Distinct dynamics of structural relaxation in the amorphous phase of poly(l-lactic acid) revealed by quiescent crystallization.

Fast scanning calorimetry (FSC) experiments were performed to investigate physical aging in amorphous and semi-crystalline poly(l-lactic acid)s (PLLAs) that were thermally crystallized under conditions leading to the α'- or α-crystalline form, and either favouring or inhibiting the development of a rigid amorphous fraction (RAF). The enthalpy of recovery was calculated after two procedures of rescaling to the content of the whole amorphous phase and also to the only content of the mobile amorphous fraction (MAF), which helped in clarifying the contribution of the RAF. From the dependence of the structural relaxation rate on the aging temperature, two regimes were evidenced for all samples. In the aging temperature domain situated close to the glass transition, the structural relaxation occurs significantly faster in the MAF. Its rate is independent of the aging temperature and is not influenced by the microstructure. However, the distance to equilibrium is higher in samples for which the coupling is strong between crystal and amorphous, implying that the time to reach equilibrium is also higher. In contrast, at low aging temperatures, for which the whole amorphous phase can be considered as solid, MAF and RAF exhibit the same structrural relaxation rate. This convergence in the relaxation kinetics by decreasing the temperature of physical aging was interpreted as the evolution of relaxation dynamics in the MAF from segmental to local. This change is highlighted by the comparison between MAF and RAF relaxation kinetics, but it occurs similarly in a pure amorphous system.

Hydroxyapatite-Based Coatings on Silicon Wafers and Printed Zirconia.

Dental surgery needs a biocompatible implant design that can ensure both osseointegration and soft tissue integration. This study aims to investigate the behavior of a hydroxyapatite-based coating, specifically designed to be deposited onto a zirconia substrate that was intentionally made porous through additive manufacturing for the purpose of reducing the cost of material. Layers were made via sol-gel dip coating by immersing the porous substrates into solutions of hydroxyapatite that were mixed with polyethyleneimine to improve the adhesion of hydroxyapatite to the substrate. The microstructure was determined by using X-ray diffraction, which showed the adhesion of hydroxyapatite; and atomic force microscopy was used to highlight the homogeneity of the coating repartition. Thermogravimetric analysis, differential scanning calorimetry, and Fourier transform infrared spectroscopy showed successful, selective removal of the polymer and a preserved hydroxyapatite coating. Finally, scanning electron microscopy pictures of the printed zirconia ceramics, which were obtained through the digital light processing additive manufacturing method, revealed that the mixed coating leads to a thicker, more uniform layer in comparison with a pure hydroxyapatite coating. Therefore, homogeneous coatings can be added to porous zirconia by combining polyethyleneimine with hydroxyapatite. This result has implications for improving global access to dental care.

Water-Induced Breaking of Interfacial Cohesiveness in a Poly(lactic acid)/Miscanthus Fibers Biocomposite.

The impact of the immersion in water on the morphology and the thermomechanical properties of a biocomposite made of a matrix of poly (lactic acid) (PLA) modified with an ethylene acrylate toughening agent, and reinforced with miscanthus fibers, has been investigated. Whereas no evidence of hydrolytic degradation has been found, the mechanical properties of the biocomposite have been weakened by the immersion. Scanning electron microscopy (SEM) pictures reveal that the water-induced degradation is mainly driven by the cracking of the fiber/matrix interface, suggesting that the cohesiveness is a preponderant factor to consider for the control of the biocomposite decomposition in aqueous environments. Interestingly, it is observed that the loss of mechanical properties is aggravated when the stereoregularity of PLA is the highest, and when increasing the degree of crystallinity. To investigate the influence of the annealing on the matrix behavior, crystallization at various temperatures has been performed on tensile bars of PLA made by additive manufacturing with an incomplete filling to enhance the contact area between water and polymer. While a clear fragilization occurs in the material crystallized at high temperature, PLA crystallized at low temperature better maintains its properties and even shows high elongation at break likely due to the low size of the spherulites in these annealing conditions. These results show that the tailoring of the mesoscale organization in biopolymers and biocomposites can help control their property evolution and possibly their degradation in water.

Promoting Interfacial Interactions with the Addition of Lignin in Poly(Lactic Acid) Hybrid Nanocomposites.

