degradation of polymers and charcterization Flashcards
what is the significance of understanding degradation (7)
-it can enhance device properties
- mechanical properties can change a various levels
- sucess/ failure of an implant
- lifespan and recyclability
- shelf life
- sterilization
What are the two polymer degradation mechanisms?
bulk erosion and surface erosion
What is surface erosion
loss of material fro the surface only resulting in predictable mass loss profiles (materials get smaller but keep shape)
What is bulk erosion
breakage of chemcial bonds in polymer chain at center of material (result is an empty chell but maintains size)
what are the three types of degradation?
oxidative, enzymatic, hydrolytic
what is oxidative degradation?
disintegration of macromolecules by action of oxygen on the substrate
what can oxidative degradation occur from
UV light or heat, with pharmacueticals, polyethylene, PP, PS
what is photooxidation and where does it occur
when UV light is present with oxygen; it occurs at the surface of the polymers
what is the result of photooxidation?
reduces molecular weight of the polymer - decreases strength
what is thermal oxidation and where does it occur
the interaction of oxygen with the polymer breaks down bonds on main macromolecule, occurs when thermal energy is higher than energy required to break the bond
what is hydrolytic degradation?
hydrolysis- cleavage of bonds in functional groups by reaction with water
in what does hydrolysis mainly occur
polymers tha take up a lot of moisture and have water-sensitive grops in polymer backbone
are hydrophilic polymers more or less suscpetible to hydrolysis compared to hydrophobic
more!
what are the two most critical factors of hydrolytic degradation
surface moisture absorption (permeability) and rate of diffusion of water within polymer
what are the three steps in the hydrolytic degradation process?
- gradual diffusion of water solution into polymer
- decrease in molecular weight (result of chain scission)
- increase in weight loss & dramatic decrease in molecular weight - collapse of polymer
two steps of hydrolysis of semicrystalline polymers
- diffusion of water into amorphous regions
- moisture penetrates and degrades crystalline regions
what increases over time due to decreased crstallinity and molecular weight in the hyrdolysis of semicrystalline polymers?
bulk erosion rate
what occurs at a constant rate in the hydrolysis of semicrystalline polymers
surface erosion rate
water diffusion os more or less restricted within crystalline regions
more
wht happens if hydrolysis occurs faster than water diffusion?
surface erosion
what happens if the rate of water diffusion is faster than hydrolysis?
bulk erosion
how to control hydrolysis? (5)
copolymerization, crosslinking, surface area to volume ratio, temperature, carbonyl bonds
what will happen if an acid or base acts as a catalyst in hydrolysis?
greatly accelerate degradation process
a lower polarity tends to decrease or increase reaction rate?
decrease