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•SMPs are an emerging class of smart polymer materials with multi-responsiveness.•Recent trends in the field of SMPs (conception, fabrication, modeling) are outlined.•A new generation ...multi-functional SMPs containing nanosized fillers is described.•The nanocomposites have enhanced mechanical, thermal and shape-memory properties.•SMPs are of great interest to fundamental research and technological innovation.
Shape-memory polymers (SMPs) as stimuli-responsive shape-changing polymers are of great interest for fundamental research and technological innovation. In this contribution, a brief review of the recent trends in the field of SMPs is presented with particular focus on their structure, shape-memory effects and working mechanism. A special attention is paid to smart multi-responsive and multi-functional SMP materials as emerging technological class. They are mainly described as shape-memory nanocomposites (SMCs) where the incorporation of functional (in)organic nanofillers in the SMP matrices is purposely carried out. Potential applications of the SMCs-based materials as medical and biomimetic devices, self-healing systems, self-deployable structures, actuators, sensors, etc. or their direct implementation in the industry are finally outlined.
Environmental concerns along with the need to develop aliphatic polycarbonate materials free of any toxic compounds have driven scientists to implement macromolecular engineering processes by ...replacing potentially toxic and carcinogenic metal-based catalysts traditionally used for the ring-opening polymerization of cyclic carbonates by organic compounds. This issue is of particular importance as aliphatic polycarbonates are gaining increasing credibility for biomedical applications owing to their biocompatibility and bioresorbability. This review provides a complete account of the various metal-free catalysts that has been developed so far as well as comprehensive investigations on the related polymerization mechanisms.
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•Effect of lignin incorporation on thermal degradation and fire behavior of PLA.•Phosphorus/nitrogen modification of lignin: enhancement of its FR effect in PLA.•Use of several ...innovative and original techniques for lignins characterization.•Gases from thermal decomposition of lignins analyzed by TGA-MS.•Gases from combustion of lignins analyzed by cone calorimeter-FTIR.
The present study focuses on the use of lignin, which is the second most abundant constituent of the biomass, as sustainable flame retardant additive for polylactide (PLA). Indeed, thanks to its aromatic structure, lignin could be advantageously used, in polymeric matrices, as a char promotor agent that can allow some reduction of the combustion rate. An original and simple approach, based on a two-step phosphorus/nitrogen chemical modification, is proposed to enhance the flame retardant effect of lignin in PLA. This approach has been applied on two different lignins, i.e. kraft and organosolv lignins. The effect of the plant origin, extraction mode of lignin as well as it chemical modification on both its structure and properties was investigated by using several characterization techniques. Fire properties and thermal behavior of PLA composites containing 20 wt% of both untreated and treated lignins were characterized by using cone calorimeter, UL-94 and thermogravimetric analysis (TGA). Results showed that the incorporation of untreated lignins led to a flame retardant action in PLA thanks to the formation of char but also to a significant loss of the thermal stability of PLA and to an important decrease of its time to ignition. In contrast, both phosphorus/nitrogen chemically treated lignins were found to limit PLA thermal degradation during melt processing as well as during TG experiments and also to significantly improve fire retardant properties allowing to reach V0 classification at UL-94. In this paper we also deeply investigated the nature of the gases evolved during thermal decomposition of treated and untreated lignins by using TGA-Mass spectrometer and cone calorimeter – FTIR couplings.
Surface-functionalization mediated through “grafting from” methods is of considerable interest as means to tailor the chemical and physical properties of functional substrates in a reliable way. The ...resulting polymer brushes, obtained by a “grafting from” strategy, are composed of grafted polymer chains tethered from one of their extremities to a surface by a covalent bond. Tuning the molecular parameters of these polymeric brushes such as the nature of monomer, the grafting density, and the chain length as well as the design of micropatterned structures enables delicate modification of the properties of these substrates, paving the way to the development of functional surfaces. In this review, we highlight recent and most important approaches to form monolayers and to subsequently elaborate homogeneous and heterogeneous coatings of polymer brushes by surface-initiated polymerization. The control of initiator molecule assembly is particularly important for the final configuration of polymer brushes. We report the creation of homopolymers and block copolymers using major controlled polymerization techniques as well as lithographic techniques aiming at the design of polymeric (micro- or nano-) patterns.
