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Solid-state lithium batteries are considered one of the most promising battery systems due to their high volumetric energy density and safety. Poly(ethylene oxide) (PEO) is the most commonly used solid polymer electrolyte in solid-state batteries. In this article, we introduce new polyphosphoester polymer electrolytes, which show improved flame retardant properties in comparison with PEO. For this purpose, new polyphosphoester copolymers were synthesized, including phosphoester, poly(ethylene glycol) (PEG) and UV cross-linkable vinyl units. Solid polymer electrolyte films based on polyphosphoester copolymers and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) were prepared by curing under UV-light. The crystallinity present in the copolymers due to the PEG segment decreases with the amount of salt in the electrolyte, as seen by DSC. Solid polymer electrolytes based on polyphosphoester copolymers show ionic conductivity values as high as 2 × 10−4 S cm−1 at 70 °C. FTIR analysis showed that lithium cations complexed with phosphoester groups provoked an increase in the lithium transference number to 0.26 as compared to that of PEO 0.17. Pyrolysis flow combustion calorimetry (PCFC) or micro-calorimetry results demonstrated the improved flame retardancy of the polyphosphoesters in comparison to a reference PEO based polymer electrolyte. The selected polyphosphoester solid electrolyte was investigated in a solid-state lithium cell Li0/polymer electrolyte/LFP battery showing a specific capacity retention close to 80% and coulombic efficiency greater than 98% over 100 cycles at 70 °C.

The synthesis and properties of hybrid poly(ε-caprolactone) (PCL)–poly(ethylene oxide) (PEO) covalent adaptable networks have been investigated.

In the recent decades, biodegradable and biocompatible polyphosphoesters (PPEs) have gained wide attention in the biomedical field as relevant substitutes for conventional aliphatic polyesters. These amorphous materials of low glass transition temperature offer promise for the design of soft scaffolds for tissue engineering. Advantageously, the easy variation of the nature of the lateral pendant groups of PPEs allows the insertion of pendent unsaturations valuable for their further cross-linking. In addition, varying the length of the pendent alkyl chains allows tuning their hydrophilicity. The present work aims at synthesizing PPE networks of well-defined hydrophilicity and mechanical properties. More precisely, we aimed at preparing degradable materials exhibiting identical hydrophilicity but different mechanical properties and vice versa. For that purpose, PPE copolymers were synthesized by ring-opening copolymerization of cyclic phosphate monomers bearing different pendent groups (e.g., methyl, butenyl, and butyl). After UV irradiation, a stable and well-defined cross-linked material is obtained with the mechanical property of the corresponding polymer films controlled by the composition of the starting PPE copolymer. The results demonstrate that cross-linking density could be correlated with the mechanical properties, swelling behavior, and degradation rate of the polymers network. The polymers were compatible to human skin fibroblast cells and did not exhibit significant cytotoxicity up to 0.5 mg mL-1. In addition, degradation products appeared nontoxic to skin fibroblast cells and showed their potential as promising scaffolds for tissue engineering.

Chemical crosslinking is an efficient tool to improve or impart new properties to conventional polymers. Especially, crosslinking imparts remarkable shape–memory properties to poly-e-caprolactone (PCL) materials. Nevertheless, the processing of networks is often tricky due to infusibility and insolubility of cross-linked chains. Therefore, the synthesis of PCL networks including thermo-reversible crosslinks based on (retro)-Diels-Alder (DA) reaction were developed to allow preserving the melt-processing while keeping the required mechanical properties below the melting point. This paper aims at studying in depth, such thermo-dependent network formation and stability. Besides conventional swelling experiments, Raman spectroscopy was revealed as a powerful tool to follow the formation of the DA adduct during the crosslinking. In combination with rheological measurements, we were able to determine the most appropriate temperatures to form the network (DA crosslinking) and to process it (retro-DA reaction) without degradation of the material.

