Polymers for Medical Applications 1. Polymers for Artificial Joints 2. Bioabsorbable Polymers for...
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Transcript of Polymers for Medical Applications 1. Polymers for Artificial Joints 2. Bioabsorbable Polymers for...
Polymers for Medical Applications
1. Polymers for Artificial Joints2. Bioabsorbable Polymers for surgical applications3. Adhesives for medical applications
1. Polymers for Artificial Joints Figure (a) Normal joint
Figure (b) replacement of the joint is required
There are several regenerative treatments, but joint replacement with an artificial joint is the most common and effective treatment
Modern Total Arthoplasty
The artificial joint has a sliding interface using a combination of a hard material against a soft material.Hard material: Metallic femoral headSoft material: Polytetrafluoroethylene (PTFE) shellCement material: cold-curing acrylic cement (polymethylmethacrylate)- to fix the components and to transfer the stress more uniformly
The soft material made of polytetrafluoroethylene (PTFE), then it was replaced by high density polyethylene (HDPE) and later by ultra high molecular weight polyethylene (UHMWPE).
UHMWPE was chosen because of its low friction coefficient, high resistance to wear, high impact resistance, high ductility and stability in the body
SOFT MATERIALS
Problems of Total Joint Replacement
What are the differences between HDPE and UHMWPE???
The differences between HDPE and UHMWPE Morphology – the chain length of the tie
molecules in UHMWPE is much higher than that in HDPE
Molecular weight – UHMWPE shows extremely high molecular weight (two to six million), in contrast to 20,000 – 30,000 for regular HDPE, LDPE & LLDPE.
Crystallinity & density of UHMWPE are lower than that of HDPE, due to the high molecular weight and chain structure
Chemical Structure
Properties of UHMWPE
Properties of UHMWPE
Processing of UHMWPE
Fabrication methods for thermoplastics cannot be applied for processing of UHMWPE
When UHMWPE is melted (> crystalline melting temp.), the resin becomes rubbery but does not flow
Why the processing of UHMWPE is complicated???
Require a combination of temperature, high pressure and time.
Methods are ram extrusion, compression molding and direct compression molding.
The objective of the methods is to apply enough temperature and pressure to fully sinter the UHMWPE particles
Processing of UHMWPE
Processing of UHMWPE
Relative weight loss vs. type of polymers
Wear properties of UHMWPE
The abrasion resistance of UHMWPE isThe highest of the various materials
Relationship between molecular weightof polyethylene and abrasion weight loss
Abrasive wear resistance is increasedWith linearly increasing molecular weight
Wear properties of UHMWPE
Problems with UHMWPE in the application of artificial joints- wear particle produced at sliding surfaces- accelerates the loosening
Wear particles
Schematic illustration of an artificial hip joint
Formation of particles with diameter < than 1 micron
Solution: Use of transfer film Lubrication; a very thin film of Polymer is transferred to theOpposing surface, lead to the Resultant coefficient of frictionBeing very low
New processing of UHMWPE
To obtain high performance implants-alter the properties of UHMWPE
1) Increased the crystallinity (without causing degradation)- by using temperature greater than 250C and pressure greter than 2,800 atm.- obtained crystallinity over 80%
2) Crosslinking UHMWPE by low-dose γ-ray sterilization in a vacum or inert gas, then stored in oxygen free environment or heat-treated at temp. below the melting point in a vacuun or inert gas
3) Addition of vitamin E- prevent the crack formation
BONE CEMENT Acrylic cement is used for the fixation of total
joint prosthesis The cements used in orthopedic surgery are
combination of prepolymerized PMMA solid particle and the liquid monomer
The powder particles are sphere (30 to 150 µm in diameter), molecular weight of 20,000 to 2 million
For the reaction to occur,prepolymerized PMMA needs to contain an initiator, dibenzoyl perioxide (BP)
The liquid monomer contains the activator N,N-dimethyl-p-toluidine (DMPT)
The monomer will polymerized on its own when exposed to light or heat.
To prevent to monomer from polymerizing, the liquid generally contain an inhibitor or retardant, hydroquinone- function to absorb free radical that may occur and initiating the polymerization
BONE CEMENT
Preparation of Bone Cement
The prepolymerized + liquid monomer (mixed together), chemical reaction begin with activator (DMPT) and the initiator (BP) combining and releasing a benzoyl peroxide free radical, and react with the monomer. Polymerization begin.
Chains with double bond converted to single bond, heat is generated as an exotherm, and the cement cure
Problems of PMMA Bone Cement1) Strong exothermic setting reaction2) Toxic effect of the monomer3) Inability to bond directly to bone - caused
loosening at the interface4) Brittle nature
- To overcome these problems, many types of bioactive bone cements have been developed.
