Exploring the potential of lignin nanoparticles in enhancing the mechanical, thermal, and bioactive properties of poly (butylene adipate-co-terephthalate).

The preparation and characterization of lignin nanoparticles (LNPs) were described. LNPs were produced via the precipitation technique. Nanocomposites of LNPs with poly (butylene adipate-co-terephthalate) (PBAT) were prepared by melt mixing with various concentrations up to 6 wt% of LNPs. The assessment of the effects of LNP addition on the mechanical, thermal, morphological, cytotoxicity, antioxidant, antibacterial, and antiviral properties of nanocomposites was carefully performed. The addition of LNPs to PBAT enhances the thermal stability of the nanocomposites. The antioxidant effect of LNPs on PBAT increased with increasing filler content. LNPs showed higher efficiency as antioxidant agents than lignin particles (LP). The tensile modulus increased by 20 % for the nanocomposites with 6 % LNPs in comparison with neat PBAT. The crystallization peak temperature of PBAT was 80 °C, which increased to 104.6 °C with the addition of 6 wt% of LNPs, suggesting their strong nucleation activity. Antibacterial tests demonstrated the bacteriostatic activities of LNP, LP, and nanocomposites. Both LP and LNP showed considerable antiviral activity against herpes simplex virus type 1 and human coronavirus 229e. The antiviral activity of LNP was concentration-dependent. The findings suggest that LNP is a promising bio-additive for PBAT and can enhance its properties for various applications, including food packaging.

Formation of UHMWPE Nanofibers during Solid-State Deformation.

A network of nanofibers is formed in situ through solid-state deformation of disentangled ultra-high molecular weight polyethylene (dis-UHMWPE) during compounding with a polyolefin elastomer below the melting temperature of dis-UHMWPE crystals. Dis-UHMWPE was prepared in the form of powder particles larger than 50 µm by polymerization at low temperatures, which favored the crystallization and prevention of macromolecules from entangling. Shearing the blend for different durations and at different temperatures affects the extent to which the grains of dis-UHMWPE powder deform into nanofibers. Disentangled powder particles could deform into a network of nanofibers with diameters between 110 and 340 nm. The nanocomposite can be further sheared for a longer time to decrease the diameter of dis-UHMWPE nanofibers below 40 nm, being still composed of ≈70 wt.% of crystalline and ≈30 wt.% of amorphous components. Subsequently, these thinner fibers begin to melt and fragment because they are thinner and also because the amorphous defects locally decrease the nanofibers' melting temperature, which results in their fragmentation and partial loss of nanofibers. These phenomena limit the thickness of dis-UHMWPE nanofibers, and this explains why prolonged or more intense shearing does not lead to thinner nanofibers of dis-UHMWPE when compounded in a polymeric matrix.

Microstructural Evolution of Poly(ε-Caprolactone), Its Immiscible Blend, and In Situ Generated Nanocomposites.

Polymer-polymer systems with special phase morphology were prepared, leading to an exceptional combination of strength, modulus, and ductility. Two immiscible polymers: poly(ε-caprolactone) (PCL) and polyhydroxyalkanoate (PHA) were used as components for manufacturing a nanoblend and a nanocomposite characterized by nanodroplet-matrix and nanofibril-matrix morphologies, respectively. Nanofibrils were formed by high shear of nanodroplets at sufficiently low temperature to stabilize their fibrillar shape by shear-induced crystallization. The effects of nanodroplet vs. nanofiber morphology on the tensile mechanical behavior of the nanocomposites were elucidated with the help of in situ 2D small-angle X-ray scattering, microcalorimetry and 2D wide-angle X-ray diffraction. For neat PCL and a PCL/PHA blend, the evolution of the structure under uniaxial tension was accompanied by extensive fragmentation of crystalline lamellae with the onset at strain e = 0.1. Limited lamellae fragmentation in the PCL/PHA composite occurred continuously over a wide range of deformations (e = 0.1-1.1) and facilitated plastic flow of the composite and was associated with the presence of a PHA nanofiber network that transferred local stress to the PCL lamellae, enforcing their local deformation. The PHA nanofibers acted as crystallization nuclei for PCL during their strain-induced melting-recrystallization.

Morphology and Plastic Yielding of Ultrahigh Molecular Weight Polyethylene.

