In vitro oxidation of high polydimethylsiloxane content biomedical polyurethanes: Correlation with the microstructure
Corresponding Author
Rebeca Hernandez
Department of Materials Science and Engineering, Pennsylvania State University, Pennsylvania
Department of Materials Science and Engineering, Pennsylvania State University, PennsylvaniaSearch for more papers by this authorJadwiga Weksler
Aortech Biomaterials, Dalmore Drive, Caribbean Park, Scoresby, Victoria 3179, Australia
Search for more papers by this authorAjay Padsalgikar
Aortech Biomaterials, Dalmore Drive, Caribbean Park, Scoresby, Victoria 3179, Australia
Search for more papers by this authorJames Runt
Department of Materials Science and Engineering, Pennsylvania State University, Pennsylvania
Search for more papers by this authorCorresponding Author
Rebeca Hernandez
Department of Materials Science and Engineering, Pennsylvania State University, Pennsylvania
Department of Materials Science and Engineering, Pennsylvania State University, PennsylvaniaSearch for more papers by this authorJadwiga Weksler
Aortech Biomaterials, Dalmore Drive, Caribbean Park, Scoresby, Victoria 3179, Australia
Search for more papers by this authorAjay Padsalgikar
Aortech Biomaterials, Dalmore Drive, Caribbean Park, Scoresby, Victoria 3179, Australia
Search for more papers by this authorJames Runt
Department of Materials Science and Engineering, Pennsylvania State University, Pennsylvania
Search for more papers by this authorAbstract
The resistance to in vitro metal ion oxidation of a polydimethylsiloxane (PDMS)-containing thermoplastic polyurethane elastomer (Elast-Eon™) is compared with that of a polyurethane consisting of the same hard segment chemistry and content, but with aliphatic polycarbonate soft segments (PCU). Scanning electron microscopy and attenuated total reflectance Fourier transform infrared spectroscopy were used to assess changes in surface morphology and chemistry. The extent of bulk degradation was assessed indirectly by dynamic mechanical analysis and small-angle X-ray scattering experiments. The findings indicate that Elast-Eon™ is more resistant to oxidation than the PCU, because of the presence of the PDMS soft segments as well as its phase separated microstructure. The PCU exhibits a rather high degree of intermixing between hard and soft segments, rendering the hard segments dissolved or trapped in the soft phase more susceptible to oxidative conditions. By contrast, we propose that the existence of a completely phase separated PDMS soft phase in Elast-Eon™ protects the remainder of the segments from oxidation. © 2008 Wiley Periodicals, Inc. J Biomed Mater Res, 2008
References
- 1 Lambda NMK,Woodhouse K,Cooper SL. Polyurethanes in Biomedical Applications. Boca Raton, FL: CRC Press; 1998.
- 2 Khan I,Smith N,Jones E,Finch DS,Cameron RE. Analysis and evaluation of a biomedical polycarbonate urethane tested in an in vitro study and an ovine arthroplasty model, Part 1: Materials selection and evaluation. Biomaterials 2005; 26: 621–631.
- 3 Stokes K. Polyether urethanes: Biostable or not? J Biomater Appl 1988; 3: 228–259.
- 4 Stokes K,McVenes R,Anderson JM. Polyurethane elastomer biostability. J Biomater Appl 1995; 9: 321–354.
- 5 Thomas RJ,Phillips RE. Studies of poly(ether)urethane pacemaker lead insulation oxidation. J Biomed Mater Res 1987; 21: 525–530.
- 6 Ward R,Anderson J,McVenes R,Stokes K. In vivo biostability of polyether polyurethanes with fluoropolymer and polyethylene oxide surface modifying endgroups; resistance to metal ion oxidation. J Biomed Mater Res A 2007; 80: 34–44.
- 7 Pinchuk L. A review of the biostability and carcinogenicity of polyurethanes in medicine and the new generation of “biostable” polyurethanes. J Biomater Sci Polym Ed 1994; 6: 226–267.
- 8 Christenson EM,Anderson JM,Hiltner A. Oxidative mechanisms of poly(carbonate urethane) and poly(ether urethane) biodegradation: In vivo and in vitro correlations. J Biomed Mater Res A 2004; 70: 245–255.
