Abstract
Heating bioabsorbable plates above Tg allows for temporary softening to facilitate adaptation to bone. This can, however, transiently alter the mechanical properties, a better understanding of which would provide further insight into the use of these polymers. Two types of unoriented l-lactide/glycolide copolymer wafer specimens (82:18 and 95:5 molar ratios) were heated to 90°C, cooled at various rates, and mechanically tested (three-point bend). Long cooling times (∼8 h) did not change mechanical properties compared to unheated controls, whereas faster cooling rates resulted in increased ductility (50–200% increase in energy to break and peak deformation), however, there was gradual recovery. Under simulated physiological incubation conditions (pH 7.4 buffer, 37°C) partial recovery occurred within 48 h. These results fit well into the theoretical framework of free volume considerations. Following rapid cooling to below Tg, the polymer is not initially at equilibrium, containing excess free volume that contributes to increased molecular mobility and ductile behavior. As equilibrium is approached, free volume decreases and the material behaves as a glassy solid. While there is little clinical consequence as regards internal fixation devices, possible transient changes in permeability and other properties could have implications in drug delivery and other applications.
Similar content being viewed by others
References
D. S. CAMINEAR, R. PAVLOVICH Jr. and W. S. PIETRZAK, J. Foot Ankle Surg. 44 (2005) 203
W. D. HOVIS, B. W. KAISER, J. T. WATSON and R. W. BUCHOLZ, J. Bone Joint Surg. 84-A (2002) 26
D. A. McGUIRE, F. A. BARBER, B. F. ELROD and L. E. PAULOS, Arthroscopy 15 (1999) 15
E. WARIS, M. NINKOVIC, C. HARPF, M. NINKOVIC and N. ASHAMMAKHI, J. Hand Surg. [Am] 29 (2004) 452
R. MITTAL, J. MORLEY, H. DINOPOULOS, E. G. DRAKOULAKIS, E. VERMANI and P. V. GIANNOUDIS, Injury 36 (2005) 333
K. PELTO-VASENIUS, E. HIRVENSALO and P. ROKKANEN, Acta Orthop Belg 62 Suppl (1996) 93
F. A. BARBER, S. J. SNYDER, J. S. ABRAMS, G. C. FANELLI and F. H. SAVOIE III, J. Shoulder Elbow Surg. 12 (2003) 535
A. R. VACCARO, J. A. CARRINO, B. H. VENGER, T. ALBERT, P. M. KELLEHER, A. HILIBRAND and K. SINGH, J. Neurosurg. 97–104 Suppl (2002) 473
B. L. EPPLEY, L. MORALES, R. WOOD, J. PENSLER, J. GOLDSTEIN, R. J. HAVLIK, M. HABAL, A. LOSKEN, J. K. WILLIAMS, F. BURSTEIN, A. A. ROZZELLE and A. M. SADOVE. Plast. Reconstr. Surg. 114 (2004) 850
W. S. PIETRZAK, Tissue Eng. 6 (2000) 425
J. A. SIMON, J. L. RICCI and P. E. DI CESARE, Am. J. Orthop. 26 (1997) 754
R. H. HAUG, C. C. STREET and M. GOLTZ, J. Oral Maxillofac. Surg. 60 (2002) 1319
S. VAINIONPAA, P. ROKKANEN and P. TORMALA, Prog. Polym. Sci. 14 (1989) 679
J. C. MIDDLETON and A. J. TIPTON, Biomaterials 21 (2000) 2335
M. VERT, P. CHRISTEL, F. CHABOT and J. LERAY, In “Macromolecular Biomaterials”, edited by G. W. Hastings and P. Ducheyne (CRC Press, Inc., Boca Raton, FL, 1984) p. 120
E. WARIS, M. NINKOVIC, C. HARPF, M. NINKOVIC and ASHAMMAKHI, J. Hand Surg. [Am] 29 (2004) 452
N. ASHAMMAKHI, R. SUURONEN, P. TORMALA and T. WARIS, J. Craniofac. Surg. 14 (2003) 247
W. S. PIETRZAK, D. R. SARVER, S. D. BIANCHINI, K D’ALESSIO, J. Biomed. Mater. Res. 38 (1997) 17
W. S. PIETRZAK, M. L. VERSTYNEN and D. R. SARVER, J. Craniofac. Surg. 8 (1997) 92
S. COX, D. P. MUKHERJEE, A. L. OGDEN, R. H. MAYUEX, K. K. K. K. SADASIVAN, J. A. ALBRIGHT and W. S. PIETRZAK, J. Foot Ankle Surg. 44 (2005) 144
M. B. HABAL, J. Craniofac. Surg. 8 (1997) 121
R. C. EDWARDS, K. D. KIELY and B. L. EPPLEY. J. Oral Maxillofac. Surg. 59 (2001) 271
D. A. GRANDE, C. HALBERSTADT, G. NAUGHTON, R. SCHWARTZ and R. MANJI, J. Biomed. Mater. Res. 34 (1997) 211
K. WHANG, D. C. TSAI, E. K. NAM, M. M. AITKEN, S. M. SPRAGUE, P. K. PATEL and K. E. HEALY. J. Biomed. Mater. Res. 42 (1998) 491
K. GARVIN and C. FESCHUK, Clin. Orthop. Relat. Res. 437 (2005) 105
W. S. PIETRZAK, M. KUMAR and B. L. EPPLEY, J. Craniofac. Surg. 14 (2003) 176
S. L. ROSEN, In “Fundamental Principals of Polymeric Materials for Practicing Engineers”. (Barnes & Noble, Inc., New York, 1971) p. 76
BILLMEYER FW Jr., In “Textbook of Polymer Science” (2nd edition,Wiley-Interscience, New York, 1971) p. 207
H. KRANZ, N. UBRICH, P. MAINCENT and R. BODMEIER, J. Pharm. Sci. 89 (2000) 1558
R. ZELKO and K. SUVEGH, Eur. J. Pharm. Sci. 21 (2004) 519
L. R. HILDEN and K. R. MORRIS, J. Pharm. Sci. 93 (2004) 3
J.-H. GUO, R. E. ROBERTSON and G. L. AMIDON, Pharm. Res. 8 (1991) 1500
G. BAYRAMOGLU and M. YAKUP ARICA. Int. J. Biol. Macromol. 30 (2005) 249
S. C. J. LOO, C. P. OOI, S. H. E. WEE and Y. C. F. BOEY, Biomaterials 26 (2005) 2827
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Pietrzak, W.S. Rapid cooling through the glass transition transiently increases ductility of PGA/PLLA copolymers: a proposed mechanism and implications for devices. J Mater Sci: Mater Med 18, 1753–1763 (2007). https://doi.org/10.1007/s10856-007-3047-0
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10856-007-3047-0