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Different types of ibuprofen-loaded, poly (D,L lactic-co-glycolic acid) (PLGA)-based implants were prepared by 3D printing (Droplet Deposition Modeling). The theoretical filling density of the mesh-shaped implants was varied from 10 to 100%. Drug release was measured in agarose gels and in well agitated phosphate buffer pH 7.4. The key properties of the implants (and dynamic changes thereof upon exposure to the release media) were monitored using gravimetric measurements, optical microscopy, Differential Scanning Calorimetry, Gel Permeation Chromatography, and Scanning Electron Microscopy. Interestingly, drug release was similar for implants with 10 and 30% filling density, irrespective of the experimental set-up. In contrast, implants with 100% filling density showed slower release kinetics, and the shape of the release curve was altered in agarose gels. These observations could be explained by the existence (or absence) of a continuous aqueous phase between the polymeric filaments and the "orchestrating role" of substantial system swelling for the control of drug release. At lower filling densities, it is sufficient for the drug to be released from a single filament. In contrast, at high filling densities, the ensemble of filaments acts as a much larger (more or less homogeneous) polymeric matrix, and the average diffusion pathway to be overcome by the drug is much longer. Agarose gel (mimicking living tissue) hinders substantial PLGA swelling and delays the onset of the final rapid drug release phase. This improved mechanistic understanding of the control of drug release from PLGA-based 3D printed implants can help to facilitate the optimization of this type of advanced drug delivery systems., (Copyright © 2023 Elsevier B.V. All rights reserved.)

3D Printing offers a considerable potential for personalized medicines. This is especially true for customized biodegradable implants, matching the specific needs of each patient. Poly(lactic-co-glycolic acid) (PLGA) is frequently used as matrix former in biodegradable implants. However, yet relatively little is known on the technologies, which can be used for the 3D printing of PLGA implants. The aim of this study was to compare: (i) Arburg Plastic Freeforming Droplet Deposition Modeling (APF DDM), and (ii) Fused Deposition Modeling (FDM) to print mesh-shaped, ibuprofen-loaded PLGA implants. During APF DDM, individual drug-polymer droplets are deposited, fusing together to form filaments, which build up the implants. During FDM, continuous drug-polymer filaments are deposited to form the meshes. The implants were thoroughly characterized before and after exposure to phosphate buffer pH 7.4 using optical and scanning electron microscopy, GPC, DSC, drug release measurements and monitoring dynamic changes in the systems' dry & wet mass and pH of the bulk fluid. Interestingly, the mesh structures were significantly different, although the device design (composition & theoretical geometry) were the same. This could be explained by the fact that the deposition of individual droplets during APF DDM led to curved and rather thick filaments, resulting in a much lower mesh porosity. In contrast, FDM printing generated straight and thinner filaments: The open spaces between them were much larger and allowed convective mass transport during drug release. Consequently, most of the drug was already released after 4 d, when substantial PLGA set on. In the case of APF DDM printed implants, most of the drug was still entrapped at that time point and substantial polymer swelling transformed the meshes into more or less continuous PLGA gels. Hence, the diffusion pathways became much longer and ibuprofen release was controlled over 2 weeks., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Scaffolds can be defined as 3D architectures with specific features (surface properties, porosity, rigidity, biodegradability, etc.) that help cells to attach, proliferate, and to differentiate into specific lineage. For bone regeneration, rather high mechanical properties are required. That is why polylactic acid (PLA) and PLA/hydroxyapatite (HA) scaffolds (10 wt.%) were produced by a peculiar fused filament fabrication (FFF)-derived process. The effect of the addition of HA particles in the scaffolds was investigated in terms of morphology, biological properties, and biodegradation behavior. It was found that the scaffolds were biocompatible and that cells managed to attach and proliferate. Biodegradability was assessed over a 5-month period (according to the ISO 13781-Biodegradability norm) through gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and compression tests. The results revealed that the presence of HA in the scaffolds induced a faster and more complete polymer biodegradation, with a gradual decrease in the molar mass (Mn) and compressive mechanical properties over time. In contrast, the Mn of PLA only decreased during the processing steps to obtain scaffolds (extrusion + 3D-printing) but PLA scaffolds did not degrade during conditioning, which was highlighted by a high retention of the mechanical properties of the scaffolds after conditioning.

