Effect of stereocomplex formation in d-lactide-containing plla on thermal behaviors and mechanical property changes using the ageing degradation test

Tsai Chin Shih, Che Tong Lin, Sheng Yang Lee, Wei Jen Chang, Nai Chia Teng, Keng Liang Ou, How Tseng

Research output: Contribution to journalArticle

Abstract

Introduction: The formation of a stereocomplex between PLLA and PDLA has been studied intensively because it increases the mechanical performance and thermal/hydrolytic resistance of polylactide-based materials; however, few studies have investigated the stereocomplex formation between PLLA and the (D-lactide)-containing PLLA copolymer. To investigate the effect of the D-lactide content of PLLA on the thermal behaviors and mechanical properties, (5D/95L) polylactide [(5D/95L)PLA], which contains a molar ratio of 5% of the D-form and 95% of the L-form of the monomer, and (15D/85L) polylactide [(15D/85L)PLA], which contains a molar ratio of 15% of the D-form and 85% of the L-form of the monomer, were used in a series of specimens. For the hydrolytic degradation test, the specimens were placed in 20-mL vials, which were filled with phosphate-buffered solution; the vials were allowed to stand at 57°C for 91 days in accordance with the ASTM F1635-95 (2000) standard test method for in vitro studies. The mechanical properties, thermal properties and crystallization behaviors were investigated using DSC and MTS, respectively. Results: The initial bending strength of the (5D/95L)PLA and (15D/85L)PLA were 35.4 and 31.1 N, respectively. After 1 week, the binding strength of the (5D/95L)PLA increased by 9.8%, and the binding strength of the (15D/85L)PLA decreased by 26%. In addition, the DSC curve of the (5D/95L)PLA demonstrated a higher melting temperature in the 1st week, and this Tc was observed in the DSC curve of the (5D/95L)PLA only during this time. The DSC curve of the (15D/85L)PLA was irregular. Discussion & Conclusions: In the (5D/95L)PLA, the recrystallization that occurred during the hydrolysis process was confirmed by the Tc and the increase in the bending strength. The stereocomplex crystallites may be formed in the (15D/85L)PLA during the degradation process. Because of the increase in the D-form monomer, the stereocomplexes were generated more easily and acted as nucleation sites. The PLLA crystal near the stereocomplex crystallites exhibited an incomplete structure, which led to a faster decrease in the bending strength. The low D-lactide content in the matrix of the PLLA did not form a stereocomplex crystallite because the surface area was not large enough to act as a nucleation site. However, the higher D-lactide-containing fraction formed a large stereocomplex crystallite. The (5D/95L)PLA demonstrated better thermal/hydrolytic resistance and mechanical stability than the (15D/85L)PLA.

Original languageEnglish
Article number1340003
JournalBiomedical Engineering - Applications, Basis and Communications
Volume25
Issue number5
DOIs
Publication statusPublished - Oct 2013

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Bending strength
Hot Temperature
Aging of materials
Monomers
Crystallites
L Forms
Heat resistance
Degradation
Mechanical properties
Nucleation
Mechanical stability
Melting point
Hydrolysis
Phosphates
Thermodynamic properties
Copolymers
Crystallization
Freezing
Crystals
Temperature

