Study of the Interplay Among Melt Morphology, Rheology and 3D Printability of Poly(Lactic Acid)/Poly(3-Hydroxybutyrate-Co-3-Hydroxyvalerate) Blends
Polymeric materials made from renewable sources that can biodegrade in the environment are attracting considerable attention as substitutes for petroleum-based polymers in many fields, including additive manufacturing and, in particular, Fused Deposition Modelling (FDM). Among the others, poly(hydro...
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MDPI AG
2025-01-01
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| Series: | Journal of Functional Biomaterials |
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| Online Access: | https://www.mdpi.com/2079-4983/16/1/9 |
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| author | Marco Costantini Flavio Cognini Roberta Angelini Sara Alfano Marianna Villano Andrea Martinelli David Bolzonella Marco Rossi Andrea Barbetta |
| author_facet | Marco Costantini Flavio Cognini Roberta Angelini Sara Alfano Marianna Villano Andrea Martinelli David Bolzonella Marco Rossi Andrea Barbetta |
| author_sort | Marco Costantini |
| collection | DOAJ |
| description | Polymeric materials made from renewable sources that can biodegrade in the environment are attracting considerable attention as substitutes for petroleum-based polymers in many fields, including additive manufacturing and, in particular, Fused Deposition Modelling (FDM). Among the others, poly(hydroxyalkanoates) (PHAs) hold significant potential as candidates for FDM since they meet the sustainability and biodegradability standards mentioned above. However, the most utilised PHA, consisting of the poly(hydroxybutyrate) (PHB) homopolymer, has a high degree of crystallinity and low thermal stability near the melting point. As a result, its application in FDM has not yet attained mainstream adoption. Introducing a monomer with higher excluded volume, such as hydroxyvalerate, in the PHB primary structure, as in poly(hydroxybutyrate-co-valerate) (PHBV) copolymers, reduces the degree of crystallinity and the melting temperature, hence improving the PHA printability. Blending amorphous poly(lactic acid) (PLA) with PHBV enhances further PHA printability via FDM. In this work, we investigated the printability of two blends characterised by different PLA and PHBV weight ratios (25:75 and 50:50), revealing the close connection between blend microstructures, melt rheology and 3D printability. For instance, the relaxation time associated with die swelling upon extrusion determines the diameter of the extruded filament, while the viscoelastic properties the range of extrusion speed available. Through thoroughly screening printing parameters such as deposition speed, nozzle diameter, flow percentage and deposition platform temperature, we determined the optimal printing conditions for the two PLA/PHBV blends. It turned out that the blend with a 50:50 weight ratio could be printed faster and with higher accuracy. Such a conclusion was validated by replicating with remarkable fidelity high-complexity objects, such as a patient’s cancer-affected iliac crest model. |
| format | Article |
| id | doaj-art-8cabd497e5cf4a3b83c6bc3e3c649d61 |
| institution | Kabale University |
| issn | 2079-4983 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Journal of Functional Biomaterials |
| spelling | doaj-art-8cabd497e5cf4a3b83c6bc3e3c649d612025-01-24T13:36:06ZengMDPI AGJournal of Functional Biomaterials2079-49832025-01-01161910.3390/jfb16010009Study of the Interplay Among Melt Morphology, Rheology and 3D Printability of Poly(Lactic Acid)/Poly(3-Hydroxybutyrate-Co-3-Hydroxyvalerate) BlendsMarco Costantini0Flavio Cognini1Roberta Angelini2Sara Alfano3Marianna Villano4Andrea Martinelli5David Bolzonella6Marco Rossi7Andrea Barbetta8Institute of Physical Chemistry, Polish Academy of Sciences, 01-224 Warsaw, PolandDepartment of Basic and Applied Sciences for Engineering, Sapienza University of Rome, 00161 Rome, ItalyInstitute for Complex Systems, National Research Council (ISC-CNR), Sapienza University of Rome, P.le A. Moro 2, 00185 Rome, ItalyDepartment of Chemistry, Sapienza University of Rome, P.le Aldo Moro 5, 00185 Rome, ItalyDepartment of Chemistry, Sapienza University