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Phase behavior and effects of microstructure on viscoelastic properties of a series of polylactides and polylactide/poly(ε-caprolactone) copolymers

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Abstract

Dynamic viscoelastic measurements were combined with differential scanning calorimetry (DSC) and atomic force microscopy (AFM) analysis to investigate the rheology, phase structure, and morphology of poly(l-lactide) (PLLA), poly(ε-caprolactone) (PCL), poly(d,l-lactide) (PDLLA) with molar composition l-LA/d-LA = 53:47, and poly(l-lactide-co-ε-caprolactone) (PLAcoCL) with molar composition l-LA/CL = 67:33. After melt conformation, both copolymers PDLLA and PLAcoCL were found to be amorphous whereas PLLA and PCL presented partial crystallinity. The copolymers and PCL were considered as thermorheologically simple according to the rheological methods employed. Therefore, data from different temperatures could be overlapped by a simple horizontal shift (a T) on elastic modulus, G′, and loss modulus, G′, versus frequency graph, generating the corresponding master curves. Moreover, these master curves showed a dependency of G″≈ω and G′≈ω 2 at low frequencies, which is a characteristic of homogeneous melts. For the first time, fundamental viscoelastic parameters, such as entanglement modulus G N 0 and reptation time τ d, of a PLAcoCL copolymer were obtained and correlated to chain microstructure. PLLA, by contrast, was unexpectedly revealed as a thermorheologically complex liquid according to the failure observed in the superposition of the phase angle (δ) versus the complex modulus (G*); this result suggests that the narrow window for rheological measurements, chosen to be close to the melting point centered at 180 °C thus avoiding thermal degradation, was not sufficient to assure an homogeneous behavior of PLLA melts. The understanding of the melt rheology related to the chain microstructural aspects will help in the understanding of the complex phase structures present in medical devices.

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Acknowledgments

The authors are grateful for funds of the Basque Government (GV/EJ) Department of Education, Universities and Research for project GIC10/152-IT-334-10 and for predoctoral grant of J. M. U., MICINN for project BIO2010-21542-C02-01, and the University of the Basque Country for project UFI11/56.

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  1. Department of Mining-Metallurgy Engineering and Materials Science, POLYMAT, School of Engineering, University of the Basque Country (EHU-UPV), Alameda Urquijo s/n, 48013, Bilbao, Spain

    Jone M. Ugartemendia & Jose R. Sarasua

  2. Polymer Science and Technology Department and POLYMAT Institute, Faculty of Chemistry, University of the Basque Country (EHU-UPV), PO Box 1072, 20080, Donostia-San Sebastian, Spain

    Maria E. Muñoz & Anton Santamaria

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  1. Jone M. Ugartemendia
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  2. Maria E. Muñoz
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  3. Jose R. Sarasua
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Correspondence to Anton Santamaria.

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Ugartemendia, J.M., Muñoz, M.E., Sarasua, J.R. et al. Phase behavior and effects of microstructure on viscoelastic properties of a series of polylactides and polylactide/poly(ε-caprolactone) copolymers. Rheol Acta 53, 857–868 (2014). https://doi.org/10.1007/s00397-014-0797-8

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