tm

 The Tg is always below the Tm 66

Effect of Side Chain Substitution, Cross-Linking,
and Branching

• Increasing the size of side groups in linear polymers such as polyethylene

will decrease the melting temperature due to the lesser perfection of
molecular packing, i.e., decreased crystallinity
• Very long side groups can be thought of as being branches.

67
Arrangement of polymer chains into linear, branched, and network structure
68
depending on the functionality of the repeating units.
 Tacticity

• Polymers capable of assuming many conformations through rotation of

valence bonds.
• Vinyl polymers have a repeating unit –CH2–CHX– where X is some
monovalent side group.
• There are three possible arrangements of side groups (X):
(1) atactic,

(2) isotactic, and

(3) syndiotactic.

69
 Tacticity
 Tacticity = the arrangement of substituents around the extended polymer chain
 E.g. Arrangement of methyl groups around chain in polypropylene
 Isotactic - chains in which all substituents are located on the same side of the
zigzag plane
 Can crystallize
 Syndiotactic - chains have substituents alternating from side to side
 Can crystallize
 Atactic - substituent groups appear at random on either side of the extended
chain backbone
 cannot crystallize  amorphous polymer results

70
 Polymers Used as Biomaterials

• Although hundreds of polymers are easily synthesized and could

be used as biomaterials only 10 to 20 polymers are mainly used in
medical device fabrications from disposable to long-term implants
• Some of the synthetic polymers used in biomedical applications
are:
– polyvinylchloride, polyethylene, polypropylene, polymethylmetacrylate,
polystyrene, polyethylenterephthalate, polytetrafluoroethylene,
polyurethane, polyamide(nylon)

71
 1. Polyvinylchloride (PVC)

• PVC is an amorphous, rigid polymer due to the large side group (Cl,
chloride) with a Tg of 75~105°C.
• To prevent the thermal degradation of the polymer (HCl could be
released), thermal stabilizers such as metallic soaps or salts are
incorporated.
Applications
• PVC sheets and films are used in blood and solution storage bags
and surgical packaging.,
• PVC tubing is commonly used in intravenous (IV) administration,
dialysis devices, catheters bottles, and cannulae.
72
 2. Polyethylene (PE)
• PE is available commercially in five major grades:
– (1) high density (HDPE),
– (2) low density (LDPE),
– (3) linear low density (LLDPE),

– (4) very low density (VLDPE), and

– (5) ultra high molecular weight (UHMWPE).

Applications
• HDPE is used in pharmaceutical bottles, nonwoven fabrics, and caps.
• LDPE is found in flexible container applications, nonwoven disposable
and laminated (or coextruded with paper) foil, and polymers for
packaging.
• LLDPE is frequently employed in pouches and bags due to its
73
excellent puncture resistance and
 2. Polyethylene (PE)

• VLDPE is used in extruded tubes.

• UHMWPE (MW > 2 × 106 g/mol) has been used for
orthopedic implant fabrications:
– An acetabular cup of total hip and
– The tibial plateau and patellar surfaces of knee joints.

74
 3. Polypropylene (PP)
• PP can be polymerized by a Ziegler–Natta stereospecific catalyst which
controls the isotactic position of the methyl group.
• Thermal (Tg: –12°C, Tm: 125~167°C), density (0.85~0.98 g/cm3), and
physical properties of PP are similar to PE.
Applications
– To make disposable hypothermic syringes
– Blood oxygenator membrane
– Packaging for devices, solutions, and drugs
– Suture
– Artificial vascular grafts
– Nonwoven fabrics etc.
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 4. Polymethylmetacrylate (PMMA)
• PMMA is best known for its exceptional light transparency (92% transmission),
high refractive index (1.49), good weathering properties, good coloring
properties, and as one of the most biocompatible polymers.

Applications
• Blood pump and reservoir
• In IV system
• Membranes for blood dialyzer
• In in vitro diagnostics.
• contact lenses and implantable ocular lenses
• dentures, and maxillofacial prostheses
• bone cement for joint prostheses fixation
76
 5. Polystyrene (PS) and Its Co-Polymers
• PS is polymerized by free radical polymerization and is usually atactic.

