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An investigation into the crystalline morphology transitions in poly-L-lactic acid (PLLA) under uniaxial deformation in the quasi-solid-state regime

[Display omitted] •The mechanical behaviour of poly-l-lactic acid depends strongly on Td.•SAXS/WAXS data showed that strain-induced crystallization occurs on drawing.•The disordered α′ crystal form was observed post-draw at Td between 60 and 80 °C.•Drawing at Td ≥ 90 °C, resulted in the ordered α cr...

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Published in:European polymer journal 2018-04, Vol.101, p.127-139
Main Authors: Billimoria, Kharmen, Heeley, Ellen L., Parsons, Nathan, Figiel, Łukasz
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Parsons, Nathan
Figiel, Łukasz
description [Display omitted] •The mechanical behaviour of poly-l-lactic acid depends strongly on Td.•SAXS/WAXS data showed that strain-induced crystallization occurs on drawing.•The disordered α′ crystal form was observed post-draw at Td between 60 and 80 °C.•Drawing at Td ≥ 90 °C, resulted in the ordered α crystal form directly.•An oriented lamellar macromorphology developed post-draw, in samples on annealing. The mechanical behaviour, crystalline and macromorphology structure development during uniaxial deformation and annealing of poly-l-lactic acid (PLLA), with varying strain rate and draw temperatures (Td) above Tg, have been investigated using small- and wide-angle X-ray scattering (SAXS/WAXS), microscopy, thermal and mechanical techniques. The mechanical behaviour of PLLA, was strongly dependent on Td where embrittlement and eventual failure were observed as Td was increased, during uniaxial drawing of the amorphous polymer. This was mirrored in the bulk surface morphology where crazing, microvoiding and cavitation occurred with increasing Td. SAXS/WAXS data showed that strain-induced crystallization occurs on drawing, but crystallite orientation decreased with increasing Td, due to chain relaxation at temperatures ≥30 °C above Tg. However, no long-range oriented lamellar macromorphology was observed post-draw directly and only developed in the samples that were step annealed at temperatures above Td. Also, the disordered α′ crystal form was observed post-draw at Td between 60 and 80 °C, whereas Td ≥ 90 °C, resulted in the ordered α crystal form directly. However, on annealing at temperatures of ≥110 °C, the α′-α crystal transition ensued and in all samples, an oriented lamellar macromorphology developed. Therefore, Td and post-draw annealing, have a significant influence on the mechanical properties, crystallinity and crystalline phase transformation in PLLA, which in-turn, affects the polymers medical and industrial applications.
doi_str_mv 10.1016/j.eurpolymj.2018.01.031
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The mechanical behaviour, crystalline and macromorphology structure development during uniaxial deformation and annealing of poly-l-lactic acid (PLLA), with varying strain rate and draw temperatures (Td) above Tg, have been investigated using small- and wide-angle X-ray scattering (SAXS/WAXS), microscopy, thermal and mechanical techniques. The mechanical behaviour of PLLA, was strongly dependent on Td where embrittlement and eventual failure were observed as Td was increased, during uniaxial drawing of the amorphous polymer. This was mirrored in the bulk surface morphology where crazing, microvoiding and cavitation occurred with increasing Td. SAXS/WAXS data showed that strain-induced crystallization occurs on drawing, but crystallite orientation decreased with increasing Td, due to chain relaxation at temperatures ≥30 °C above Tg. However, no long-range oriented lamellar macromorphology was observed post-draw directly and only developed in the samples that were step annealed at temperatures above Td. Also, the disordered α′ crystal form was observed post-draw at Td between 60 and 80 °C, whereas Td ≥ 90 °C, resulted in the ordered α crystal form directly. However, on annealing at temperatures of ≥110 °C, the α′-α crystal transition ensued and in all samples, an oriented lamellar macromorphology developed. 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The mechanical behaviour, crystalline and macromorphology structure development during uniaxial deformation and annealing of poly-l-lactic acid (PLLA), with varying strain rate and draw temperatures (Td) above Tg, have been investigated using small- and wide-angle X-ray scattering (SAXS/WAXS), microscopy, thermal and mechanical techniques. The mechanical behaviour of PLLA, was strongly dependent on Td where embrittlement and eventual failure were observed as Td was increased, during uniaxial drawing of the amorphous polymer. This was mirrored in the bulk surface morphology where crazing, microvoiding and cavitation occurred with increasing Td. SAXS/WAXS data showed that strain-induced crystallization occurs on drawing, but crystallite orientation decreased with increasing Td, due to chain relaxation at temperatures ≥30 °C above Tg. However, no long-range oriented lamellar macromorphology was observed post-draw directly and only developed in the samples that were step annealed at temperatures above Td. Also, the disordered α′ crystal form was observed post-draw at Td between 60 and 80 °C, whereas Td ≥ 90 °C, resulted in the ordered α crystal form directly. However, on annealing at temperatures of ≥110 °C, the α′-α crystal transition ensued and in all samples, an oriented lamellar macromorphology developed. 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The mechanical behaviour, crystalline and macromorphology structure development during uniaxial deformation and annealing of poly-l-lactic acid (PLLA), with varying strain rate and draw temperatures (Td) above Tg, have been investigated using small- and wide-angle X-ray scattering (SAXS/WAXS), microscopy, thermal and mechanical techniques. The mechanical behaviour of PLLA, was strongly dependent on Td where embrittlement and eventual failure were observed as Td was increased, during uniaxial drawing of the amorphous polymer. This was mirrored in the bulk surface morphology where crazing, microvoiding and cavitation occurred with increasing Td. SAXS/WAXS data showed that strain-induced crystallization occurs on drawing, but crystallite orientation decreased with increasing Td, due to chain relaxation at temperatures ≥30 °C above Tg. However, no long-range oriented lamellar macromorphology was observed post-draw directly and only developed in the samples that were step annealed at temperatures above Td. Also, the disordered α′ crystal form was observed post-draw at Td between 60 and 80 °C, whereas Td ≥ 90 °C, resulted in the ordered α crystal form directly. However, on annealing at temperatures of ≥110 °C, the α′-α crystal transition ensued and in all samples, an oriented lamellar macromorphology developed. Therefore, Td and post-draw annealing, have a significant influence on the mechanical properties, crystallinity and crystalline phase transformation in PLLA, which in-turn, affects the polymers medical and industrial applications.</abstract><cop>Oxford</cop><pub>Elsevier Ltd</pub><doi>10.1016/j.eurpolymj.2018.01.031</doi><tpages>13</tpages><oa>free_for_read</oa></addata></record>
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subjects Annealing
Cavitation
Crazing
Crystal structure
Crystalline morphology
Crystallinity
Crystallization
Deformation
Industrial applications
Mechanical properties
Morphology
Orientation
Phase transitions
Poly-l-lactic acid
Polycrystals
Polylactic acid
SAXS/WAXS
Small angle X ray scattering
Solid state physics
Strain rate
Uniaxial deformation
title An investigation into the crystalline morphology transitions in poly-L-lactic acid (PLLA) under uniaxial deformation in the quasi-solid-state regime
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