The present review relates to the field of nanocomposite materials comprising a thermoplastic nanofibrillar phase dispersed in a matrix that is also thermoplastic. The fact of forming the nanofibrillar phase in situ during melt processing gives it the role of a reinforcing nanofiller for thermoplastic materials. This paper discusses the major factors influencing the formation of self-reinforced nanofibrillar polymer composite (NFC) materials throughout manufacturing steps. More specifically, the rheological considerations allowing the prediction of the in situ nanofibrillation during melt blending and post-processing as well as the methods of production of these polymer nanocomposites are described. The major challenges related to the future development in the field of NFCs are addressed. The concept of self-reinforced nanofibrillar polymer materials shows great potential in lightweight eco-design processes and represents a new approach to polymer nanocomposite recycling for a variety of industrial applications.

Biodegradable PLA/PBSA multinanolayer nanocomposites were obtained from semi-crystalline poly(butylene succinate- co -butylene adipate) (PBSA) nanolayers filled with nanoclays and confined against amorphous poly(lactic acid) (PLA) nanolayers in a continuous manner by applying an innovative coextrusion technology. The cloisite 30B (C30B) filler incorporation in nanolayers was considered to be an improvement of barrier properties of the multilayer films additional to the confinement effect resulting to forced assembly during the multilayer coextrusion process. 2049-layer films of ~300 µm thick were processed containing loaded PBSA nanolayers of ~200 nm, which presented certain homogeneity and were mostly continuous for the 80/20 wt% PLA/PBSA composition. The nanocomposite PBSA films (monolayer) were also processed for comparison. The presence of exfoliated and intercalated clay structure and some aggregates were observed within the PBSA nanolayers depending on the C30B content. A greater reduction of macromolecular chain segment mobility was measured due to combined effects of confinement effect and clays constraints. The absence of both polymer and clays interdiffusions was highlighted since the PLA glass transition was unchanged. Besides, a larger increase in local chain rigidification was evidenced through RAF values due to geometrical constraints initiated by close nanoclay contact without changing the crystallinity of PBSA. Tortuosity effects into the filled PBSA layers adding to confinement effects induced by PLA layers have caused a significant improvement of water barrier properties through a reduction of water permeability, water vapor solubility and water vapor diffusivity. The obtaining barrier properties were successfully correlated to microstructure, thermal properties and mobility of PBSA amorphous phase.

Bio-based poly(l-lactide)/poly(amide-11) blends (PLA/PA11, 80/20 w/w) and poly(l-lactide)/poly(amide-6) blends (PLA/PA6, 80/20 w/w) are processed by twin-screw extrusion followed by injection-moulding and key rheological parameters controlling their morphologie are investigated. The same work is done using the same PLA modified by a multi-step reactive extrusion route with an epoxy-based chain extender to obtain modified poly(lactide)/poly(amide-11) (PLA-j/PA11 80/20 w/w) blends. The morphologies of the extruded materials and of the injection moulded parts are characterized by SEM and their formation is deeply discussed via rheological investigation to highlight the contribution of viscosity, elasticity and interfacial tension. The existence of a critical shear rate related to the transition from nodular to fibrillar morphology is highlighted and the results are in good agreement with the condition of fibrillation Ca/Ca (crit) ≥ 4. Interestingly, with the exception of PLA/PA6 specimens, all blends obviously display uniform thin-thread fibrillar morphologies after injection-moulding. Compared with pure PLA, a drastic increase of the ductility was observed in the blends exhibiting a fiberlike structure without meanwhile sacrificing the stiffness. This study confirms that, through the appropriate choice of blend components (viscosity and elasticity ratio, flow conditions, interfacial tensions) the in situ fibrillation concept provides access, at a reasonable cost, to new materials with improved thermomechanical performances, without sacrificing weight and ability to be recycled., Competing Interests: There are no conflits to declare., (This journal is © The Royal Society of Chemistry.)

