Composites Based on Poly(Lactic Acid) (PLA) and SBA-15: Effect of Mesoporous Silica on Thermal Stability and on Isothermal Crystallization from Either Glass or Molten State

Several composites based on an <i>L</i>-rich poly(lactic acid) (PLA) with different contents of mesoporous Santa Barbara Amorphous (SBA-15) silica were prepared in order to evaluate the effect of the mesoporous silica on the resultant PLA materials by examining morphological aspects, cha...

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Main Authors: Tamara M. Díez-Rodríguez, Enrique Blázquez-Blázquez, Ernesto Pérez, María L. Cerrada
Format: Article
Language:English
Published: MDPI AG 2020-11-01
Series:Polymers
Subjects:
Online Access:https://www.mdpi.com/2073-4360/12/11/2743
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spelling doaj-5da308e5269b4a82a27aa69e6a7baf4c2020-11-25T04:01:23ZengMDPI AGPolymers2073-43602020-11-01122743274310.3390/polym12112743Composites Based on Poly(Lactic Acid) (PLA) and SBA-15: Effect of Mesoporous Silica on Thermal Stability and on Isothermal Crystallization from Either Glass or Molten StateTamara M. Díez-Rodríguez0Enrique Blázquez-Blázquez1Ernesto Pérez2María L. Cerrada3Instituto de Ciencia y Tecnología de Polímeros (ICTP-CSIC), Juan de la Cierva 3, 28006 Madrid, SpainInstituto de Ciencia y Tecnología de Polímeros (ICTP-CSIC), Juan de la Cierva 3, 28006 Madrid, SpainInstituto de Ciencia y Tecnología de Polímeros (ICTP-CSIC), Juan de la Cierva 3, 28006 Madrid, SpainInstituto de Ciencia y Tecnología de Polímeros (ICTP-CSIC), Juan de la Cierva 3, 28006 Madrid, SpainSeveral composites based on an <i>L</i>-rich poly(lactic acid) (PLA) with different contents of mesoporous Santa Barbara Amorphous (SBA-15) silica were prepared in order to evaluate the effect of the mesoporous silica on the resultant PLA materials by examining morphological aspects, changes in PLA phases and their transitions, and, primarily, the influence on some final properties. Melt extrusion was chosen for the obtainment of the composites, followed by quenching from the melt to prepare films. Completely amorphous samples were then attained, as deduced from X-ray diffraction and differential scanning calorimetry (DSC) analyses. Thermogravimetric analysis (TGA) results demonstrated that the presence of SBA-15 particles in the PLA matrix did not exert any significant influence on the thermal decomposition of these composites. An important nucleation effect of the silica was found in PLA, especially under isothermal crystallization either from the melt or from its glassy state. As expected, isothermal crystallization from the glass was considerably faster than from the molten state, and these high differences were also responsible for a more considerable nucleating role of SBA-15 when crystallizing from the melt. It is remarkable that the PLA under analysis showed very close temperatures for cold crystallization and its subsequent melting. Moreover, the type of developed polymorphs did not accomplish the common rules previously described in the literature. Thus, all the isothermal experiments led to exclusive formation of the α modification, and the observation of the α’ crystals required the annealing for long times at temperatures below 80 °C, as ascertained by both DSC and X-ray diffraction experiments. Finally, microhardness (MH) measurements indicated a competition between the PLA physical aging and the silica reinforcement effect in the as-processed amorphous films. Physical aging in the neat PLA was much more important than in the PLA matrix that constituted the composites. Accordingly, the MH trend with SBA-15 content was strongly dependent on aging times.https://www.mdpi.com/2073-4360/12/11/2743PLA and SBA-15 compositesthermal stabilityisothermal crystallizationpolymorphismmicrohardness
collection DOAJ
language English
format Article
sources DOAJ
author Tamara M. Díez-Rodríguez
Enrique Blázquez-Blázquez
Ernesto Pérez
María L. Cerrada
spellingShingle Tamara M. Díez-Rodríguez
Enrique Blázquez-Blázquez
Ernesto Pérez
María L. Cerrada
Composites Based on Poly(Lactic Acid) (PLA) and SBA-15: Effect of Mesoporous Silica on Thermal Stability and on Isothermal Crystallization from Either Glass or Molten State
Polymers
PLA and SBA-15 composites
thermal stability
isothermal crystallization
polymorphism
microhardness
author_facet Tamara M. Díez-Rodríguez
Enrique Blázquez-Blázquez
Ernesto Pérez
María L. Cerrada
author_sort Tamara M. Díez-Rodríguez
title Composites Based on Poly(Lactic Acid) (PLA) and SBA-15: Effect of Mesoporous Silica on Thermal Stability and on Isothermal Crystallization from Either Glass or Molten State
title_short Composites Based on Poly(Lactic Acid) (PLA) and SBA-15: Effect of Mesoporous Silica on Thermal Stability and on Isothermal Crystallization from Either Glass or Molten State
title_full Composites Based on Poly(Lactic Acid) (PLA) and SBA-15: Effect of Mesoporous Silica on Thermal Stability and on Isothermal Crystallization from Either Glass or Molten State
title_fullStr Composites Based on Poly(Lactic Acid) (PLA) and SBA-15: Effect of Mesoporous Silica on Thermal Stability and on Isothermal Crystallization from Either Glass or Molten State
title_full_unstemmed Composites Based on Poly(Lactic Acid) (PLA) and SBA-15: Effect of Mesoporous Silica on Thermal Stability and on Isothermal Crystallization from Either Glass or Molten State
title_sort composites based on poly(lactic acid) (pla) and sba-15: effect of mesoporous silica on thermal stability and on isothermal crystallization from either glass or molten state
publisher MDPI AG
series Polymers
issn 2073-4360
publishDate 2020-11-01
description Several composites based on an <i>L</i>-rich poly(lactic acid) (PLA) with different contents of mesoporous Santa Barbara Amorphous (SBA-15) silica were prepared in order to evaluate the effect of the mesoporous silica on the resultant PLA materials by examining morphological aspects, changes in PLA phases and their transitions, and, primarily, the influence on some final properties. Melt extrusion was chosen for the obtainment of the composites, followed by quenching from the melt to prepare films. Completely amorphous samples were then attained, as deduced from X-ray diffraction and differential scanning calorimetry (DSC) analyses. Thermogravimetric analysis (TGA) results demonstrated that the presence of SBA-15 particles in the PLA matrix did not exert any significant influence on the thermal decomposition of these composites. An important nucleation effect of the silica was found in PLA, especially under isothermal crystallization either from the melt or from its glassy state. As expected, isothermal crystallization from the glass was considerably faster than from the molten state, and these high differences were also responsible for a more considerable nucleating role of SBA-15 when crystallizing from the melt. It is remarkable that the PLA under analysis showed very close temperatures for cold crystallization and its subsequent melting. Moreover, the type of developed polymorphs did not accomplish the common rules previously described in the literature. Thus, all the isothermal experiments led to exclusive formation of the α modification, and the observation of the α’ crystals required the annealing for long times at temperatures below 80 °C, as ascertained by both DSC and X-ray diffraction experiments. Finally, microhardness (MH) measurements indicated a competition between the PLA physical aging and the silica reinforcement effect in the as-processed amorphous films. Physical aging in the neat PLA was much more important than in the PLA matrix that constituted the composites. Accordingly, the MH trend with SBA-15 content was strongly dependent on aging times.
topic PLA and SBA-15 composites
thermal stability
isothermal crystallization
polymorphism
microhardness
url https://www.mdpi.com/2073-4360/12/11/2743
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