Degradation of Materials in the Biological Environment

1. Physiologic system is harsh environment and leads to rapid or gradual breakdown of many materials 2. There are multiple mechanisms to rid the body of foreign substances 3. Biodegradation is the chemical breakdown of materials by the action of living organisms which leads to changes in the physical properties of the implanted material a. Result of short-term or long-term reactions 4. Metallic Corrosion a. Corrosion is an unwanted chemical reaction of a metal with its environment i. Body is very aggressive and hostile in terms of corrosion of metallic implants b. Oxidation i. Anode ii. Generates electrons c. Reduction i. Cathode ii. Consumes electrons d. In all cases, the anodic reaction rate must equal the cathodic reaction rate e. If the environment is acidic, hydrogen ions are reduced to form hydrogen gas f. To determine the electrode potential, difference is measured between the metal and a standard hydrogen electrode i. Formed by bubbling hydrogen through a layer of finely divided platinum black g. The more negative the value of potential for the oxidation of the metal, the greater the tendency of the metal to undergo an oxidative reaction h. Titanium readily forms a resistant bititanium oxide layer that inhibits further corrosion i. Makes it ideal in biomedical devices i. Galvanic (Bimetallic) Corrosion: A form of corrosion that corresponds to a typical electrochemical cell i. Two different types of metals are electrically coupled in the body ii. A physiologic fluid becomes the electrolyte completing the circuit iii. The more active metal will undergo anodic dissolution at an accelerated rate. j. Crevice Corrosion: small crevice makes local reaction occur rapidly

Degradation of Polymers 1. Degradation of Polymers a. Hydrolysis b. Stress Cracking c. Ester Groups d. Attack of polymers by bodily fluids 2. Effect of Implantation on Polymers a. Where debris are present: attack by human immune system

3. Hydrolysis is the scission (cutting) of susceptible molecular functional groups by the reaction with water a. May be catalyzed by: acids, bases, or enzymes 4. Cleavable groups: ester/carbonyl bonded to heterochain elements 5. Rate of hydrolysis tends to increase: a. Polar groups which enhance hydrophilicity i. Therefore suck in H2O b. Low crystallinity c. Low or negligible cross-linking density d. High ratio of exposed surface area to volume e. Mechanical stress f. High proportion of hydrolysable groups in the main or side chains 6. Polyether urethane stress cracking is characterized by surface attack of the polymer resulting in chemical changes 7. Soft: below glass transition temperature 8. Hard: above glass transition temperature 9. Cracks are proportional to the amount of both the applied and residual stress present and are relative to the ether (soft segment) content Polymers in Medicine

1. Thermal Properties a. Amorphous polymers used at temperatures above their Tg and are rubbery b. Semicrystalline polymers will exhibit a broad distribution of melting temperatures, Tm. c. Viscoelastic response can be used to classify thermal behavior of polymers

2. Biopolymers a. Synthetic polymers that undergo various rates of degradation in the body Surface Lecture
1. The surface of a material is known to be uniquely reactive 2. The surface of a material is different from the bulk 3. Common Methods to Characterize Biomaterial Surfaces a. Contact Angles b. ESCA c. FTIR-ATR d. SEM 4. Contact Angle Analysis a. Surface tension can be defined as the work of making a unit area of new surface 5. ESCA Advantages a. Little sample preparation 6. Atomic Force Microscopy a. AFM is one of the foremost tools for imaging, measuring and manipulating matter at the nanoscale b. The information is gathered by feeling the surface of a specimen with a mechanical probe c. Piezoelectric elements are used to provide accurate and precise movements of components so as to enable very precise scanning 7. AFM Tapping mode a. The tip is oscillated at a frequency near the resonate frequency of the cantilever. b. The tip barely grazes the specimen surface. c. The force developed by the interaction of the tip and the surface will affect the amplitude and frequency of oscillation of the cantilever tip. d. This phase shift provides information describing the viscoelastic, mechanical properties of the surface. e. Advantages i. Provides a three dimensional profile of the surface of the specimen ii. Samples require no special treatment. iii. High resolution of about 2 nm verses 1 micron for SEM. f. Disadvantages i. AFM scans slow requiring several minutes versus real time for SEM

Differential Scanning Calorimetry 1. Basic principle: a sample and a reference (empty pan) are heated at a specified rate, i.e. 10 deg C per minute, while the differential power is measured to maintain the required equal temperatures 2. Thermal transitions such as melting give rise to an endothermic (heat in) peak whereas crystallization is exothermic (heat out)

Fourier Transform Infrared Spectrometer 1. Basis: Interaction of IR electromagnetic radiation with mass 2. IR Spectrum: absorption intensity as a function of wave number or wavelength 3. Advantages a. Constancy of absorption wave numbers makes possible the determination of functional groups b. Spectra act as a fingerprint of the molecule. c. Quantitative analysis is often possible because the intensity of absorption is a measure of concentration. d. Also can be useful in determining the degree of orientation of stretched polymer films and fibers. 4. The interaction of the IR radiation with mass is governed by the physics of quantum mechanics. 5. Only those vibrations that are accompanied by a change in dipole moment result in infrared absorption. Gel Permeation Chromatography (GPC) 1. One of the most useful methods for routine determination of average molecular mass and molecular mass distribution of polymers. 2. GPC is a form of liquid chromatography in which the molecules are separated according to their molecular size 3. The continuous flow of the solvent leads to separation of the molecules according to size with the larger molecules being eluded first. Tissue Response Lecture
1. Four Cardinal Signs a. Robor (redness) b. Tumor (swelling) c. Calore (Tissue Heating) d. Dolore (Pain) 2. Inflammation is defined as the reaction of vascularized living tissue due to local injury 3. Wound healing process a. Flow: vasodilation (expansion of blood vessels resulting from relaxation of smooth muscle cells within the vessel walls), increase in blood flow, and removal of debris b. Permeability: increase in permeability of blood vessel wall leads to exudation c. Exudation: escape of fluids, proteins and blood cells from the vascular system into site of injured tissue

Scanning Electron Microscope (SEM)