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In situ-generated nanofibrillar polymer–polymer composites are excellent candidates for the production of polymer materials, with high mechanical and SME properties. Their special feature is the high degree of dispersion of the in situ-generated nanofibers and the ability to form entangled nanofiber structures with high aspect ratios through an end-to-end coalescence process, which makes it possible to effectively reinforce the polymer matrix and, in many cases, increase its ductility. The substantial interfacial area, created by the in situ formed fiber/matrix morphology, significantly strengthens the interfacial interactions, which are crucial for shape fixation and shape recovery. Using the polylactide/bio-polyamide (PLA/PA) system as an example, it is shown that in situ PA fibrillation improves the mechanical and shape-memory properties of PLA. The modulus of elasticity increases by a factor of 1.4, the elongation at break increases by a factor of 30, and the shape-strain/fixity ratio and shape recovery increase from 80.2 to 97.4% and from 15.5 to 94.0%, respectively. The morphology of the minor PA phase is crucial. The best result is achieved when a physically entangled nanofibrous network is formed. [ABSTRACT FROM AUTHOR]

Structural changes in polylactide/polybutylene terephthalate (PLA/PBT) and glycol‐modified polyethylene terephthalate/polybutylene terephthalate (PET‐G/PBT) polymer blends at a pressure of 1 GPa and room temperature in combination with shear deformation are investigated. High pressure torsion (HPT) is chosen as the compatibilization technique. Based on solid‐state NMR data, it is found that the compatibility of immiscible polymers is significantly improved under high pressure conditions in combination with shear deformation. It is assumed that the thickness of the deformed polymer layers decreases to the thickness of the interphase and it can be a fully interphase material. [ABSTRACT FROM AUTHOR]

The mechanical behavior of polymer materials is heavily influenced by a phenomenon known as crazing. Crazing is a precursor to damage and leads to the formation of cracks as it grows in both thickness and tip size. The current research employs an in situ SEM method to investigate the initiation and progression of crazing in all-biopolymeric blends based on Polyhydroxyalkanoates (PHAs). To this end, two chemically different grades of PHA, namely poly(hydroxybutyrate) (PHB) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBHV), were melt-blended with polybutyrate adipate terephthalate (PBAT). The obtained morphologies of blends, the droplet/fibrillar matrix, were highly influenced by the plasticity of the matrices as well as the content of the minor phase. Increasing the concentration of PBAT from 15 to 30 wt.% resulted in the brittle to ductile transition. It changed the mechanism of plastic deformation from single craze-cracking to homogeneous and heterogeneous intensified crazing for PHB and PHBHV matrices, respectively. Homogeneous tensile crazes formed perpendicularly to the draw direction at the initial stages of deformation, transformed into shear crazes characterized by oblique edge propagation for the PHBHV/PBAT blend. Such angled crazes suggested that the displacement might be caused by shear localized deformation. The crazes' strength and the time to failure increased with the minor phase fibers. These fibers, aligned with the tensile direction and spanning the width of the crazes, were in the order of a few micrometers in diameter depending on the concentration. The network of fibrillar PBAT provided additional integrity for larger plastic deformation values. This study elucidates the mechanism of crazing in PHA blends and provides strategies for controlling it. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Nascent ultrahigh molecular weight polyethylene (UHMWPE) is a thermoplastic material, consisting of nodular-fibrillar structure making it too much porous. At the present work, the effect of both particle morphology and chain entanglements on the sintering of UHMWPE was investigated. Neck growth for particles of three different commercial grades was determined as a function of time at isothermal sintering temperatures. A comparison between the experimental data and predictions from a theoretical model based on Maxwell constitutive equations revealed a complicated effect of particle size and morphology. It was observed that at early stages of sintering, Bellehumeur's model was in an excellent agreement with the experimental data, while it was deviated at late stages when the neck growth ratio (y/a) exceeds 0.8. Unlike commercially entangled samples, melted disentangled powder particles did not flow toward each other even after a long time had elapsed. Disentangled UHMWPE pellets, sintered for 10 min near the melting temperature, showed great transparency indicating low air voids and developing the sintering process, while grain boundaries remained undeveloped for entangled pellets. [ABSTRACT FROM AUTHOR]

The shear-induced and cellulose-nanofiber nucleated crystallization of two novel aliphatic–aromatic copolyesters is outlined due to its significance for the in situ generation of biodegradable nanocomposites, which require the crystallization of nanofibrous sheared inclusions at higher temperatures. The shear-induced non-isothermal crystallization of two copolyesters, namely, poly(butylene adipate-co-succinate-co-glutarate-co-terephthalate) (PBASGT) and poly(butylene adipate-co-terephthalate) (PBAT), was studied following a light depolarization technique. To have a deep insight into the process, the effects of the shear rate, shear time, shearing temperature and cooling rate on the initiation, kinetics, growth and termination of crystals were investigated. Films of 60 μm were subjected to various shear rates (100–800 s−1) for different time intervals during cooling. The effects of the shearing time and increasing the shear rate were found to be an elevated crystallization temperature, increased nucleation density, reduced growth size of lamella stacks and decreased crystallization time. Due to the boosted nucleation sites, the nuclei impinged with each other quickly and growth was hindered. The effect of the cooling rate was more significant at lower shear rates. Shearing the samples at lower temperatures, but still above the nominal melting point, further shifted the non-isothermal crystallization to higher temperatures. As a result of cellulose nanofibers' presence, the crystallization of PBAT, analyzed by DSC, was shifted to higher temperatures. [ABSTRACT FROM AUTHOR]

The paper discusses the possibility of using in situ generated hybrid polymer-polymer nanocomposites as polymeric materials with triple shape memory, which, unlike conventional polymer blends with triple shape memory, are characterized by fully separated phase transition temperatures and strongest bonding between the polymer blends phase interfaces which are critical to the shape fixing and recovery. This was demonstrated using the three-component system polylactide/polybutylene adipateterephthalate/cellulose nanofibers (PLA/PBAT/CNFs). The role of in situ generated PBAT nanofibers and CNFs in the formation of efficient physical crosslinks at PLA-PBAT, PLA-CNF and PBAT-CNF interfaces and the effect of CNFs on the PBAT fibrillation and crystallization processes were elucidated. The in situ generated composites showed drastically higher values of strain recovery ratios, strain fixity ratios, faster recovery rate and better mechanical properties compared to the blend. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]