Materials Degradation

Chapter
6
6.1 summary

6.2 polymers
6.3 metals and ceramics
6.4 Pathological calcification
Today 6.3 then 6.2
Wed
polymers that we want to degrade
Fri
part of 6.4 + nanobes

Executive summary of the whole

chapter:
Degradation
Material

Could be Bad
Inflammatory Material
or toxic
Failure
Leachate

Could be
Good

Polymer

maybe

YES

YES

Metal

YES

NO

Ceramic

Maybe

NO
(synergy)
NO

YES

METALS Inside the body is warm, wet, salty and oxygenated. Perfect
conditions for corrosion, so the biocompatible metals listed earlier
are those which resist corrosion under these conditions. This does
not mean that corrosion is never a problem; conditions which
increase corrosion can cause it to happen even in these resistant
materials (see section 6.3 for a very basic description of corrosion).
The most likely conditions are:
1. crevice corrosion : the dissolved oxygen can get used up in a
crevice (crack, or under a nut or washer) and this makes the same
metal in the crevice and on the outside have different
electrochemical potential - crevice material corrodes faster.
2. galvanic couple : when two different metals are near to each other,
they form the terminals of a (short-circuited) battery and the anode
corrodes. Example: dental amalgam (tin, silver) corrodes much
faster if it is placed next to a gold crown.

3. grain boundary corrosion - grain boundaries are usually less

stable. So can have a cell between grain boundary and grain
(voltage small, but they are very near to each other, so resistance
low, can get a current) Cold worked regions are also less stable
than annealed regions. (thermo!)
4. fretting - corrosion + mechanical wear. Ti forms a stable TiO2
surface layer, but if that gets scraped off, a new layer will
oxidize .... and so on.
Localized corrosion is unlikely to cause a mechanical failure of the
implant. More likely, the products of corrosion will cause problems
in the surrounding tissue.
synergy refers to a case where the metal ions, products of corrosion,
catalyze polymer degradation and thus cause device failure in a
device containing both

CERAMICS The situation for ceramics is also straightforward;

structural ceramics like alumina are completely inert in the body. Your
alumina implant will long outlast your body.

The ceramics that are changed in the body are generally designed to
do so, e.g bioglass, calcium phosphate cements... are meant to be
chemically altered -- then we call them resorbable or bioerodible (both
good!) and not degrading (bad!). If a hydroxyapatite coating is partially
dissolved as bone is formed in contact with the implant we do not say
degrading we say remodeling (good!)

POLYMERS are not so quickly dealt with.. Table 2 p412

Sorption
Swelling
Softening
Dissolution
Mineralization 6.4
Extraction
Crystallization
Decrystallization

Thermolysis

Oxidation

Chemical

Both

Stress cracking

Chemical
Thermooxidative

Solvolysis

Physical

Radical scission
Depolymerization

Hydrolysis
Alcoholysis
Aminolysis, etc.

Photolysis ..Visible UV
Radiolysis ..-rays, X-rays, ebeam

Fracture-induced radical reactions

POLYMERS are not so quickly dealt with.. Table 2 p412

Sorption
uptake
Swelling
of water
Softening
or lipids
Dissolution
Mineralization 6.4
Extraction
Crystallization
Decrystallization

Thermolysis

Oxidation

Chemical

Both

Stress cracking

Chemical
Thermooxidative

Solvolysis

Physical

Radical scission
Depolymerization

Hydrolysis
Alcoholysis
Aminolysis, etc.

Photolysis ..Visible UV
Radiolysis ..-rays, X-rays,
e-beam (from sterilization)

Fracture-induced radical reactions

The most serious degradation is usually chemical. The properties

degrade because the polymer molecules break up into smaller
pieces. This may happen:
a) by itself at body temperature (thermolysis) - reversal of an
addition reaction
b) due to oxidation - body fluids contain dissolved oxygen, and
white blood cells make powerful oxidizing agents such as
hydrogen peroxide and hypochlorous acid (bleach) during
inflammation.
c) by reaction with water (hydrolysis) - reversal of a condensation
reaction
d) due to radiation (radiolysis) - important because components
may be sterilized by exposure to radiation and thus damaged
before you even start.
Of these (b) and (c) are most important. You can choose not
to use materials that suffer from (a). If (d) is a problem change
sterilization method (perhaps to ethylene oxide), but it may be very
difficult to avoid (b) and (c)