The structure, morphology, and mechanical properties of two compression-molded grades of ultrahigh-molecular-weight polyethylene (UHMWPE) and, for comparison, one conventional linear polyethylene (HDPE) were studied. Compression molding resulted in some preferred orientation of lamellae in the compression direction in UHMWPE samples, while no preferred orientation in HDPE. The mean crystal thickness estimated from the size distribution agrees better with those obtained from small-angle X-ray scattering (SAXS) and mechanical yield data than the thickness determined from the melting peak temperature. Microscopic examination of microtomed and etched UHMWPE samples showed that the lamellae are in the form of platelets with the width and length in the range of 300-700 nm. The lamellae radiate from primary nuclei forming small embryonal spherulites; their radial growth ends at 0.3-0.7 µm from the center. There is no evidence of branching and secondary nucleation from those primary lamellae. Because the lamellae are radially ordered, there is no parallel stacking of lamellae. Samples were subjected to deformation by plane-strain compression at a constant true strain rate. In axial UHMWPE samples, where lamellae were preferentially oriented along the loading direction, the second yield was clearly observed. The second yield was found to be related to the deformation instability leading to kinking of lamellae oriented initially along the loading direction. Kinking was clearly shown by SAXS and microscopic observation of microtomed and etched samples. No cooperativity of kinking was observed because the lamellae are arranged in small spherulites and not parallel in stacks. The stress-strain curves were fitted with model curves assuming crystal plasticity and network elasticity in the amorphous component. The effective density of the molecular network within the amorphous phase depended on the molecular weight of UHMWPE.

Plasticization of Polylactide after Solidification: An Effectiveness and Utilization for Correct Interpretation of Thermal Properties.

Polylactide/triethyl citrate (PLA/TEC) systems were prepared in two ways by introducing TEC to solidified polymer matrix (SS) and by blending in a molten state (MS) to investigate the effectiveness of the plasticization process after solidification of polylactide. The plasticization processes, independently of way of introducing the TEC into PLA matrix, leads to systems characterized by similar stability, morphology and properties. Some differences in mechanical properties between MS and SS systems result primarily from the difference in the degree of crystallinity/crystal thickness of the PLA matrix itself. Based on the presented results, it was concluded that the plasticization process after solidification of polylactide is an alternative to the conventional method of modification-blending in a molten state. Then, this new approach to plasticization process was utilized for interpretation of thermal properties of PLA and PLA/TEC systems. It turned out that double melting peak observed at DSC thermograms does not result from the melting of a double population of crystals with different lamellar thickness, or the melting of both the α' and α crystalline phase (commonly used explanations in literature), but is associated with the improvement of perfection of crystalline structure of PLA during heating process.

Nanofibrillar Green Composites of Polylactide/Polyhydroxyalkanoate Produced in Situ Due to Shear Induced Crystallization.

This study addresses the new concept of in situ inducing fibrillar morphology (micro or nanofibrils) of a minority component based on the simultaneous occurrence of orientation and shear induced crystallization of polymer fibers directly at the stage of extrusion in a single step. This possibility is demonstrated by using two entirely bio-sourced polymers: polylactide (PLA) and polyhydroxyalkanoate (PHA) as components. The shear induced crystallization allowed crystallization of PHA nanofibers immediately after applying high shear rate and elongation strain, avoiding subsequent cooling to initiate crystallization. Shearing of PHA increased non-isothermal crystallization temperature by 50 °C and decreased the temperature range in which the transition from a molten state to a crystallized one occurs by 17 °C. SEM observations demonstrate the successful transformation of the dispersed PHA phase into nanofibrils with diameters of nearly 200 nm. The transition from the droplets of PHA to fibers causes the brittle-to-ductile transition of the PLA matrix at a low concentration of PHA and contributes to the simultaneous increase of its rigidity and strength.

In situ generation of sustainable PLA-based nanocomposites by shear induced crystallization of nanofibrillar inclusions.

In situ formation of polymer nanofibrils during compounding with a second polymer followed by their immediate solidification due to shear induced crystallization for two pairs of polymers is described. Sustainable green biopolymer-biopolymer nanocomposites of polylactide (PLA) were then fabricated based on two copolyesters forming nanofibrils during shearing: poly(butylene adipate-co-succinate-co-glutarate-co-terephthalate) (PBASGT) and poly(butylene adipate-co-terephthalate) (PBAT). The shear induced crystallization allowed solidification of PBASGT or PBAT nanofibers immediately under applying a high shear rate without subsequent cooling. The melt memory unveiling as a self-nucleation facilitated shear-induced crystallization. Formation of nanofibril-matrix morphology led to an exceptional combination of strength, modulus and ductility. In situ SEM observation of the tensile test revealed crazing as a dominant mechanism for PLA deformation. However, addition of PBASGT or PBAT resulted in intensified crazing followed by shear banding. Increase of PBASGT or PBAT concentration promoted the brittle-to-ductile transition of the PLA matrix. At the same time, PBAT or PBASGT nanofibers span PLA craze surfaces and at large strain, when PLA craze tufts get broken, they bridge the craze gaps resulting in an increase of both strength and plasticity of PLA.

Orientation of PVDF α and γ crystals in nanolayered films.