Keywords

  • Ageing test
  • Bone plate
  • PLLA
  • Stereocomplex

ASJC Scopus subject areas

  • Biophysics
  • Biomedical Engineering
  • Bioengineering

Cite this

@article{b23d55b0e84d4eac810a4d78ef04d061,
title = "Effect of stereocomplex formation in d-lactide-containing plla on thermal behaviors and mechanical property changes using the ageing degradation test",
abstract = "Introduction: The formation of a stereocomplex between PLLA and PDLA has been studied intensively because it increases the mechanical performance and thermal/hydrolytic resistance of polylactide-based materials; however, few studies have investigated the stereocomplex formation between PLLA and the (D-lactide)-containing PLLA copolymer. To investigate the effect of the D-lactide content of PLLA on the thermal behaviors and mechanical properties, (5D/95L) polylactide [(5D/95L)PLA], which contains a molar ratio of 5{\%} of the D-form and 95{\%} of the L-form of the monomer, and (15D/85L) polylactide [(15D/85L)PLA], which contains a molar ratio of 15{\%} of the D-form and 85{\%} of the L-form of the monomer, were used in a series of specimens. For the hydrolytic degradation test, the specimens were placed in 20-mL vials, which were filled with phosphate-buffered solution; the vials were allowed to stand at 57°C for 91 days in accordance with the ASTM F1635-95 (2000) standard test method for in vitro studies. The mechanical properties, thermal properties and crystallization behaviors were investigated using DSC and MTS, respectively. Results: The initial bending strength of the (5D/95L)PLA and (15D/85L)PLA were 35.4 and 31.1 N, respectively. After 1 week, the binding strength of the (5D/95L)PLA increased by 9.8{\%}, and the binding strength of the (15D/85L)PLA decreased by 26{\%}. In addition, the DSC curve of the (5D/95L)PLA demonstrated a higher melting temperature in the 1st week, and this Tc was observed in the DSC curve of the (5D/95L)PLA only during this time. The DSC curve of the (15D/85L)PLA was irregular. Discussion & Conclusions: In the (5D/95L)PLA, the recrystallization that occurred during the hydrolysis process was confirmed by the Tc and the increase in the bending strength. The stereocomplex crystallites may be formed in the (15D/85L)PLA during the degradation process. Because of the increase in the D-form monomer, the stereocomplexes were generated more easily and acted as nucleation sites. The PLLA crystal near the stereocomplex crystallites exhibited an incomplete structure, which led to a faster decrease in the bending strength. The low D-lactide content in the matrix of the PLLA did not form a stereocomplex crystallite because the surface area was not large enough to act as a nucleation site. However, the higher D-lactide-containing fraction formed a large stereocomplex crystallite. The (5D/95L)PLA demonstrated better thermal/hydrolytic resistance and mechanical stability than the (15D/85L)PLA.",
keywords = "Ageing test, Bone plate, PLLA, Stereocomplex",
author = "Shih, {Tsai Chin} and Lin, {Che Tong} and Lee, {Sheng Yang} and Chang, {Wei Jen} and Teng, {Nai Chia} and Ou, {Keng Liang} and How Tseng",
year = "2013",
month = "10",
doi = "10.4015/S1016237213400036",
language = "English",
volume = "25",
journal = "Journal of Chinese Corrosion Engineering",
issn = "1016-2372",
publisher = "World Scientific Publishing Co. Pte Ltd",
number = "5",

}

TY - JOUR

T1 - Effect of stereocomplex formation in d-lactide-containing plla on thermal behaviors and mechanical property changes using the ageing degradation test