Section 6.3 continues by listing groups that can be hydrolyzed in Fig 1

ester, amide, urethane, ether, urea, imide, even cyanoacrylate
(superglue) i.e. most things the stable list in Fig 2 is much shorter!
O

O
C

N
H

H2O

OH

H2 N

Amide + water => acid + primary amine

Similarly for Ester + water => acid + alcohol
O

O
H2O

H2 N
O C OH
N
H
Urethane + water => alcohol + amine
=> ~ COH
H2N ~ + CO2
O

Similarly for a urea linkage

O

O
N
H

N
H

H2O

N
H

=> ~ NH2

OH

H2N ~ + CO2

And an anhydride
O

O
O

H 2O

OH
O

H2 N

OH

Cyanoacrylate is unusual in that a CC bond in the main chain

is broken by hydrolysis only possible because of the nearby
CN groups! See p 413 for ugly but complete diagrams
Factors increasing hydrolysis:
More hydrolyzable groups (Duh!)
More water access
More hydrophilic groups
Lower crystallinity
More surface area or - better porosity
Few cross-links
All these last also encourage swelling due to water access

Aromatic esters are much more stable than aliphatic esters; so

aliphatic esters are used as bioerodible materials designed to degrade
while poly(ethylene terephthalate), PET, is stable enough to make
textiles and coke bottles, and replacements for arteries. Nevertheless,
when there is inflammation, producing ONOO and other nasties like
ClO and dropping the local pH below 5, PET lasts only months.
Fig 3 shows a bunch of polyurethanes that have been used in implants.
A polyurethane can be anything that contains NHCOO But normally
the urethane links a hard segment (rigid chain) to a soft segment
(flexible chain). All three in Fig 3 have MDI as the monomer for the
hard segment (Methyl Diphenyl Diisocyanate) draw this.

Esters degrade much more easily than ethers, urethanes faster than
ureas, so Fig 3 shows a progression from rapid degradation by hydrolysis..
to degradation by oxidation .. To much slower degradation but error in 3 rd
one

We (I) don't care enough

about chemical
mechanisms of oxidation
to worry about Fig 4, but
the following Figure 5 of
oxidizable groups shows
that going from ester to
ether will increase
oxidative degradation while
it reduces hydrolysis.

The text has a detailed example of the degradation of the insulation

round the leads of pacemakers. It is a very practical one, because if
the insulation fails, the electrical signal is short-circuited and the
heart does not get the proper stimulation. The manufacturers were
surprised twice:
1.
that stress + the oxidizing conditions in the body (from
macrophages etc.) could produce large cracks and failure (fig 11)
2.
that metal ions from minor local corrosion could trigger
oxidation that made the plastic turn brittle, crack and fragment.
There were recalls and ( 800 or more) lawsuits.
Stress cracking is a common problem in polymers, but classically due
to agents that reduce the surface energy (detergents) making it
energetically cheaper to form cracks. Here oxidation makes the
surface more brittle, allowing cracks to start. Adsorbed proteins may
also act to reduce the surface energy.

According to the text, only adherent WBCs could oxidize the

polyurethane sufficiently; tests in vitro showed no damage unless
hydrogen peroxide was added to the mix (and tests in animals showed
none either.... I do not know whether the tests were not run for long
enough, or the animal's reaction to the implant was sufficiently different
not to show the effect). Cobalt ions enable rapid oxidation of the
polyurethane in body fluid: again tests did not show this to be a problem
until after many clinical failures.
What do you do? once the failure mode is known, the polyurethane can
be designed to resist the degradation.
Alternatively, it would seem obvious to switch to silicone rubber insulation
great electrical properties, inert in the body, dos not hydrolyze or
oxidize. But it is not slippery like the polyurethane is, so it is much more
difficult for the surgeon to push through the tissues when it is being
installed.
---- Materials that are more difficult for the surgeon do not get used!