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3.051/BE.340

Lecture 4
Biomaterials Surfaces: Chemistry (Continued)
In the corrosion of metallic implants, further considerations arise with
the complexity of biological fluids.
In vivo environment
pH 7.4
T = 37C
anions: Cl , PO3 , HCO3 (bicarbonate)
cations: Na+, K+, Ca2+, Mg2+
Pitting and Crevice Corrosion: localized attacks resulting in rapid Mz+
release at discrete sites
initiated at local failure of passive film
pitting: surface defect; crevice: region of restricted transport
remaining surface acts as cathode rapid penetration at
defect (oxidation = reduction)
catalyzed by presence of Cl-, which replaces bound water
autocatalyzed by acidity from rxn in confined volume

Image removed due to copyright considerations.

Photo of CoCr hip prosthesis, from J.J. Jacobs et al,

Corrosion of Metal Orthopaedic Implants, J.
Bone and Joint Surgery 80-A, 268 (1998).

3.051/BE.340
Ex. Stainless steels in Aqueous Soln:
For Cr contents below 12.5 at%: FeOOH resides at surface in hydrated
form: FeOx(OH)ynH2O (iron oxyhydroxide hydrate)
In absence of Cl-, slow dissolution:
FeOOH + H2O Fe3+ + 3OH
With Cl- present: FeOOH + Cl- FeOCl + OH
FeOCl + 2H2O Fe3+ + Cl- + 2OH
Low solubility Fe3+ precipitates as Fe(OH)3 (rust)

restricted transport

oxide
Fe2O3

S.S.

(Fe,Cr)2 O3
Fe-9Cr

Breakdown of passivation layer until reaching metal:

Fe Fe2+ + 2e
accelerated
corrosion!

attracts Cl
Fe2+ + 2Cl- + 2H2 O Fe(OH)2 + 2HCl
local acidity in
pit or crevice

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Outside pit or crevice:

Fe2+ Fe3+ + eO2 + 2H2 O + 4e- 4OH

Fe3+ + 3(OH)- Fe(OH)3

precipitates, further
restricting transport

Steel composition effects:

Cr: For Cr > 12.5 at%: surface is hydrated CrOOH (chromium
oxyhydroxide), i.e., CrOx(OH)3-2xnH2 O
renders S.S. surface passive
increases susceptibility to pitting/crevice corrosion (CrCl3
solutions have low/negative pH!)
Mo: dissolution rate in pits/crevices (mechanism?)

Influence of other ions found in vivo:

Ca2+ and Mg2+: decrease corrosion rate

form precipitates on metal surfaces

(CO2 + H2O H+ + HCO3-)

Ca2+ + HCO3- + OH- CaCO3 + H2 O
Mg2+ + 2OH- Mg(OH)2

precipitates

O2 influx restricted inhibits cathodic reduction

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Biological Factors Influencing Corrosivity:

O2 levels (( O2 corrosion; anodiccathodic)
pH variations (inflammation/infection pH)
Cellular activity (e.g., phagocytic cells local in oxidant conc.)
Protein-Mz+ binding (Mz+ carried away Mz+ dissolution)

e.g., cytochrome oxidase, peroxidase, catalase bind Fe2+

Protein adsorption ( O2 access to surface)

Bacterial oxidation of Fe2+ to Fe3+ ( anodic rxn/Fe2+ dissolution)
Mechanically generated stresses

Localized stress Mz+ dissolution

Defects (terraces, steps): less bonds Mz+ dissolution

Corrosions Influence on in vivo Performance:

Immunological sensitization; e.g., Ni & Cr allergic response
Wear debris initiates biological cascade
(foreign body response, bone loss)
Loss of implant structural integrity (mechanical failure)
Metal ion toxicity: Al, Ni, Cr, V, Co, Ti; levels in blood/organs
Carcinogenicity (tumors at implant sites, leukemia/lymphoma

correlation with CoCr implants)

3.051/BE.340

Like metallic implants, some polymers used in biomaterials applications

are susceptible to chemical reactions that lead to degradation, in some
cases intentionally.

