Journal of Materials Science

, Volume 48, Issue 1, pp 424–440 | Cite as

Chemical and thermomechanical tailoring of the shape memory effect in poly(ε-caprolactone)-based systems

  • Massimo Messori
  • Micaela Degli Esposti
  • Katia Paderni
  • Stefano Pandini
  • Simone Passera
  • Theonis Riccò
  • Maurizio Toselli
Article
First Online:
Received:
Accepted:

Abstract

The thermally activated shape memory response of polymeric materials results from a combination of the material molecular architecture with the thermal/deformational history, or ‘programming’. In this work, we investigate the shape memory response of systems based on poly(ε-caprolactone) (PCL) so as to explore the adoption of proper chemical and thermomechanical tailoring routes. Cross-linked semicrystalline PCL-based materials are prepared by different molecular architectures starting from linear, three- and four-arms star PCL functionalized with methacrylate end groups, allowing to tune the melting temperature, T m, ranging between 36 and 55 °C. The materials’ ability to display the shape memory is investigated by the application of proper thermomechanical cycles on specimens deformed at two different temperatures (23 and 65 °C, i.e. below and above the T m, respectively). The shape memory response is studied under dynamic thermal conditions in thermally activated recovery tests, to identify the typical transformation temperatures, and under isothermal conditions at given recovery temperatures, to monitor shape recovery as a function of time. All the specimens are capable of full recovery on specific thermal ranges influenced by both melting and deformation temperatures. Specimens deformed above T m are able to recover the whole deformation in a very narrow temperature region close to T m, while those deformed at room temperature display broader recovery processes, those onset at about 30 °C. Isothermal tests reveal that when the deformed material is subjected to a constant recovery temperature, the amount of recovered strain and the time required strongly depend on the particular combination of melting temperature, deformation temperature and recovery temperature.

Keywords

Shape Memory Deformation Temperature Shape Memory Effect Shape Recovery Shape Memory Polymer 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.
This is a preview of subscription content, log in to check access.

Notes

Acknowledgements

The authors thank Prof. Francesco Pilati of the University of Modena and Reggio Emilia (Italy) for the fruitful scientific discussion and his fundamental support. The authors would like to acknowledge Regione Lombardia and INSTM Consortium (Firenze, Italy) for providing financial support to the present research.

Supplementary material

10853_2012_6757_MOESM1_ESM.pdf (1.5 mb)
Supplementary material 1 (PDF 1512 kb)

