Kenneth B. Stokes

Polyether Polyurethanes: Biostable or Not?

Certain polyether polyurethanes have been shown to be biostable in long-term implant studies. Others retain good bulk properties, but have been shown to develop cracks on their tissue contacting surfaces. Two cracking mechanisms have been identified, in vivo stress cracking and metal ion oxidation. Stress cracking is the result of an interaction between the in vivo mammalian environment and residual stress (strain) in the implanted polymer. Mild autooxidation can be initiated by stress cracking. More extensive autooxidation can be initiated and propagated by corrosion of metallic device components, especially the corrosion products of cobalt. Both mechanisms are controllable, thus, do not necessarily preclude the use of polyether polyurethanes in implantable devices.

The in vivo auto-oxidation of polyether polyurethane by metal ions

The first large scale use of polyether polyurethane elastomers in long term human implants was as insulation for cardiac and neurologic pacing leads. While the performance of these polymers has generally been very good over a 14-year period, several failure mechanisms have been discovered that involve interactions between the devices, materials and the body. One of these is auto-oxidation of soft segment ether through the intermediate action of certain transition metal ions, derived from conductor wires by corrosion processes. Biologically produced oxidants appear to be an accelerating factor. In this study, Pellethane 2363-80A tubing containing conductor coils or mandrels of various metals or controls were implanted in rabbits. Explants were analyzed as a function of implant time by optical and scanning electron microscopy, electron dispersive analysis by X-ray, stress-strain, FTIR, GPC and AA spectrophotometry. Only cobalt produced bulk oxidative degradation while surface damage was found in the presence of cobalt bearing alloys. No evidence of significant auto-oxidation was found in the presence of silver, nickel, chromium, molybdenum, iron, titanium, platinum, 304 stainless steel, glass or empty tubing. The combination of polyether polyurethane and metals (especially those containing cobalt) in an implantable device must be carefully evaluated for biostability prior to human use.

Autooxidative Degradation of Implanted Polyether Polyurethane Devices

While certain polyether polyurethanes have been shown to be biostable, undesirable interactions between polymer, the body environment and device can occur. For example, the corrosion products of metallic parts can cause relatively rapid autooxidation of polyether soft segments. This phenomenon was first demonstrated in our laboratories by immersing polyurethane test specimens in metal ion solutions of different oxidation potentials. Subsequently, the mechanism was reasonably duplicated by immersing Pellethane 2363-80A insulated cardiac pacing leads in 3%, 37°C hydrogen peroxide. In vivo studies after 1 year show that corrosion products from pure Co and Fe produce the most rapid degradation of the polyurethane.

Factors and Interactions Affecting the Performance of Polyurethane Elastomers in Medical Devices

Polyurethanes offer the greatest versatility in compositions and properties of any family of polymers. For implantable medical devices, a few specific elastomeric polyurethane compositions have demonstrated a combination of toughness, durability, biocompatibility and biostability not achieved by any other available material. Because of the complex behavior of implantable polyurethanes in the body environment, designers and fabricators of polyurethane-containing devices must pay particular attention to the choice of composition and design of components. Subsequent treatment during qualification, fabrication, sterilization, storage, implantation, in vivo operation and explantation also determine the performance and provide the means for assessing the efficacy of the polyurethane in the implanted device.