Novel potentially biobased aliphatic-aromatic copolyesters poly(butylene succinate-co-butylene furandicarboxylate) (PBSFs) in full composition range were successfully synthesized from ...2,5-furandicarboxylic acid (FA), succinic acid (SA), and 1,4-butanediol (BDO) via an esterification and polycondensation process using tetrabutyl titanate (TBT) or TBT/La(acac)(3) as catalyst. The copolyesters were characterized by size exclusion chromatography (SEC), Fourier transform infrared (FTIR), (1)H NMR, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), and their tensile properties were also evaluated. The weight average molecular weight (M(w)) ranges from 39,000 to 89,000 g/mol. The copolyesters are random copolymers whose composition is well controlled by the feed ratio of the diacid monomers. PBSFs have excellent thermal stability. The glass transition temperature (T(g)) increases continuously with φ(BF) and agrees well with the Fox equation. The crystallizability and T(m) decrease with increasing butylene furandicarboxylate (BF) unit content (φ(BF)) from 0 to 40 mol %, but rise again at φ(BF) of 50-100 mol %. Consequently, the tensile modulus and strength decrease, and the elongation at break increases with φ(BF) in the range of 0-40 mol %. At higher φ(BF), the modulus and strength increase and the ultimate elongation decreases. Thus, depending on φ(BF), the structure and properties of PBSFs can be tuned ranging from crystalline polymers possessing good tensile modulus (360-1800 MPa) and strength (20-35 MPa) to nearly amorphous polymer of low T(g) and high elongation (~600%), and therefore they may find applications in thermoplastics as well as elastomers or impact modifiers.
Vulcanized and devulcanized ground tire rubber microparticles have been used as a minor phase in acrylonitrile butadiene styrene copolymer (ABS) and thermoplastic polyolefins (TPO) for the ...development of materials with desired functionalities by 3D printing. These polymers have been selected because they (i) present part of the plastic waste generated by the automotive industry and (ii) have totally different properties (ABS for its stiffness and robustness and TPO for its softness and ductility). The study aims to improve the circular economy of the automotive industry by proposing a promising route for recycling the generated tire rubber waste. In this respect, emergent technology for plastic processing such as 3D printing is used, as part of the additive manufacturing technologies for the prolongated end of life of recycled plastics originated from automotive waste such as ABS and TPO. The obtained results revealed that (i) the composites are suitable for successful filament production with desired composition and diameter required for successful 3D printing by fused deposition modeling, and that (ii) the optimization of the composition of the blends allows the production of materials with interesting mechanical performances. Indeed, some of the investigated ABS-recycled rubber tire blends exhibit high impact properties as TPO-based composites do, which in addition exhibits elongation at break higher than 500% and good compression properties, accompanied with good shape recovery ratio after compression.
Poly(lactic acid) or polylactide (PLA), a biodegradable polyester produced from renewable resources, is used for various applications (biomedical, packaging, textile fibers and technical items). Due ...to its inherent properties, PLA has a key-position in the market of biopolymers, being one of the most promising candidates for further developments.
Unfortunately, PLA suffers from some shortcomings, whereas for the different applications specific end-use properties are required. Therefore, the addition of reinforcing fibers, micro- and/or nanofillers, and selected additives within PLA matrix is considered as a powerful method for obtaining specific end-use characteristics and major improvements of properties.
This review highlights recent developments, current results and trends in the field of composites based on PLA. It presents the main advances in PLA properties and reports selected results in relation to the preparation and characterization of the most representative PLA composites. To illustrate the possibility to design the properties of composites, a section is devoted to the production and characterization of innovative PLA-based products filled with thermally-treated calcium sulfate, a by-product from the lactic acid production process. Moreover, are emphasized the last tendencies strongly evidenced in the case of PLA, i.e., the high interest to diversify its uses by moving from biomedical and packaging (biodegradation properties, “disposables”) to technical applications (“durables”).
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Melatonin (MLT) is a biological modulator of circadian and seasonal rhythms and reproduction. The photoperiodic information is detected by retinal photoreceptors and transmitted through nerve ...transmissions to the pineal gland, where MLT is synthesized and secreted at night into the blood. MLT interacts with two G protein-coupled receptors, MT.sub.1 and MT.sub.2 . The aim of our work was to provide evidence for the presence of MLT receptors in the ovine pineal gland and define their involvement on melatonin secretion. For the first time, we identified the expression of MLT receptors with the specific 2-.sup.125 I-MLT agonistic radioligand in ovin pinealocytes. The values of Kd and Bmax are 2.24 ± 1.1 nM and 20 ± 6.8 fmol/mg. MLT receptors are functional and inhibit cAMP production and activate ERK1/2 through pertussis toxin-sensitive G.sub.i/o proteins. The MLT receptor antagonist/ inverse agonist luzindole increased cAMP production (189 ± 30%) and MLT secretion (866 ± 13%). The effect of luzindole on MLT secretion was additive with the effect of well-described activators of this pathway such as the beta-adrenergic agonist isoproterenol and the alpha-adrenergic agonist phenylephrine. Co-incubation of all three compounds increased MLT secretion by 1236 ± 199%. These results suggest that MLT receptors are involved in the negative regulation of the synthesis of its own ligand in pinealocytes. While adrenergic receptors promote MLT secretion, MLT receptors mitigate this effect to limit the quantity of MLT secreted by the pineal gland.
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