References

  1. 1.
    Otsuka K, Wayman CM (1999) Shape memory materials. University Press, CambridgeGoogle Scholar
  2. 2.
    Huang WM, Ding Z, Wang CC, Wei J, Zhao Y, Purnawali H (2010) Mater Today 13(7–8):51Google Scholar
  3. 3.
    Leng JS, Lan X, Liu YJ, Du SY (2011) Prog Mater Sci 56(7):1077. doi: 10.1016/J.Pmatsci.2011.03.001 CrossRefGoogle Scholar
  4. 4.
    Lendlein A, Langer R (2002) Science 296(5573):1673. doi: 10.1126/science.1066102 CrossRefGoogle Scholar
  5. 5.
    Yakacki CM, Shandas R, Safranski D, Ortega AM, Sassaman K, Gall K (2008) Adv Funct Mater 18(16):2428. doi: 10.1002/Adfm.200701049 CrossRefGoogle Scholar
  6. 6.
    Xie T, Rousseau IA (2009) Polymer 50(8):1852. doi: 10.1016/J.Polymer.2009.02.035 CrossRefGoogle Scholar
  7. 7.
    Gall K, Mikulas M, Munshi NA, Beavers F, Tupper M (2000) J Intel Mater Syst Struct 11(11):877Google Scholar
  8. 8.
    Sokolowski WM, Tan SC (2007) J Spacecraft Rockets 44(4):750. doi: 10.2514/1.22854 CrossRefGoogle Scholar
  9. 9.
    Hu J (2007) Shape memory polymers and textiles. Woodhead Publishing, CambridgeCrossRefGoogle Scholar
  10. 10.
    Browne AL, Johnson NL (2008) Hood assembly utilizing active materials based mechanisms. US Patent US2008197674Google Scholar
  11. 11.
    Browne AL, Johnson NL (2005) Shape memory polymer seat assemblies. US Patent US2005218710Google Scholar
  12. 12.
    Alexander PW, Browne AL, Johnson NL, Mankame N, Muhammad H, Wanke T (2007) Active material based tunable property automotive brackets. WO2007056639Google Scholar
  13. 13.
    Lendlein A, Behl M, Hiebl B, Wischke C (2010) Expert Rev Med Devic 7(3):357. doi: 10.1586/Erd.10.8 CrossRefGoogle Scholar
  14. 14.
    Pitt CG (1990) Drugs Pharm Sci 45:71Google Scholar
  15. 15.
    Barot G, Rao IJ (2006) Z Angew Math Phys 57(4):652. doi: 10.1007/S00033-005-0009-6 CrossRefGoogle Scholar
  16. 16.
    Westbrook KK, Parakh V, Chung T, Mather PT, Wan LC, Dunn ML, Qi HJ (2010) J Eng Mater-T Asme 132 (4). doi: 10.1115/1.4001964
  17. 17.
    Xu WX, Yin RY, Lin L, Yu Y (2008) Prog Chem 20(1):140Google Scholar
  18. 18.
    Ren WT, Kline WM, McMullan PJ, Griffin AC (2011) Phys Status Solidi B 248(1):105. doi: 10.1002/Pssb.201083972 CrossRefGoogle Scholar
  19. 19.
    Liu YP, Gall K, Dunn ML, Greenberg AR, Diani J (2006) Int J Plast 22(2):279. doi: 10.1016/J.Ijplas.2005.03.004 CrossRefGoogle Scholar
  20. 20.
    Wang ZD, Li ZF, Wang LY, Xiong ZY, Wang ZD, Li ZF, Wang LY, Xiong ZY (2010) J Appl Polym Sci 118(3):1406. doi: 10.1002/App.32420 Google Scholar
  21. 21.
    Chen X, Nguyen TD (2011) Mech Mater 43(3):127. doi: 10.1016/J.Mechmat.2011.01.001 CrossRefGoogle Scholar
  22. 22.
    Lendlein A, Kelch S (2002) Angewandte Chemie Int Edn 41(12):2034CrossRefGoogle Scholar
  23. 23.
    Liu C, Qin H, Mather PT (2007) J Mater Chem 17(16):1543. doi: 10.1039/B615954k CrossRefGoogle Scholar
  24. 24.
    Song L, Hu W, Wang GJ, Niu GG, Zhang HB, Cao H, Wang KJ, Yang HA, Zhu SQ (2010) Macromol Biosci 10(10):1194. doi: 10.1002/Mabi.201000028 CrossRefGoogle Scholar
  25. 25.
    Liu CD, Mather PT (2002) J Appl Med Plast 6(2):47Google Scholar
  26. 26.
    Behl M, Lendlein A (2007) Soft Matter 3(1):58. doi: 10.1039/B610611k CrossRefGoogle Scholar
  27. 27.
    Alteheld A, Feng YK, Kelch S, Lendlein A (2005) Angewandte Chemie-Int Edn 44(8):1188. doi: 10.1002/anie.200461360 CrossRefGoogle Scholar
  28. 28.
    Miaudet P, Derre A, Maugey M, Zakri C, Piccione PM, Inoubli R, Poulin P (2007) Science 318(5854):1294. doi: 10.1126/Science.1145593 CrossRefGoogle Scholar
  29. 29.
    Xie T (2010) Nature 464(7286):267. doi: 10.1038/Nature08863 CrossRefGoogle Scholar
  30. 30.
    Kratz K, Madbouly SA, Wagermaier W, Lendlein A (2011) Adv Mater 23(35):4058. doi: 10.1002/Adma.201102225 CrossRefGoogle Scholar
  31. 31.
    Chen SJ, Hu JL, Yuen CWM, Chan LK, Zhuo HT (2010) Polym Adv Technol 21(5):377. doi: 10.1002/Pat.1523 Google Scholar
  32. 32.
    Luo XF, Mather PT (2010) Adv Funct Mater 20(16):2649. doi: 10.1002/Adfm.201000052 CrossRefGoogle Scholar