Wide-angle X-ray scattering in conjunction with pole figure technique was used to study the texture of poly(vinylidene fluoride) (PVDF) α and γ phase crystals in nanolayered polysulfone/poly(vinylidene fluoride) films (PSF/PVDF) produced by layer-multiplying coextrusion. In all as-extruded PSF/PVDF films, the PVDF nanolayers crystallized into the α phase crystals. A large fraction of those crystals was oriented with macromolecular chains perpendicular to the PSF/PVDF interface as evidenced from the (021) pole figures. Further refinement of the texture occurs during isothermal recrystallization at 170 °C in conjunction with transformation of α to γ crystals. The γ crystals orientation was probed with the (004) pole figures showing the c-axis of PVDF γ crystals perpendicular to the PSF/PVDF interface. The thinner the PVDF layers the stronger the orientation of γ crystals. It was proven that the X-ray reflections from the (021) planes of α crystals and from the (004) planes of γ crystals are not overlapped with other reflections and can be effectively used for the texture determination of PVDF nanolayers in multilayered PSF/PVDF films.

Gauche-trans transitions in amorphous polymers under annealing: lattice model and polarized light scattering.

The driving force of density fluctuation of amorphous polymer films under annealing processes was evaluated synthetically in terms of thermodynamics on the basis of the logarithmic light intensity as a function of annealing time. The time dependence of ln(I) of polyethylene (terephthalate) (PET) as an example for characterizing an amorphous state was classified into three stages: the first stage (stage I), where ln(I) showed insignificant changes with time; the second stage (stage II), where ln(I) increased linearly; and the third stage (stage III), where the intensity deviated from the linear relationship and tended to level off. The density fluctuation by chain diffusion, termed quasi-spinodal decomposition, in stage II was analyzed in terms of an increase of trans-conformation of an amorphous chain in stage I. To provide conclusive evidence, the orientation function of chain segments was calculated by using a lattice model that accounts for entropic and energetic characters. The former character is associated with segmental orientation due to the effect of chain stiffness of Kuhn segments characterized by a rod with a relatively large length-to-width ratio x , whereas the latter is associated with thermotropic systems with anisotropic polarizabilities. By using the theoretical orientation function, Hv light scattering patterns were calculated by a statistical approach in which the optical axis of a PET chain segment was chosen along the direction perpendicular to the benzene ring. This selection was justified by comparison of the three principal refractive indexes of a PET chain. The calculated patterns provided a clear X-type lobe, when the correlation between optical elements concerning the rotational fluctuation became stronger. The calculated patterns were in good agreement with the patterns observed in stage III. The series of experimental and theoretical results indicated that the conversion from gauche- to trans-conformation plays an important role to derive the density fluctuation of amorphous polymer chains associated with the initiation of crystallization.

Confined crystallization of polyethylene oxide in nanolayer assemblies.

The design and fabrication of ultrathin polymer layers are of increasing importance because of the rapid development of nanoscience and nanotechnology. Confined, two-dimensional crystallization of polymers presents challenges and opportunities due to the long-chain, covalently bonded nature of the macromolecule. Using an innovative layer-multiplying coextrusion process to obtain assemblies with thousands of polymer nanolayers, we discovered a morphology that emerges as confined polyethylene oxide (PEO) layers are made progressively thinner. When the thickness is confined to 20 nanometers, the PEO crystallizes as single, high-aspect-ratio lamellae that resemble single crystals. Unexpectedly, the crystallization habit imparts two orders of magnitude reduction in the gas permeability.

Plastic deformation of amorphous poly(L/DL-lactide): structure evolution and physical properties.

Plastic deformation of amorphous, thermally noncrystallizable poly(L/DL-lactide) 70/30 (P(L/DL)LA) was induced by a plane-strain compression in a channel-die at different temperatures, above the glass transition (Tg) from 60 to 90 degrees C. Samples undeformed (reference) and deformed to different compression ratios, from 4.6 to 23.0, were studied by X-ray diffraction, thermally modulated differential scanning calorimetry, light microscopy, and mechanical methods-viscoelastic and tensile tests. The effects of the compression ratios and deformation temperatures on the final structure and properties of the P(L/DL)LA were evaluated. It was revealed that plastic deformation transformed an amorphous P(L/DL)LA (thermally noncrystallizable) to a crystalline fibrillar texture oriented in the flow direction. Fibrillar texture was formed in spite of the tendency of the plane-strain compression to form single-crystal-like texture. The crystallite size in the transverse direction was small, up to 90 angstroms at the highest compression ratio. No evidence of lamellar organization and features of supermolecular structure were detected by small-angle X-ray scattering and light microscopy, respectively. The oriented samples exhibited a low crystallinity degree at the level of 6-9% at the highest compression ratio. The main transformation mechanism was shear and orientation-induced crystallization. The crystalline phase was in the alpha crystallographic modification of poly(lactide) typically formed in more stereoregular poly(lactide) by thermal treatment. The glass transition increased with the increase of compression ratio reflecting the increase of orientation of the polymer chains. The tensile strength of deformed samples was improved considerably in comparison to that of the reference sample.