Three grades are available:

• unmodified general purpose PS (GPPS, Tg: 100°C)
• high impact PS (HIPS)
• PS foam
• GPPS has good transparency, lack of color, ease of fabrication, thermal
stability, low specific gravity (1.04~1.12 g/cm3), and relatively high modulus
• HIPS contains a rubbery modifier which forms chemical bonding with the
growing PS chains.
Applications
• Tissue culture flasks, roller bottles, and filter wares.
77
 6. Polyesters
• Polyesters such as polyethyleneterephthalate (PET) are frequently
found in medical applications due to their unique chemical and physical
properties.
• It is highly crystalline with a high melting temperature (Tm: 265°C),
hydrophobic, and resistant to hydrolysis in dilute acids.
Applications
• Artificial vascular graft
• Sutures
• Meshes

78
 7. Polyamides (Nylons)
• Polyamides are known as nylons and are designated by the number of
carbon atoms in the repeating units.

• They have excellent fiber-forming ability due to interchain hydrogen

bonding and a high degree of crystallinity, which increases strength in
the fiber direction.

• Nylons are hygroscopic and lose their strength in vivo when implanted.

79
 8. Fluorocarbon Polymers
• The best known fluorocarbon polymer is polytetrafluoroethylene (PTFE),
commonly known as Teflon.
• Other polymers containing fluorine are polytrifluorochloroethylene
(PTFCE), polyvinylfluoride (PVF), and fluorinated ethylene propylene
(FEP).
• PTFE is made from tetrafluoroethylene under pressure with a peroxide
catalyst in the presence of excess water for removal of heat.
• Usually the powders are sintered to above 327°C under pressure to
produce implants.

80
 9. Rubbers
• Natural rubber is made mostly from the latex of the Hevea brasiliensis
tree and the chemical formula is the same as that of cis-1,4
polyisoprene.
• Natural rubber was found to be compatible with blood in its pure
form.
• Synthetic rubbers were developed to substitute for natural rubber.
• The synthetic rubbers have rarely been used to make implants.

81
 10. Polyurethanes
• Polyurethanes are usually thermosetting polymers.

Thermoplastic polymers: softens when heated and hardens when

cooled and vice versa
Thermosetting polymers: permanently hard (do not soften when
heated)
• The polyurethane rubber is quite strong and has good resistance to
oil and chemicals.
Applications
• To coat implants

82
 11. Polyacetal, Polysulfone, and
Polycarbonate
• Polyacetals and polysulfones are being tested as implant
materials, while polycarbonates have found their
applications in heart/lung assist devices, food packaging,
etc.
• Polyacetals display an excellent resistance to most
chemicals and to water over wide temperature ranges.

83
 12. Biodegradable Polymers
• Several biodegradable polymers such as polylactide (PLA),
polyglycolide (PGA), poly(glycolide-co-lactide) (PLGA),
poly(dioxanone), poly(trimethylene carbonate), poly(carbonate), and so
on have been used extensively or tested on a wide range of medical
applications due to their good biocompatibility, controllable
biodegradability, and relatively good processability.
• PLA, PGA, and PLGA are bioresorbable polyesters.
• These polymers degrade by nonspecific hydrolytic scission of their
ester bonds.

84
 12. Biodegradable Polymers
• The degradation time of PLGA can be controlled from
weeks to over a year by varying the ratio of monomers
and the processing conditions.
• The hydrolysis of PLA yields lactic acid, which is a
normal by product of anaerobic metabolism in the human
body and is incorporated in the tricarboxylic acid (TCA)
cycle to be finally excreted by the body as carbon
dioxide and water.

85
 12. Biodegradable Polymers

• PGA biodegrades by a combination of hydrolytic scission

and enzymatic (esterase) action producing glycolic acid
which either can enter the TCA cycle or is excreted in urine
and can be eliminated as carbon dioxide and water.
• It might be a suitable biomaterial for use in tissue
engineered repair systems in which cells are implanted
within PLGA films or scaffolds and in drug delivery systems
in which drugs are loaded within PLGA microspheres.

86
 12. Biodegradable Polymers

• PGA (Tm: 225–230°C, Tg: 35–40°C) can be melt spun into fibres which
can be converted into bioresorbable sutures, meshes, and surgical
products.
• PLA (Tm: 173–178°C, Tg: 60–65°C) exhibits high tensile strength and
low elongation resulting in a high modulus suitable for load-bearing
applications such as in bone fracture fixation.
• Poly-p-dioxanone (Tm: 107–112°C, Tg: ~10°C) is a bioabsorbable
polymer that can be fabricated into flexible monofilament surgical
sutures.