- 9 Mathur AB,Collier M,Wiggins M,Schubert MA,Hiltner A,Anderson JM. In vivo biocompatibility and biostability of modified polyurethanes. J Biomed Mater Res 1997; 36: 247.
- 10 Boretos JW,Pierce WS. Segmented polyurethane: A new elastomer for biomedical applications. Science 1967; 158: 1481–1482.
- 11 Takahara A,Coury AJ,Hergenrother RW,Cooper SL. Effect of soft segment chemistry on the biostability of segmented polyurethanes. I. ‘In vitro’ oxidation. J Biomed Mater Res 1991; 25: 341–356.
- 12 Gunatillake PA,Martin DJ,Meijs GF,McCarthy SJ,Adhikari R. Designing biostable polyurethane elastomers for biomedical implants. Aust J Chem 2003; 56: 545–557.
- 13 Ward R,Anderson JM,McVenes R,Stokes K. In vivo biostability of polysiloxane polyether polyurethanes: Resistance to metal ion oxidation. J Biomed Mater Res A 2006; 77: 380–389.
- 14 Ward R,Anderson J,McVenes R,Stokes K. In vivo biostability of polysiloxane polyether polyurethanes: Resistance to biologic oxidation and stress cracking. J Biomed Mater Res A 2006; 77: 580–589.
- 15 Coury AJ,Stokes K,Cahalan PT,Slaikeu PC. Biostability considerations for implantable polyurethanes. Life Support Syst 1987; 1: 25–39.
- 16 Wiggins M,MacEwan M,Anderson J,Hiltner A. Effect of soft segment chemistry on polyurethane biostability during in vitro fatigue loading. J Biomed Mater Res A 2004; 68: 668–683.
- 17 Adhikari R,Gunatillake PA,Bown M. Effect of polydimethylsiloxane macrodiol molecular weight on properties and morphology of polyurethane and polyurethaneurea. J Appl Polym Sci 2003; 90: 1565–1573.
- 18 Martin DJ,Poole Warren LA,Gunatillake PA,McCarthy SJ,Meijs GF,Schindhelm K. Polydimethylsiloxane/polyether-mixed macrodiol-based polyurethane elastomers: Biostability. Biomaterials 2000; 21: 1021–1029.
- 19 Gunatillake PA,Meijs GF,McCarthy SJ,Adhikari R. Poly(dimethylsiloxane)/poly(hexamethylene oxide) mixed macrodiol based polyurethane elastomers. I. Synthesis and properties. J Appl Polym Sci 2000; 76: 2026–2040.
- 20 Adhikari R,Gunatillake PA,McCarthy SJ,Meijs GF. Mixed macrodiol-based siloxane polyurethanes: Effect of the comacrodiol structure on properties and morphology. J Appl Polym Sci 2000; 78: 1071–1082.
- 21 Rhodes N,Shortland A,Hunt J,Doherty P,Williams D. In: In vivo Biostability of Polyurethanes Purported to be Biologically Stable, Society for Biomaterials, 25th Annual Meeting, Rhode Island, 1999; p 62.
- 22 Simmons A,Hyvarinen J,Odell RA,Martin DJ,Gunatillake PA,Noble KR,Poole-Warren LA. Long-term in vivo biostability of poly(dimethylsiloxane)/poly(hexamethylene oxide) mixed macrodiol-based polyurethane elastomers. Biomaterials 2004; 25: 4887–4900.
- 23
Schubert MA,Wiggins M,Hiltner A,Anderson JM.
Role of oxygen in biodegradation of poly(ether urethane urea) elastomers.
J Biomed Mater Res
1997;
34:
519–530.
10.1002/(SICI)1097-4636(19970315)34:4<519::AID-JBM12>3.0.CO;2-7 CAS PubMed Web of Science® Google Scholar
- 24 Schubert MA,Wiggins M,Schaefer M,Hiltner A,Anderson JM. Oxidative biodegradation mechanisms of biaxially strained poly(ether urethane urea) elastomers. J Biomed Mater Res 1995; 29: 337–347.
- 25 Russell TP,Lin JS,Spooner S,Wignall GD. Intercalibration of small-angle X-ray and neutron scattering data. J Appl Cryst 1988; 21: 629–638.