  33. 33.
    Zotzmann J, Behl M, Hofmann D, Lendlein A (2010) Adv Mater 22(31):3424. doi: 10.1002/Adma.200904202 CrossRefGoogle Scholar
  34. 34.
    Behl M, Bellin I, Kelch S, Wagermaier W, Lendlein A (2009) Adv Funct Mater 19(1):102. doi: 10.1002/Adfm.200800850 CrossRefGoogle Scholar
  35. 35.
    Bellin I, Kelch S, Langer R, Lendlein A (2006) Proc Nat Acad Sci USA 103(48):18043. doi: 10.1073/Pnas.0608586103 CrossRefGoogle Scholar
  36. 36.
    Sun L, Huang WM (2010) Soft Matter 6:4403. doi: 10.1039/c0sm00236d CrossRefGoogle Scholar
  37. 37.
    Moeller M, Hedrick JL, Degée P, Dubois P (2001) Ring Opening Polymerization. In: Buschow KHJr, Robert WC, Merton CF et al. (eds) Encyclopedia of Materials: Science and Technology. Elsevier, Oxford, pp 8202-8216. doi: 10.1016/b0-08-043152-6/01470-4
  38. 38.
    Lendlein A, Schmidt AM, Schroeter M, Langer R (2005) J Polym Sci Pol Chem 43(7):1369. doi: 10.1002/Pola.20598 CrossRefGoogle Scholar
  39. 39.
    Sanda F, Sanada H, Shibasaki Y, Endo T (2002) Macromolecules 35(3):680. doi: 10.1021/Ma011341f CrossRefGoogle Scholar
  40. 40.
    Khonakdar HA, Jafari SH, Rasouli S, Morshedian J, Abedini H (2007) Macromol Theor Simul 16(1):43. doi: 10.1002/Mats.200600041 CrossRefGoogle Scholar
  41. 41.
    Gall K, Yakacki CM, Liu YP, Shandas R, Willett N, Anseth KS (2005) J Biomed Mater Res A 73A(3):339. doi: 10.1002/Jbm.A.30296 CrossRefGoogle Scholar
  42. 42.
    Liu YP, Gall K, Dunn ML, McCluskey P (2003) Smart Mater Struct 12(6):947CrossRefGoogle Scholar
  43. 43.
    Hu JL, Ji FL, Wong YW (2005) Polym Int 54(3):600. doi: 10.1002/Pi.1745 CrossRefGoogle Scholar
  44. 44.
    Wong YS, Xiong Y, Venkatraman SS, Boey FYC (2008) J Biomater Sci Polym Edn 19(2):175CrossRefGoogle Scholar
  45. 45.
    Xie T, Page KA, Eastman SA (2011) Adv Funct Mater 21(11):2057. doi: 10.1002/Adfm.201002579 CrossRefGoogle Scholar
  46. 46.
    Yakacki CM, Nguyen TD, Likos R, Lamell R, Guigou D, Gall K (2011) Polymer 52(21):4947. doi: 10.1016/J.Polymer.2011.08.027 CrossRefGoogle Scholar
  47. 47.
    Yakacki CM, Shandas R, Lanning C, Rech B, Eckstein A, Gall K (2007) Biomaterials 28(14):2255. doi: 10.1016/J.Biomaterials.2007.01.030 CrossRefGoogle Scholar
  48. 48.
    Azra C, Plummer CJG, Manson JAE (2011) Smart Materials & Structures 20 (8). doi: 10.1088/0964-1726/20/8/082002
  49. 49.
    Meyerhoff G, Appelt B (1979) Macromolecules 12(5):968CrossRefGoogle Scholar
  50. 50.
    Miller RL (1992) Crystallographic data for various polymers. In: E.H. BJaI (ed) Polymer Handbook, 3rd Ed. John Wiley and Sons, New York, p VI/62Google Scholar
  51. 51.
    Jain SR, Sekkar V, Krishnamurthy VN (1993) J Appl Polym Sci 48(9):1515CrossRefGoogle Scholar
  52. 52.
    Flory PJ (1953) Principles of polymer chemistry. Cornell University Press, IthacaGoogle Scholar
  53. 53.
    Wang SF, Yaszemski MJ, Knight AM, Gruetzmacher JA, Windebank AJ, Lu LC (2009) Acta Biomater 5(5):1531. doi: 10.1016/J.Actbio.2008.12.015 CrossRefGoogle Scholar
  54. 54.
    Nojima S, Hashizume K, Rohadi A, Sasaki S (1997) Polymer 38(11):2711CrossRefGoogle Scholar
  55. 55.
    Wang SF, Yaszemski MJ, Gruetzmacher JA, Lu LC (2008) Polymer 49(26):5692. doi: 10.1016/J.Polymer.2008.10.021 CrossRefGoogle Scholar
  56. 56.
    Fu Q, Men Y, Strobl G (2003) Polymer 44(6):1927CrossRefGoogle Scholar
  57. 57.
    Men YF, Rieger J, Strobl G (2003) Phys Rev Lett 91 (9). doi:  10.1103/Physrevlett.91.095502

Copyright information

© Springer Science+Business Media, LLC 2012

Authors and Affiliations

  • Massimo Messori
    • 1
  • Micaela Degli Esposti
    • 1
  • Katia Paderni
    • 1
  • Stefano Pandini
    • 2
  • Simone Passera
    • 2
  • Theonis Riccò
    • 2
  • Maurizio Toselli
    • 3
  1. 1.Department of Engineering ‘Enzo Ferrari’University of Modena and Reggio EmiliaModenaItaly
  2. 2.Department of Mechanical and Industrial EngineeringUniversity of BresciaBresciaItaly
  3. 3.Department of Civil, Environmental and Materials EngineeringUniversity of BolognaBolognaItaly

Personalised recommendations