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Thermally induced time dependence of mechanical properties in biomedical grade polyurethanes.

The time dependence of the mechanical properties of segmented urethanes as well as urethane-urea systems were monitored after the materials had been given a short thermal treatment followed by rapid cooling. Both linear and crosslinked materials were studied but the major focus was on many of the common biomedical grade urethanes. As had been noted in earlier studies on nonmedical segmented urethanes from this laboratory, many of the biomedical grade materials also showed time-dependent changes in mechanical properties that can be directly related to time-dependent changes in the degree of domain structure (microphase separation) that may occur in these segmented copolymers. Interestingly, those systems possessing significant amounts of urea linkage show little or no significant time-dependent changes in structure or properties following thermal treatment. The effect of chemical cross-linking can also influence the domain formation process and its thermal stability. The ramifications of these time dependent effects may have bearing on the biomaterial applications of segmented urethane polymers.

Adhesiveness↗

Angular dependent ESCA and infrared studies of segmented polyurethanes.

The understanding of surface bonding and composition of complex polymer mixtures used for biomedical implant materials can be accomplished by a combination of techniques. In this study, vibrational spectroscopic probes of bulk and surface bonding and composition are combined with measurements with angular dependent X-Ray Photoelectron Spectroscopy (XPS or ESCA). These data provide a detailed description in the surface composition of Biomer and Avcothane, commercially available biomedical grade polymers and model systems polydimethylsiloxane (DMS) and Avcomat, all of which have been cast as smooth films from solution. Impurities are observed segregated in the near surface region sampled by ESCA which are not observed in the surface infrared results. Both Attenuated Total Reflectance (ATR) and Photoacoustic (PA) sampling are utilized, ATR to provide a depth profile and demonstrate the higher surface sensitivity of PA sampling. The combined results describe the depth of segregation of DMS blocks in Avcothane, the presence of DMS within the topmost 20 A in Biomer, and similar impurities in the model polymers. These results point out the need for multitechnique approach and the control of sample preparation and morphology in understanding complex polymer surfaces.

Biocompatible Materials↗

Biodegradation of a polyurethane in vitro.

This study examines the effect of in vitro exposure to enzymes on the performance properties of Biomer, a segmented polyetherurethane used in a number of blood-contacting devices such as catheters, heart assist pumps, and chambers for artificial hearts. The ultrathin samples were treated with two proteolytic enzymes, papain and urease, for periods of 1-6 months at 37 degrees C. The treated Biomer samples were subjected to chemical and physical analysis. Effects of biodegradation by the enzymes were assessed by fatigue tests, gel permeation chromatography (GPC), and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) analysis. Papain was found to be more effective in degrading the polymer than urease. Mechanisms for enzymic degradation are proposed.

Biodegradation, Environmental↗

Physicochemical characterization of a hydrophilic microporous polyurethane vascular graft.

There is still a need for a viable small-diameter synthetic vascular graft. The expanded PTFE device appears to be the best presently available, but is still inferior to the autologous saphenous vein. Recently, a novel microporous, small-diameter vascular graft fabricated from Mitrathane, a polyether urethane urea (PEUU), has been developed. In this article, we report the findings of an in vitro evaluation of the morphological, mechanical, and chemical properties of this new device. The results are compared with those of established vascular prostheses made from alternative materials including expanded PTFE and bovine heterograft, and with natural blood vessels. The PEUU graft displays good mechanical properties in spite of the presence of some structural defects or anomalies. In particular it compares favorably to the expanded PTFE device by providing both superior radial compliance and improved suture tearing strength.

Animals↗

Viscoelastic behavior of polyurethane vascular prostheses.