Poly(vinylidene difluoride) (PVDF) displays attractive ferroelectric/piezoelectric properties and its polar β-crystals are specifically targeted for achieving electroactive applications. However, their direct crystallization from the melt state represents a challenging task that has never been addressed using melt-state processes. The use of poly(methyl methacrylate) (PMMA) is herein investigated to promote the PVDF polar β-phase using melt-blending and extrusion-calendering technologies. The presence of the β-phase is here confirmed by ATR-FTIR and WAXS experiments with blends at a PMMA content as low as 5 wt%. The key role of PMMA for the β-phase crystallization from the melt state was unambiguously highlighted with the help of Flash DSC experiments in non-isothermal cooling mode from the melt state. PMMA is able to efficiently shift the α-to-β crystal transition to lower cooling rates (>100-200 °C s-1), making the achievement of the PVDF polar β-phase for these blends compatible with conventional processing tools. A crystal phase diagram is proposed for the PVDF/PMMA blends to highlight the dual effects of both PMMA and cooling rate on the PVDF crystallization during melt-processing. Ferroelectric properties were even observed for the blends containing PMMA up to 10 wt% with the highest remanent polarization obtained at 5 wt% PMMA. After 10 wt% PMMA, a progressive transition from ferroelectric to pseudo-linear dielectric behavior is observed more likely due to the presence of PMMA in the interlamellar amorphous phase of the polar PVDF spherulites as shown by SAXS experiments. In this work, we successfully demonstrated that PMMA plays a key role in the crystallization of PVDF polar crystals from the melt state, enabling large-scale and continuous extrusion processing of PVDF-based materials with attractive dielectric properties for sensing and harvesting applications.

Potato and pea starches were processed on a twin-screw extruder under various moisture and thermomechanical conditions, chosen to keep material temperature T e close to starch melting temperature, T m , whilst avoiding die expansion. Extruded rods were analysed by asymmetrical flow field flow fractionation coupled with light scattering, X-ray diffraction, DSC, and light microscopy with image analysis. Molar mass of extruded materials decreased more for potato than for pea starch, when specific mechanical energy SME increased, likely because of larger amylopectin sensitivity to shear. No crystallinity was detected when ΔT = (T m -T e ) ≤ 0. Residual gelatinization enthalpy ΔH g decreased with ΔT. As illustrated by larger ΔT values for ΔH g  = 0, decreasing moisture favored melting, likely by increasing solid friction. The fraction of granular remnants of potato starch was inversely correlated to SME. These results could be explained by considering starch melting during extrusion as a suspension of solid particles embedded in a continuous amorphous matrix., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Prednisolone is known to exist in two anhydrous solid polymorphic forms. The substance is known to degrade upon melting, resulting in erroneous melting data, as shown by the widely scattered results reported in the literature. In this article, thermal analyses carried out at different scan rates show that the onset temperature and the enthalpy value of the signal increase with the scan rate and reach plateau values for high scan rates. Owing to flash scanning calorimetry, the plateau value for the temperature has been identified as the "true" temperature of melting of both polymorphs. This consistent set of new thermodynamic data on the two solid forms leads to the conclusion that both forms are unambiguously enantiotropes of each other. The solid-solid transition has been observed experimentally for the first time and has been confirmed by calculation.

Composites composed of polyesters, poly(butylene succinate) (PBS) or poly[(butylene succinate)-co-(butylene adipate)] (PBSA), and 5 wt% of montmorillonite (CNa) or organo-modified montmorillonite (C30B) were melt-processed and transformed into films by either compression-molding or extrusion-calendering. XRD, rheological measurements and TEM images clearly indicated that films containing CNa are microcomposites, while nanocomposites were observed for those containing C30B. Using Flash DSC, it was possible, for the first time, not only to measure the heat capacity step at the glass transition of these two materials in their amorphous state, but also to investigate whether the preparation technique influenced the Rigid Amorphous Fraction (RAF) in our PBS- and PBSA-based nanocomposites. In this work, we have successfully shown the correlation between the microstructure of the films and their barrier properties, and especially the role played by the RAF. Indeed, the lowest permeabilities to gases and to water were determined in the films containing the highest RAF in both PBS- and PBSA-based materials.

Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P3HB-co-4HB) films containing various contents of organo-modified montmorillonite C30B nanoclays were prepared by melt intercalation. Wide angle X-ray diffraction measurements and transmission electron microscopy observations evidenced aggregated and intercalated structures with individual nanoclay platelets in the nanocomposites and an orientation of nanoclays. Differential scanning calorimetry measurements showed that the nanoclay did not influence the crystalline structure of the matrix because it is mainly located in the polymer amorphous phase. The influence of the filler on the barrier properties of the film was evaluated by water diffusion, gas permeation (CO2, N2, O2) and liquid water sorption measurements. A decrease of the N2 permeability was measured due to the tortuosity effect of the filler associated with a decrease of the solubility within the matrix. The influence of the filler was more marked for O2 due to the larger decrease of O2 solubility. In contrast, the CO2 permeability increased whatever the filler content because of a facilitated transport mechanism due induced by the presence of quaternary ammonium cations on the C30B surface. The decrease of the water permeability with the filler was explained by a competition between the kinetic (diffusivity) and thermodynamic (solubility) contributions defining the permeability process.

Starch was combined with plasticizers such as glycerol, sorbitol, glycerol/sorbitol and urea/ethanolamine blends by means of high shear extrusion process to prepare thermoplastic starch (TPS). Effect of storage time and plasticizers on the structural stability of melt processed TPS was investigated. Morphological observation, X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy reveal that melt extrusion process is efficient in transforming granular starch into a plasticized starch for all plasticizer compositions. XRD analysis highlights major changes in the microstructure of plasticized starch, and dependence of crystalline type and degree of crystallinity mainly on the plasticizer composition and storage time. Dynamical mechanical analysis (DMA) yields a decrease of the peak intensity of loss factor with aging time. The effect of ageing on tensile strength also appears to be highly dependent on the plasticizer composition. Thus, through different plasticizer combinations and ageing, starch-based materials with significant differences in tensile properties can be obtained, which may be tuned to meet the requirements of a wide range of applications., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The aim of this paper is to understand the influence of plasticizer and plasticizer amount on the mechanical and deformation behaviors of plasticized starch. Glycerol, sorbitol and mannitol have been used as plasticizers. After extrusion of the various samples, dynamic mechanical analyses and video-controlled tensile tests have been performed. It was found that the nature of plasticizer, its amount as well as the aging of the material has an impact on the involved deformation mechanism. The variations of volume deformation could be explained by an antiplasticization effect (low plasticizer amount), a phase-separation phenomenon (excess of plasticizer) and/or by the retrogradation of starch., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Blends based on plasticized-wheat starch (as matrix or rich phase) and poly(ethylene oxide) (PEO) (as dispersed phase) were prepared by melt processing in a twin-screw extruder. The extrusion of the plasticized-starch is significantly facilitated by blending with PEO. Plasticized-starch and PEO are immiscible in the range of the investigated blend ratios (90/10-50/50). The phase inversion takes place when the PEO content is 50 wt.% in the blend. Both the thermal stability and the tensile properties of plasticized-starch are improved by blending with PEO. Also, a synergistic effect between plasticized-starch and PEO is noticed at 25-40 wt.% PEO content in the blend, the Young's modulus of the materials obtained being the highest and higher than both neat polymer components at those blending ratios., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Novel bionanocomposites based on halloysite nanotubes as nanofillers and plasticized starch as polymeric matrix were successfully prepared by melt-extrusion for the first time. Both modified and non modified halloysites were added at different weight contents. The structural, morphological, thermal and mechanical properties of plasticized starch/halloysites nanocomposites were investigated. Melt-compounding appears to be a suitable process to uniformly disperse nanotubes in the plasticized starch matrix. Interactions between plasticized starch and halloysites in the nanocomposites and microstructure modifications were monitored using Fourier transfer infrared spectroscopy, X-ray diffraction and dynamic mechanical analysis. Addition of halloysite nanotubes slightly enhances the thermal stability of starch (onset temperature of degradation delayed to higher temperatures). The tensile mechanical properties of starch are also significantly improved (up to +144% for Young's modulus and up to +29% for strength) upon addition of both modified and unmodified halloysites, interestingly without loss of ductility. Modified halloysites lead to significantly higher Young's modulus than unmodified halloysites., (Copyright © 2012 Elsevier Ltd. All rights reserved.)