- 26 Garrett JT,Lin JS,Runt J. Influence of preparation conditions on microdomain formation in poly(urethane urea) block copolymers. Macromolecules 2002; 35: 161–168.
- 27 Garrett JT,Runt J,Lin JS. Microphase separation of segmented poly(urethane urea) block copolymers. Macromolecules 2000; 33: 6353–6359.
- 28 Leung LM,Koberstein JT. Small-angle scattering analysis of hard microdomain structure and microphase mixing in polyurethane elastomers. J Polym Sci Part B: Polym Phys 1985; 23: 1883–1913.
- 29 Bonart R,Mueller. Phase separation in urethane elastomers as judged by low-angle X-ray-scattering. I. Fundamentals. J Macromol Sci Phys 1974; 10: 177–189.
- 30 Bonart R. Phase separation in urethane elastomers as judged by low-angle x-ray-scattering. I. Experimental results. J Macromol Sci Phys 1974; 10: 345–357.
- 31 Peebles LH. Hard block length distribution in segmented block copolymers. Macromolecules 1976; 9: 58–61.
- 32 Hernandez R,Weksler J,Padsalgikar A,Runt J. Microstructural organization of three phase polydimethylsiloxane-based segmented polyurethanes. Macromolecules 2007; 40: 5441–5449.
- 33 McCarthy SJ,Meijs GF,Mitchell S,Gunatillake PA,Heath G,Brandwood A,Schindhelm K. In vivo-degradation of polyurethanes: Transmission-FTIR microscopic characterization of polyurethanes sectioned by cryomicrotomy. Biomaterials 1997; 18: 1387–1409.
- 34 Anderson JM,Hiltner A,Wiggins MJ,Schubert MA,Collier TO,Kao WJ,Mathur AB. Recent advances in biomedical polyurethane biostability and biodegradation. Polym Int 1998; 46: 163–171.
- 35
Fare S,Petrini P,Motta A,Cigada A,Tanzi M.
Synergistic effects of oxidative environments and mechanical stress on in vitro stability of polyetherurethanes and polycarbonateurethanes.
J Biomed Mater Res
1999;
45:
62–74.
10.1002/(SICI)1097-4636(199904)45:1<62::AID-JBM9>3.0.CO;2-F CAS PubMed Web of Science® Google Scholar
- 36
Tang YW,Labow RS,Santerre JP.
Enzyme-induced biodegradation of polycarbonate-polyurethanes: Dependence on hard-segment chemistry.
J Biomed Mater Res
2001;
57:
597–611.
10.1002/1097-4636(20011215)57:4<597::AID-JBM1207>3.0.CO;2-T CAS PubMed Web of Science® Google Scholar
- 37 Christenson EM,Dadsetan M,Anderson J,Hiltner A. Biostability and macrophage mediated foreign body reaction of silicone-modified polyurethanes. J Biomed Mater Res A 2005; 74: 141–155.
- 38
Wu L,Weisberg D,Runt J,Felder G,Snyder AJ,Rosenberg G.
An investigation of the in vivo stability of poly(ether urethaneurea) blood sacs.
J Biomed Mater Res
1999;
44:
371.
10.1002/(SICI)1097-4636(19990315)44:4<371::AID-JBM2>3.0.CO;2-I CAS PubMed Web of Science® Google Scholar
- 39 Shibayama M,Kawauchi T,Kotani T,Nomura S,Matsuda T. Structure and properties of fatigued segmented poly(urethaneurea)s. I. Segment orientation mechanism due to fatigue. Polym J 1986; 18: 719–733.
- 40 Kojio K,Nonaka Y,Masubuchi T,Furukawa M. Effect of the composition ratio of copolymerized poly(carbonate) glycol on the microphase-separated structures and mechanical properties of polyurethane elastomers. J Polym Sci Part B: Polym Phys 2004; 42: 4448–4458.
- 41 Tang YW,Labow RS,Revenko I,Santerre JP. Influence of surface morphology and chemistry on the enzyme catalyzed biodegradation of polycarbonate-urethanes. J Biomater Sci Polym Ed 2002; 13: 463–483.
- 42 Yilgor E,Burgaz E,Yurtsever E,Yilgor I. Comparison of hydrogen bonding in polydimethylsiloxane and polyether based urethane and urea copolymers. Polymer 2000; 41: 849–857.