A method of evaluating the in vitro viscoelastic properties of microfibrous Biomer poly(ether-urethane-urea) vascular prostheses is outlined. Quasi-static and dynamic tests were carried out on Biomer grafts of diameter between 3.4 mm and 3.8 mm and wall thickness between 0.25 mm and 0.55 mm. It is shown that the quasi-static compliance of a Biomer graft may be determined from an equation relating transmural pressure, radius, and longitudinal strains in terms of the graft dimensions and material constants. The dynamic compliance spectra were evaluated as a function of the longitudinal and circumferential strains and temperature. Although the ratio of dynamic compliance to quasi-static compliance was linearly related to the logarithm of frequency it was not significantly affected by strains or temperature over the relevant ranges studied. Employing the usual assumptions of linear isotropic incremental elastic theory the dynamic elastic and viscous moduli were calculated as a function of frequency. Biomer grafts were more viscous than canine carotid and femoral arteries, especially at the higher frequencies. The variation in the ratio of dynamic to static incremental modulus with frequency was similar to that observed in the femoral arteries by Bergel (J. Physiol., 156, 458-469 (1961)).

Blood Vessel Prosthesis↗

Blood hemolysis by PTFE and polyurethane vascular prostheses in an in vitro circuit.

In order to improve understanding of the appearance of bright yellow stains in vivo (consecutive to the absorption of bilirubin) on a novel microporous, hydrophilic polyetherurethaneurea vascular prosthesis, the in vitro hemolytic activity of the material was compared with expanded polytetrafluoroethylene and silicone rubber. The results show that the tendency of the polyetherurethaneurea to produce free hemoglobin is low, so that the yellow staining observed is likely to be a result of the contact between the polymer and thrombi: Bilirubin is produced because of hemoglobin degradation in the thrombi rather than an active hemolysis on the surface of the prosthesis itself.

Biocompatible Materials↗

Hydrophilic microporous polyurethane versus expanded PTFE grafts as substitutes in the carotid arteries of dogs. A limited study.

A novel, microporous, hydrophilic polyether urethane-urea (PEUU) vascular graft was compared with expanded PTFE in the canine carotid artery. At implantation times ranging from 4 h to 6 months, all the PEUU grafts were found to be occluded while of the PTFE grafts, only those implanted for 1 week and 6 months were blocked. Histopathological analysis of the explanted grafts and their capsules revealed an ongoing inflammatory reaction at the anastomotic sites of the PEUU grafts.

Animals↗

Analysis of in vitro enzymatic and oxidative degradation of polyurethanes.

In vitro biodegradation studies were performed to assess the long-term stability of poly(ether urethane) (PEU) implants. Three PEU's and one poly(ester urethane) were treated with enzymes characteristic of those released from inflammatory cells during the foreign body reaction. In addition, the effect of hydrogen peroxide was observed to examine oxidative degradation. Polymers were prepared as thin films on glass, gold, silver, and copper substrates to test the possibility of metal-catalyzed degradation. Molecular weights and polydispersities of the polymers were measured by gel permeation chromatography (GPC) before and after treatment. Changes in peak shape and location were also monitored. The results demonstrate that varying degrees of both enzymatic and oxidative degradation occurred.

Chymotrypsin↗

The hydrolytic stability of Mitrathane (a polyurethane urea)--an x-ray photoelectron spectroscopy study.

The hydrolytic stability of microporous Mitrathane polyetherurethane urea vascular prostheses has been evaluated at pH 7 and pH 9, at 37 degrees, 60 degrees, and 80 degrees C for time periods of up to 968 days. Mechanical strength was evaluated using a hydrodynamic burst test and surface chemical changes by x-ray photoelectron spectroscopy. The samples held at 80 degrees C showed the greatest mechanical strength loss which corresponded to the hydrolysis of the urethane groups. It was concluded that the gross in vivo surface degradation of Mitrathane prostheses, observed after six months, could not have been caused by simple chemical hydrolysis alone, as the polymer was found to be stable at 37 degrees C for at least 11 months.

Animals↗

Heparinizable segmented polyurethanes containing poly-amidoamine blocks.

A poly-ether-urea-urethane was synthesized by copolymerization of 4,4'-diphenylmethanediisocyanate (MDI), propanediamine, and poly-oxytetra-methylene glycol (M.W. 1000). Two other corresponding copolymers were also synthesized by adding amino terminated poly-amidoamine macromonomers, purposely synthesized, so as to insert relatively small amounts (6 and 15 weight %) of two types of poly-amidoamine segments in the final product. Of the three copolymers several physicochemical and mechanical properties have been determined, and their heparin adsorption ability, blood compatibility, and cytotoxicity evaluated.

Adsorption↗