87
Silicon Biomaterials

88
 CHEMICAL STRUCTURE AND
NOMENCLATURE OF SILICONES
• Silicones: general category of synthetic polymers with backbone
made of repeating silicon to oxygen bonds.
• Silicon atoms also bonded to organic groups – usually methyl
groups

• Siloxane: basic repeating unit in silicones

89
 CHEMICAL STRUCTURE AND
NOMENCLATURE OF SILICONES
• Most common silicone is polydimethylsiloxane (PDMS)

• Other groups (e.g., phenyl, vinyl and trifluoropropyl) can be

substituted for the methyl groups along the chain.
• Having organic groups attached to inorganic backbone gives
silicones unique properties
• Can use as fluids, emulsions, compounds, resins, and elastomers.

90
 Silicones
• Most common are the polydimethylsiloxanes (PDMS) that are
trimethylsilyloxy terminated

• Silicones are mostly linear polymers and liquids, even for large values of
n.
• Main chain unit (–(Si(CH3)2 O)n–) often represented by letter D

91
 Silicones
• Silicon atom is connected with two oxygen atoms  capable
of expanding within the polymer in two directions.
• Easy to get confused between silicon (Si, a metallic element),
silica (SiO2, an inorganic compound) and silicone (a
polymeric compound)

92
 Surface Properties of Silicones
• Have a low surface tension
• Capable of wetting most surfaces
• Hydrophobic because of hydrocarbons facing out
• Surface tension in a good range for biocompatible elastomers
• Capable of wetting themselves, which promotes good film
formation and good surface covering
• Glass transition temperatures very low
• Have a high permeability to oxygen, nitrogen, or water vapor,
even though liquid water is not capable of wetting a silicone
surface

93
Medical Fibers and
Biotextiles

94
 Medical Textiles
• Medical Textiles : medical products and devices including
wound dressings, bandages, biotextiles, tissue engineered
scaffolds, and vascular implants.
• Fibers and textiles in medicine now very common
– New and innovative fibers, structures, and therapies have been
developed

95
 Applications of Medical Textiles

Manufactured from a wide range of processes

• Tapes in dental floss and toothbrushes

• (extruded polymers )

• Sutures and to replace damaged tendons and ligaments

• (braided textiles)

• Bandages, vascular grafts and hernia meshes

• (woven and knitted materials)

• Extracorporeal devices
• (hollow fibre membranes)

• Wound dressings, hygiene products and protective clothing

• (non-woven)
96
 Medical Fibers
• Textile-based medical devices made from monofilament, multifilaments, or staple fibers
– These are made from synthetic polymers, natural polymers, or genetically engineered
polymers
• When choosing a fiber configuration and polymer for an application, device design and use
requirements should be considered
• Eg. Collagen-based implantable hemostatic wound dressings:
– loose powder (Avitine)
– nonwoven mats (Helistat and Surgicel Fibrillar Hemostat),
– knitted collagen fibrils (Surgicel Nu-Knit)

97
 Medical Fibers
• Fibers can be made from nonabsorbable synthetic polymers such as:
– poly(ethylene terephthalate) (PET)

– polyester (e.g., Dacron)

– polytetrafluoroethylene (e.g., Teflon) PET

– Absorbable synthetic materials such as polylactide (PLA)

and polyglycolide (PGA)

• Natural materials (biopolymers), such as collagen or polysaccharides like

alginates, have also been used to fabricate medical devices

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 Medical Fibers
• Cotton: still commonly used for bandages, surgical sponges,
drapes, surgical apparel, and surgical gowns
– Recently cotton has been replaced in many applications by coated
nonwoven disposable fabrics, especially in cases when nonabsorbency
is critical.

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 Synthetic Fibers
• Various synthetic fibers used in medical devices.
• Starting in the 1950s, various materials evaluated for use in vascular grafts
– Eg. Vinyon (PVC copolymer), acrylic polymers, poly(vinyl alcohol), nylon,
polytetrafluoroethylene (PTFE), and polyester (PET)

• Today, only PTFE and PET still used for vascular grafts since they are
reasonably inert, flexible, resilient, durable, and resistant to biological
degradation
– The most durable for implants.

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 Polymer and Fiber Selection

• Need to consider duration of body contact, device mechanical

properties, fabrication restrictions, and sterilization methods

• Eg. Polypropylene successfully used in many implantable applications

• Polypropylene has excellent characteristics in terms of tissue

compatibility and can be fabricated into a graft material with adequate

mechanical strength

• Unsure whether graft will remain stable and survive as a long-term

implant.
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 Absorbable Synthetic Fibers
Are Polymers that are designed to be absorbed over time when placed in the body.

 Used in sutures, but also experimentally for neurological, vascular graft, and tissue scaffold

applications.