of Rome, P.le Aldo Moro 5, 00185 Rome, ItalyDepartment of Chemistry, Sapienza University of Rome, P.le Aldo Moro 5, 00185 Rome, ItalyDepartment of Biotechnology, University of Verona, Via Strada Le Grazie 15, 37134 Verona, ItalyDepartment of Basic and Applied Sciences for Engineering, Sapienza University of Rome, 00161 Rome, ItalyDepartment of Chemistry, Sapienza University of Rome, P.le Aldo Moro 5, 00185 Rome, ItalyPolymeric materials made from renewable sources that can biodegrade in the environment are attracting considerable attention as substitutes for petroleum-based polymers in many fields, including additive manufacturing and, in particular, Fused Deposition Modelling (FDM). Among the others, poly(hydroxyalkanoates) (PHAs) hold significant potential as candidates for FDM since they meet the sustainability and biodegradability standards mentioned above. However, the most utilised PHA, consisting of the poly(hydroxybutyrate) (PHB) homopolymer, has a high degree of crystallinity and low thermal stability near the melting point. As a result, its application in FDM has not yet attained mainstream adoption. Introducing a monomer with higher excluded volume, such as hydroxyvalerate, in the PHB primary structure, as in poly(hydroxybutyrate-co-valerate) (PHBV) copolymers, reduces the degree of crystallinity and the melting temperature, hence improving the PHA printability. Blending amorphous poly(lactic acid) (PLA) with PHBV enhances further PHA printability via FDM. In this work, we investigated the printability of two blends characterised by different PLA and PHBV weight ratios (25:75 and 50:50), revealing the close connection between blend microstructures, melt rheology and 3D printability. For instance, the relaxation time associated with die swelling upon extrusion determines the diameter of the extruded filament, while the viscoelastic properties the range of extrusion speed available. Through thoroughly screening printing parameters such as deposition speed, nozzle diameter, flow percentage and deposition platform temperature, we determined the optimal printing conditions for the two PLA/PHBV blends. It turned out that the blend with a 50:50 weight ratio could be printed faster and with higher accuracy. Such a conclusion was validated by replicating with remarkable fidelity high-complexity objects, such as a patient’s cancer-affected iliac crest model.https://www.mdpi.com/2079-4983/16/1/9poly(3-hydroxybutyrate-co-3-hydroxyvalerate)polylactic acidpolymer blendsrheology of polymer meltsfused deposition modelling |
| spellingShingle | Marco Costantini Flavio Cognini Roberta Angelini Sara Alfano Marianna Villano Andrea Martinelli David Bolzonella Marco Rossi Andrea Barbetta Study of the Interplay Among Melt Morphology, Rheology and 3D Printability of Poly(Lactic Acid)/Poly(3-Hydroxybutyrate-Co-3-Hydroxyvalerate) Blends Journal of Functional Biomaterials poly(3-hydroxybutyrate-co-3-hydroxyvalerate) polylactic acid polymer blends rheology of polymer melts fused deposition modelling |
| title | Study of the Interplay Among Melt Morphology, Rheology and 3D Printability of Poly(Lactic Acid)/Poly(3-Hydroxybutyrate-Co-3-Hydroxyvalerate) Blends |
| title_full | Study of the Interplay Among Melt Morphology, Rheology and 3D Printability of Poly(Lactic Acid)/Poly(3-Hydroxybutyrate-Co-3-Hydroxyvalerate) Blends |
| title_fullStr | Study of the Interplay Among Melt Morphology, Rheology and 3D Printability of Poly(Lactic Acid)/Poly(3-Hydroxybutyrate-Co-3-Hydroxyvalerate) Blends |
| title_full_unstemmed | Study of the Interplay Among Melt Morphology, Rheology and 3D Printability of Poly(Lactic Acid)/Poly(3-Hydroxybutyrate-Co-3-Hydroxyvalerate) Blends |
| title_short | Study of the Interplay Among Melt Morphology, Rheology and 3D Printability of Poly(Lactic Acid)/Poly(3-Hydroxybutyrate-Co-3-Hydroxyvalerate) Blends |
| title_sort | study of the interplay among melt morphology rheology and 3d printability of poly lactic acid poly 3 hydroxybutyrate co 3 hydroxyvalerate blends |
| topic | poly(3-hydroxybutyrate-co-3-hydroxyvalerate) polylactic acid polymer blends rheology of polymer melts fused deposition modelling |
| url | https://www.mdpi.com/2079-4983/16/1/9 |
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