AU - Shih, Tsai Chin

AU - Lin, Che Tong

AU - Lee, Sheng Yang

AU - Chang, Wei Jen

AU - Teng, Nai Chia

AU - Ou, Keng Liang

AU - Tseng, How

PY - 2013/10

Y1 - 2013/10

N2 - Introduction: The formation of a stereocomplex between PLLA and PDLA has been studied intensively because it increases the mechanical performance and thermal/hydrolytic resistance of polylactide-based materials; however, few studies have investigated the stereocomplex formation between PLLA and the (D-lactide)-containing PLLA copolymer. To investigate the effect of the D-lactide content of PLLA on the thermal behaviors and mechanical properties, (5D/95L) polylactide [(5D/95L)PLA], which contains a molar ratio of 5% of the D-form and 95% of the L-form of the monomer, and (15D/85L) polylactide [(15D/85L)PLA], which contains a molar ratio of 15% of the D-form and 85% of the L-form of the monomer, were used in a series of specimens. For the hydrolytic degradation test, the specimens were placed in 20-mL vials, which were filled with phosphate-buffered solution; the vials were allowed to stand at 57°C for 91 days in accordance with the ASTM F1635-95 (2000) standard test method for in vitro studies. The mechanical properties, thermal properties and crystallization behaviors were investigated using DSC and MTS, respectively. Results: The initial bending strength of the (5D/95L)PLA and (15D/85L)PLA were 35.4 and 31.1 N, respectively. After 1 week, the binding strength of the (5D/95L)PLA increased by 9.8%, and the binding strength of the (15D/85L)PLA decreased by 26%. In addition, the DSC curve of the (5D/95L)PLA demonstrated a higher melting temperature in the 1st week, and this Tc was observed in the DSC curve of the (5D/95L)PLA only during this time. The DSC curve of the (15D/85L)PLA was irregular. Discussion & Conclusions: In the (5D/95L)PLA, the recrystallization that occurred during the hydrolysis process was confirmed by the Tc and the increase in the bending strength. The stereocomplex crystallites may be formed in the (15D/85L)PLA during the degradation process. Because of the increase in the D-form monomer, the stereocomplexes were generated more easily and acted as nucleation sites. The PLLA crystal near the stereocomplex crystallites exhibited an incomplete structure, which led to a faster decrease in the bending strength. The low D-lactide content in the matrix of the PLLA did not form a stereocomplex crystallite because the surface area was not large enough to act as a nucleation site. However, the higher D-lactide-containing fraction formed a large stereocomplex crystallite. The (5D/95L)PLA demonstrated better thermal/hydrolytic resistance and mechanical stability than the (15D/85L)PLA.

AB - Introduction: The formation of a stereocomplex between PLLA and PDLA has been studied intensively because it increases the mechanical performance and thermal/hydrolytic resistance of polylactide-based materials; however, few studies have investigated the stereocomplex formation between PLLA and the (D-lactide)-containing PLLA copolymer. To investigate the effect of the D-lactide content of PLLA on the thermal behaviors and mechanical properties, (5D/95L) polylactide [(5D/95L)PLA], which contains a molar ratio of 5% of the D-form and 95% of the L-form of the monomer, and (15D/85L) polylactide [(15D/85L)PLA], which contains a molar ratio of 15% of the D-form and 85% of the L-form of the monomer, were used in a series of specimens. For the hydrolytic degradation test, the specimens were placed in 20-mL vials, which were filled with phosphate-buffered solution; the vials were allowed to stand at 57°C for 91 days in accordance with the ASTM F1635-95 (2000) standard test method for in vitro studies. The mechanical properties, thermal properties and crystallization behaviors were investigated using DSC and MTS, respectively. Results: The initial bending strength of the (5D/95L)PLA and (15D/85L)PLA were 35.4 and 31.1 N, respectively. After 1 week, the binding strength of the (5D/95L)PLA increased by 9.8%, and the binding strength of the (15D/85L)PLA decreased by 26%. In addition, the DSC curve of the (5D/95L)PLA demonstrated a higher melting temperature in the 1st week, and this Tc was observed in the DSC curve of the (5D/95L)PLA only during this time. The DSC curve of the (15D/85L)PLA was irregular. Discussion & Conclusions: In the (5D/95L)PLA, the recrystallization that occurred during the hydrolysis process was confirmed by the Tc and the increase in the bending strength. The stereocomplex crystallites may be formed in the (15D/85L)PLA during the degradation process. Because of the increase in the D-form monomer, the stereocomplexes were generated more easily and acted as nucleation sites. The PLLA crystal near the stereocomplex crystallites exhibited an incomplete structure, which led to a faster decrease in the bending strength. The low D-lactide content in the matrix of the PLLA did not form a stereocomplex crystallite because the surface area was not large enough to act as a nucleation site. However, the higher D-lactide-containing fraction formed a large stereocomplex crystallite. The (5D/95L)PLA demonstrated better thermal/hydrolytic resistance and mechanical stability than the (15D/85L)PLA.

KW - Ageing test

KW - Bone plate

KW - PLLA

KW - Stereocomplex

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