 Degrade by hydrolysis or enzymatic degradation into nontoxic by-products

 Break down via:

 Erosion process starting on exterior surface of fiber and continues until fiber totally

absorbed

 Or bulk erosion mechanism using autocatalytic process that starts in center of the fiber

 Caution: risk of blockage in blood vessel if small pieces polymer break off during erosion or

absorption process

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 Modified Natural Fibers
•Natural fibers have evolved to be particularly suited for medical applications

•Cellulose (obtained from cotton or wood pulp) one of the most common fiber-forming

biopolymers.

•Cellulose fibers are highly absorbent , therefore they are commonly used in feminine

hygiene products, diapers, and other absorbable applications.

– Typically are not used in the body – cause inflammatory reactions

•Can be an advantage (eg Surgicel) where response caused by cellulose can be used to

form a blood clot and stop internal bleeding.

•Fibers created from modified polysaccharides including alginates, xanthan gum,

chitosan, dextran, and reticulated cellulose are being researched.

– These come from algae, crustacean shells, and bacterial fermentation

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 Chitosan
Chitosan - used to fabricate surgical sutures and meshes
 Under investigation for use as a substrate or scaffold for tissue-engineered
materials.

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 Silk & Collagen
Natural fibers widely used in medicine for multiple applications.

• Silk from the silkworm - Bombyx mori - used for decades as a suture

– Silk fibers are fine so they are braided to make thicker yarn bundles

• Collagen used in a reconstituted form or in natural state

– Reconstituted collagen from enzymatic chemical treatment of bovine

skin or tendon and reconstitution into fibrils

– Fibrils spun into fibers and fabricated into textile structures or can be

left in their native fibrillar form for use in hemostatic mats and tissue-

engineered substrates
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 Silk & Collagen

• “Catgut” - natural collagen- based suture material

– Obtained from ovine intestine

– Cross-linked and cut into narrow strips

– One of the first bioabsorbable fibers used in surgery

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 Construction
Fibers are fabricated into textile structure to obtain the desired mechanical and biological

properties

• Typical biotextile structures: nonwovens, wovens, knits, and braids

– Many variations exist

• Construction type usually a compromise between desired and actual fabricated properties
– Eg. Woven fabrics typically stronger and fabricated with lower porosities or water/blood permeability

than knits, but are stiffer, less flexible, and more difficult to handle and suture

• Knits have higher permeability than woven designs and are easier to suture, but may dilate

after implantation

• Braids flexible, but can be unstable (except when subject to longitudinal load - as in the case of

a suture)
– Multilayer braids more stable, but are thicker and less flexible (than unidimensional braids)
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 Nonwovens
• Nonwoven - a textile structure produced directly from fibers

– (without intermediate step of yarn production)

• Average pore size of nonwoven web depends on density of fibers and

average fiber diameter.

– Some tissue-engineered substrates under development use nonwovens to form

the underlying tissue scaffold.

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 Woven Fabrics
Woven : Textile configuration where the primary structural yarns are

oriented at 90◦ to each other

 have low elongation and high breaking strength in both directions

Water permeability important parameter used to assess textile structures

for vascular implants

 measure of the water flux through a fabric (under controlled conditions, given in

units of ml cm-2 min-1)

 Used to determine if “pre-clotting” (graft material clotted with patients blood in

advance) is necessary to make the fabric nonpermeable to blood after implantation

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 Woven Fabrics

The water permeability of the woven graft fabrics can

be controlled through the weaving and finishing process

Many variations in design are possible

The choice of graft by surgeon often based on “ease of

handling” or “ease of suturing” rather than long-term

performance.

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 Knits
• Made by interloping yarns in horizontal rows and vertical
columns of stitches

• Softer, more flexible and have better handling

characteristics than woven graft designs

• Can be built with water permeability values as high as

5,000 ml cm−2 min-1 and still maintain structural stability

• Highly porous graft materials usually coated with collagen

or gelatin to avoid need for ‘pre-clotting’
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 Knits
• Fabric open and requires processing to tighten loop structure
and lower permeability
 Chemical or thermal shrinking agent
• Easier to suture and has good handling, can sometimes
expand.

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 Braids
• Used as suture materials and anterior
cruciate ligament (ACL) prostheses
• Braid structures:
– interlace even number of yarns (to form Braid structure
diamond, regular, or Hercules
structure)
– Can be two or three-dimensional
– A myriad of structural forms
• Many forms can be achieved with 3D
braiding

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Flat braider and braid