To improve the biochemical properties of PMMA bone cement, many types of bioactive particle fillers have been added into the cement
Example of particle fillers are glass ceramic, titania (anatase & rutile), etc
Recent studies on Bone Cement + titania particles (K. Goto et al., Biomaterials 26 (2005))
Figure (c)Shows directContactBetween bone (B)And Cement (C), while Figure (b)Shows softTissue layerLess than 10 um. The softTissue layerIn (a) and (d)Is thickerThan (b) and (c)
2. Bioabsorbable Polymers for surgical applications Polymeric materials and composites have been
used in medical applications; tissue replacement, support of tissues and delivery of drugs
Based on their behavior in living tissue, polymeric biomaterials can be divided into;
1)Biostable 2) Bioabsorbable (biodegradable/bioresorbable)
Biostable Polymers
Are inert Cause minimal response in surrounding
tissue Retain their properties for years Example: polyethylene, polypropylene; used
for endoprostheses and sutures
Bioabsorbable (biodegradable/bioresorbable) Temporary internal fixation, can be partially
and fully bioabsorbable material Bioabsorbable implant preserve the structure
of tissue at the early stage of the healing, example in bone, tendon and tissue
After that, the implant decomposes, and stress are gradually transferred to the healing tissue
Bioabsorption of the materials induced by the metabolism of the organism
Bioabsorbable surgical devices need no removal
Requirements for bioabsorbable materials;a) noncarcinogenic, tissue compatible,
nontoxic, etcb) Should not cause morbidityc) Must provide adequate mechanical strength
and stiffnessd) Degradation should occur by hydrolysis in
aqueous media
Bioabsorbable (biodegradable/bioresorbable)
Bioabsorbable Polymers for surgical applications1) Suture Materials
- Polyglycolid acid (PGA) and Polylactic acid (PLA) have been used as synthetic bioabsorbable sutures
- Bioabsorbable sutures are used in the fixation of bone fractures,closure of soft tissue wound, etc
A Typical Suture Line
Polyglycolid Acid (PGA) and Polylactic (PLA)
PGA - High molecular weight, hard, tough crystalline polymer, Tm at about 224-226ºC, Tg of 36ºC.
PLA – Tm of 174-184ºC, Tg of 57ºC. Such polymers can be processed into fibers,
films, rods, screws, plates, clamps, etc Advantages of polymeric materials compared
to metal and ceramics; easy and cheap to make
2) Porous Composites
- Combining bioabsorbable polymers in porous and nonporous materials
- Hydroxyapatite powders and blocks have applications in the bone surgery, e.g. to fill the defects
- Since porous ceramics are brittle, the toughness has been increased by combining them with polymers
Bioabsorbable Polymers for surgical applications
3) Drug Delivery System
- Polymeric devices for the controlled release of drugs and antibiotic have been studied
- These polymers show several advantages over traditional repeated dosage methods
- This technique can save patients from being exposed to greater amounts of drug at the desired site of action
Bioabsorbable Polymers for surgical applications
4) Partially Bioabsorbable Device
- The reinforcement of bioabsorbable polymeric matrices with biostable fibers produce strong, partially bioabsorbable materials
- Example; PLA matrix reinforced with carbon fiber, copolymer MMA and N-vinylpyrrolidone reinforced polyamide fibers, etc used for ligaments, tendon, scaffolds, etc.
Bioabsorbable Polymers for surgical applications
Example of Bioabsorbable materials in artificial skin Skin damage following severe burns or ulcers, such
as diabetic foot ulcers, is notoriously difficult to heal. This is because the dermis cells will not regenerate
in the absence of a matrix on which to grow Recently the development of tissue engineering
and, in particular, artificial skin has presented advances in this area
These artificial skins (keratinocyte seeded IntegraTM, DermagraftTM, and ApligraftTM which contain neonatal cells in combination with matrices formed from bovine collagen or the soluble suture materials polylactic and polyglycolic acids) provide a matrix for dermis growth and the neonatal cells contained in them produce growth factors which promote healing
3. Adhesives for medical applications
The use of surgical tissue adhesives in medicine has developed over 40 years
Traditionally, the area of tissue reattachment or repair following surgery has been dominated by sutures, staples and wiring
Recently, there is a huge potential for tissue adhesives in clinical practice
Pressure Sensitive Adhesives (PSAs) PSAs have been used for adhering wound
dressing to skin PSAs have Tg in the range of -20 to -60ºC,
which means they are soft materials at room temp.
These soft polymers are able to flow and wet out on to a surface and are able to adherence to that surface
The bond formed between PSA and substrate is not permenant and can be broken with a measurable force
Mid-19th century, the first adhesive plasters were used, the first aid application of dressing become more demanding, and undergone significant development
Early adhesive formulations were based on blends of natural rubber and resin.
Now PSAs were dominated by acrylic copolymer
Pressure Sensitive Adhesives (PSAs)
1) Should be permanently and aggressively tacky, adhere with only slight finger pressure
2) Form a strong bond with surfaces
3) Sufficient cohesiveness that it can be removed without leaving a residue
4) Need to be chemically and biologically accepted to the skin-no irritation or sensitization
Requirement for PSAs
Requirement for PSAs
5) Adhesives must have sufficient flow to ensure intimate surface contact
6) Must be able to cope with moisture at the skin without compromising performance
7) PSAs should be easily removed with minimal trauma to the skin
Example of First Aid Dressing
Adhesive TypesAcrylic Polymer Widely used due to natural adhesive behavior
and wide scope of formulation/property tailoring
PSAs are typically copolymer composed of ‘hard’ monomer and ‘soft’ monomer
The Tg of the resultant polymer can be controlled by the ratio of hard and soft monomers
The nature of alkyl group, R’, can be used to dictate the adhesives properties, by varying the chain length and hydrophilic/hydrophobic nature of the group
Chain length
Rubber-Based PSAs
Early medical adhesives were based on natural rubber
Now changed to synthetic elastomers such as polyisoprene and polyisobutylene
Polyisobutylene tend to pack tightly, results in low air and moisture permeability
The low Tg of these materials produce flexible material, that are naturally tacky, allowing the polymer to wet out the skin surface
Silicones - Used since mid 1960, have been utilized for
tapes, dressing, bandages Typically formulated from silicone resins and
polydimethyl siloxane gum To impart cohesive strength, the polymer and
resin are crosslink to form a network The properties of the final adhesives can be
controlled by ratio of component and the cross-link density
Types of Transdermal Drug Delivery Designs
More recently, silicone adhesives were used in transdermal drug delivery system-controlled entry of pharmaceutical into the blood
Delivery of an active ingredient through the skin and into the blood vessels before delivery into the target organ