3. Polymer Hydrolysis
Polymer hydrolysis involves the scission of susceptible molecular
groups by reaction with H2O.
May be acid, base or enzyme catalyzed

Not surface-limited if water penetrates bulk

a) Molecular & Structural Factors Influencing Hydrolysis

Bond Stability
Hydrophobicity: hydrophobicity hydrolysis
MW & architecture: higher MW hydrolysis
Morphology
crystallinity hydrolysis
porosity hydrolysis

Tg: less mobility hydrolysis

Bond Stability
Susceptible linkages at bonds where resonance stabilized intermediates
are possible
O

Esters: R- C -O-R + H2O R- C -OH + HO-R

3.051/BE.340

Example 1: poly(lactide-co-glycolide)
Properties: rapid degradation, amorphous, Tg ~ 45-55C

Uses: bioresorbable sutures, controlled release matrices,

tissue engineering scaffolds

(-O-CH(CH3)-C -)x-r-(-O-CH 2- C -)y

lactic acid
glycolic acid

Example 2: polyethylene terephthalate (Dacron)

Properties: very slow hydrolysis, semicrystalline, Tg ~ 69C
Uses: vascular grafts, arterial patches, heart pumps
O

C O- CH2 - CH2 -]N

[-O C

base-catalyzed polyester hydrolysis:

OH

OR

O
C

O
C

OH

O
R
H

+ HOR + OH
OH

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acid-catalyzed polyester hydrolysis:

H+ X

OR

+
O

C
R
H

OR

O-H
C
R

H X

O
R

O+

H
O

C
R

+ HOR

H3O+ X

OH

Amides: R- C -NH-R + H2O R-C -OH + H2N-R

amide or peptide linkage,

also found in proteins!

Example: Nylon 6,6

(-NH-(CH2)6-NH- C -(CH2)4-C -)N
poly(hexamethylene adipamide)
Properties: ~9% H2O uptake, semicrystalline, Tg~50C

Uses: removable sutures, prosthetic joints

3.051/BE.340

Anhydrides: R- C -O-C -R + H2 O R-C-OH + HO-C -R

O

(-(CH2)8- C -O-C -)N

Example: poly(sebacic acid anyhydride)

Properties: rapid degradation (surface-based)
Uses: drug delivery matrices

Ethers: R-O-R + H2O + H+ R-CH2-OH + HO-CH2-R

Example: polyethylene oxide (PEO)

(-CH2-O-CH2-)N

Properties: water soluble, semicrystalline, Tg ~ -60C

Uses: hydrogels, protein-resistant coatings
O

Urethanes: R-NH- C -O-R + H2O R-NH- C -OH + HO-R

Example: polyether urethane

O
[(-(CH2)4-O-)x C -NH

O
CH2

NHC -O-]N [hard block]

Properties: soft block of SPU Biomer, slow hydrolysis

Uses: pacemaker lead sheaths & connectors

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Ureas: R-NH-C -NH-R + H2 O R-NH- C -OH + H2N-R

O

Carbonates: R-O- C -O-R + H2O R-O- C -OH + HO-R

Rates of Hydrolysis: anhydride > ester > amide > ether

Stable Polymer Chemistries:

Olefins
e.g., UHMWPE: joint cup liners
Halogenated hydrocarbons
e.g., PVC: catheters; PTFE: vascular grafts
Siloxanes
e.g., PDMS: soft tissue prostheses
Sulfones
e.g., PSf: renal dialysis membranes

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3.051/BE.340
b) Biological Factors Influencing Hydrolysis
pH variations

inflammation/infection pH, catalyzes hydrolysis

Hydrolasesenzymes that catalyze hydrolytic reactions

Proteolases: catalyze hydrolysis of peptide bonds
Esterases: catalyze hydrolysis of ester bonds
Produced by phagocytic cells

c) Influence of Hydrolysis on In Vivo Performance

Loss of structural integrity

e.g., i) polyester urethanes: rapid degradation in orthopedic

reconstructions (no longer used)
ii) PET fibers: deterioration after long periods in
cardiovascular applications
Toxicity/mutagenicity

e.g., i) segmented polyurethanes (SPUs): suspected

tumorigenicity of degradation products
ii) cyanoacrylates (soft tissue adhesive):
hydrolysis generates formaldehyde