In this paper, the calorimetric response of the amorphous phase was examined in hybrid nanocomposites which were prepared thanks to a facile synthetic route, by adding reduced graphene oxide (rGO), Cloisite 30B (C30B), or multiwalled carbon nanotubes (MWCNT) to lignin-filled poly(lactic acid) (PLA). The dispersion of both lignin and nanofillers was successful, according to a field-emission scanning-electron microscopy (FESEM) analysis. Lignin alone essentially acted as a crystallization retardant for PLA, and the nanocomposites shared this feature, except when MWCNT was used as nanofiller. All systems exhibiting a curtailed crystallization also showed better thermal stability than neat PLA, as assessed from thermogravimetric measurements. As a consequence of favorable interactions between the PLA matrix, lignin, and the nanofillers, homogeneous dispersion or exfoliation was assumed in amorphous samples from the increase of the cooperative rearranging region (CRR) size, being even more remarkable when increasing the lignin content. The amorphous nanocomposites showed a signature of successful filler inclusion, since no rigid amorphous fraction (RAF) was reported at the filler/matrix interface. Finally, the nanocomposites were crystallized up to their maximum extent from the glassy state in nonisothermal conditions. Despite similar degrees of crystallinity and RAF, significant variations in the CRR size were observed among samples, revealing different levels of mobility constraining in the amorphous phase, probably linked to a filler-dimension dependence of space filling.

Impact of Nanoconfinement on Polylactide Crystallization and Gas Barrier Properties.

The barrier properties of poly(l-lactide) (PLLA) were investigated in multinanolayer systems, probing the effect of confinement, the compatibility between the confining and the confined polymer, crystal orientation, and amorphous phase properties. The multilayer coextrusion process was used to confine PLLA between two amorphous polymers (polystyrene, PS; and polycarbonate, PC), which have different chemical affinities with PLLA. Confined PLLA layers of approximately 20 nm thickness were obtained. The multinanolayer materials were annealed at different temperatures to obtain PLLA crystallites with distinct polymorphs. PLLA annealed in PC/PLLA films at 120 °C afforded a crystallinity degree up to 65%, and PLLA annealed in PC/PLLA or PS/PLLA films at 85 °C had a crystallinity degree of 45%. WAXS measurements evidenced that the PLLA lamellas between PS layers had a mixed in-plane and on-edge orientation. PLLA lamellas between PC layers were uniquely oriented in-plane. DMA results evidenced a shift of the PC glass transition toward lower temperature, suggesting the possible presence of an interphase. The development of the rigid amorphous fraction (RAF) in the amorphous phase during annealing was impacted by the confiner polymer. The RAF content of semicrystalline PLLA was about 15% in PC/PLLA, whereas it was neglectable in PS/PLLA. The oxygen barrier properties appeared to be governed by RAF content, and no impact of the PLLA polymorph or the crystalline orientation was observed. This study shows that the confinement of PLLA on itself does not impact barrier properties but that the proper choice of the confiner polymer can lead to decrease the phase coupling which creates the RAF. It is the prevention of RAF that decreases permeability.

Biodegradable PLA/PBSA Multinanolayer Nanocomposites: Effect of Nanoclays Incorporation in Multinanolayered Structure on Mechanical and Water Barrier Properties.

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.

Quantifying Polymer Chain Orientation in Strong and Tough Nanofibers with Low Crystallinity: Toward Next Generation Nanostructured Superfibers.

Advanced fibers revolutionized structural materials in the second half of the 20th century. However, all high-strength fibers developed to date are brittle. Recently, pioneering simultaneous ultrahigh strength and toughness were discovered in fine (<250 nm) individual electrospun polymer nanofibers (NFs). This highly desirable combination of properties was attributed to high macromolecular chain alignment coupled with low crystallinity. Quantitative analysis of the degree of preferred chain orientation will be crucial for control of NF mechanical properties. However, quantification of supramolecular nanoarchitecture in NFs with low crystallinity in the ultrafine diameter range is highly challenging. Here, we discuss the applicability of traditional as well as emerging methods for quantification of polymer chain orientation in nanoscale one-dimensional samples. Advantages and limitations of different techniques are critically evaluated on experimental examples. It is shown that straightforward application of some of the techniques to sub-wavelength-diameter NFs can lead to severe quantitative and even qualitative artifacts. Sources of such size-related artifacts, stemming from instrumental, materials, and geometric phenomena at the nanoscale, are analyzed on the example of polarized Raman method but are relevant to other spectroscopic techniques. A proposed modified, artifact-free method is demonstrated. Outstanding issues and their proposed solutions are discussed. The results provide guidance for accurate nanofiber characterization to improve fundamental understanding and accelerate development of nanofibers and related nanostructured materials produced by electrospinning or other methods. We expect that the discussion in this review will also be useful to studies of many biological systems that exhibit nanofilamentary architectures and combinations of high strength and toughness.

Reducing the Gap between the Activation Energy Measured in the Liquid and the Glassy States by Adding a Plasticizer to Polylactide.

The kinetic fragility of a glass-forming liquid is an important parameter to describe its molecular mobility. In most polymers, the kinetic fragility index obtained from the glassy state by thermally stimulated depolarization current is lower than the one determined in the liquid-like state by dielectric relaxation spectroscopy, as shown in this work for neat polylactide (PLA). When PLA is plasticized to different extents, the fragility calculated in the liquid-like state progressively decreases, until approaching the value of fragility calculated from the glass, which on the other hand remains constant with plasticization. Using the cooperative rearranging region (CRR) concept, it is shown that the decrease of the fragility in the liquid-like state is concomitant with a decrease of the cooperativity length. By splitting the fragility calculated in the liquid, in two contributions: volume and energetic, respectively, dependent and independent on cooperativity, we observed that the slope of the fragility plot in the glass is equivalent to the energetic contribution of the fragility in the liquid. It is then deduced that the difference between the slopes of the relaxation time dependence calculated in both glass and liquid is an indicator of the cooperative character of the segmental relaxation when transiting from liquid to glass. As the main structural consequence of plasticization lies in the decrease of interchain weak bonds, it is assumed that these bonds drive the size of the CRR. In contrast, the dynamics in the glass are independent on plasticization structural effects.

Structure and Barrier Properties of Multinanolayered Biodegradable PLA/PBSA Films: Confinement Effect via Forced Assembly Coextrusion.

Multilayer coextrusion processing was applied to produce 2049-layer film of poly(butylene succinate-co-butylene adipate) (PBSA) confined against poly(lactic acid) (PLA) using forced assembly, where the PBSA layer thickness was about 60 nm. This unique technology allowed to process semicrystalline PBSA as confined polymer and amorphous PLA as confining polymer in a continuous manner. The continuity of PBSA layers within the 80/20 wt % PLA/PBSA layered films was clearly evidenced by atomic force microscopy (AFM). Similar thermal events to the reference films were revealed by thermal studies; indicating no diffusion of polymers during the melt-processing. Mechanical properties were measured for the multilayer film and the obtained results were those expected considering the fraction of each polymer, revealing the absence of delamination in the PLA/PBSA multinanolayer film. The confinement effect induced by PLA led to a slight orientation of the crystals, an increase of the rigid amorphous fraction (RAF) in PBSA with a densification of this fraction without changing film crystallinity. These structural changes allowed to strongly improve the water vapor and gas barrier properties of the PBSA layer into the multilayer film up to two decades in the case of CO2 gas. By confining the PBSA structure in very thin and continuous layers, it was then possible to improve the barrier performances of a biodegradable system and the resulting barrier properties were successfully correlated to the effect of confinement on the microstructure and the chain segment mobility of the amorphous phase. Such investigation on these multinanolayers of PLA/PBSA with the aim of evidencing relationships between microstructure implying RAF and barrier performances has never been performed yet. Besides, gas and water permeation results have shown that the barrier improvement obtained from the multilayer was mainly due to the reduction of solubility linked to the reduction of the free volume while the tortuosity effect, as usually expected, was not really observed. This work brings new insights in the field of physicochemical behaviors of new multilayer films made of biodegradable polyesters but also in interfacial processes due to the confinement effect induced in these multinanolayer structures obtained by the forced assembly coextrusion. This original coextrusion process was a very advantageous technique to produce eco-friendly materials with functional properties without the help of tie layer, additives, solvents, surface treatments, or inorganic fillers.

Water barrier properties in biaxially drawn poly(lactic acid) films.

Crystallization is among the easiest ways to improve polymer barrier properties because of the tortuosity increase within the material and the strong coupling between amorphous and crystalline phases. In this work, poly(lactic acid) (PLA) films have undergone α' thermal crystallization or different drawing processes. Although no effect of α' thermal crystallization on water permeability is observed, the drawing processes lead to an enhancement of the PLA barrier properties. This work clearly shows that, in the case of PLA, the crystallinity degree is not the main parameter governing the barrier properties contrary to the crystalline and amorphous phase organizations which play a key role. X-ray analyses confirm that the macromolecular chain orientation in the amorphous phase is the main cause of the improvement of the drawn PLA water barrier property. This improvement is due to the orthotropic structure formation for sufficient draw ratios, particularly when using the Simultaneous Biaxial drawing mode. Moreover, independently of the draw conditions, the drawing process tends to reduce the plasticization coefficient. Consequently, the drawn material barrier properties are not much affected by the water passage.