Photochemically cross-linked shape-memory polymer (SMP) materials have been achieved by functionalizing chain-ends of star-shaped poly(ϵ-caprolactone) (PCL) with 7-hydroxypropoxy-4-methylcoumarin followed by photodimerization of these end-groups. The kinetics of the network formation in function of the photosensitizer concentration has been studied by swelling experiments and rheology. Thanks to the design of a dedicated homemade mold, highly reproducible irradiation conditions have been achieved allowing to study the network formation and properties, especially the shape-memory properties, in relation to the coumarin dimerization degree as determined by Raman spectroscopy. In optimized conditions, PCL-based SMP materials exhibiting high fixity and recovery have been achieved in remarkably short irradiation time, typically 5 min. In addition, the precise control of the network cross-link density with the irradiation time, so as the high stability of the formed networks toward temperature variations was also demonstrated allowing the fine-tuning of the network properties by the irradiation process. Finally, the reversible character of the coumarin dimerization under light irradiation of appropriate wavelength has been quantified by Raman spectroscopy. The dimer photocleavage allows the photoreconfiguration of the networks offering the ability to modify the "permanent" shape of the SMP material, while preserving the excellent shape-memory properties.

In this paper, we present a small (25×25×3 mm3) power module that integrates two silicon-carbide (SiC) JFETs to form an inverter leg. This module has a “sandwich” structure, i.e. the power devices are placed between two ceramic substrates, allowing for heat extraction from both sides of the dies. All interconnects are made by silver sintering, which offers a very high temperature capability (the melting point of pure silver being 961 °C). The risk of silver migration is assessed, and we show that Parylene-HT, a dielectric material that can sustain more than 300 °C, can completely coat the module, providing adequate protection.

Local treatment using drug loaded implants allows decreasing seric concentrations of the active ingredient with the purpose of limiting side effects and reaching perfect observance. Nowadays, some diseases are already treated with implants, but generally, by subcutaneous or intra vaginal implantation. In this work, a new implant device dedicated to the intra-peritoneal cavity was developed. For this purpose, a core-membrane polymer implant was selected. We propose an original method to determine the most appropriate membrane to control the release based on the use of Franz cells. The ability of the implant to release a constant quantity of an active ingredient will be assessed by testing implants in vitro. Finally, intra peritoneal cavity and subcutaneous in vivo implantation has been achieved in order to confirm the controlled and local release of the active ingredient.

International audience; Silver sintering is a promising alternative to high melting point (HMP) solders which contain lead. Indeed, it offers better thermal and electrical properties, and can operate at higher temperature. However, silver tends to migrate in presence of electric field, oxygen (or moisture) and high temperature, causing short circuits. In this paper, we assess the extend of this issue, and we evaluate the protective effect of a thin layer of parylene. It is shown that silver migration occurs rapidly (tens to hundred of hours at 300°C), but that parylene offers a good mitigation of this issue.

National audience; Silver sintering is a promising alternative to high melting point (HMP) solders which contain lead. Indeed, it offers better thermal and electrical properties, and can operate at higher temperature. Currently, several implementations of this technique are available, based on various silver particles sizes and sintering additives. This paper presents a review of the different implementations, and gives practical details about one of them, based on silver nanoparticles. One specific aspect is highlighted: the metal finish of the DBC substrate. It has a major impact on the quality of the sintered joint: with some finishes, the adhesion is excellent (more than 50 MPa), while it is poor with some others (lower than 10 MPa).

International audience; Silicon Carbide (SiC) Junction-Field Effect Transistors (JFETs) are attractive devices for power electronics. Their high temperature capability should allow them to operate with a reduced cooling system. However, experiments described in this paper conclude to the existence of runaway conditions in which these transistors will reach destructive temperatures.

Three-arm (A(2)B) and four-arm (A(2)B(2)) star-shaped copolymers based on biocompatible and biodegradable hydrophobic poly(epsilon-caprolactone) (PCL) (A arms) and biocompatible and bioeliminable hydrophilic poly(ethylene oxide) (PEO) (B arms) were synthesized by the coupling of an omega-azide terminated PEO chains with PCL chain bearing one (A(2)B) or two (A(2)B(2)) alkyne functions at the middle of the chain by the copper mediated azide-alkyne cycloaddition (CuAAC). The amphiphilic behavior of these different stars was confirmed by micellization experiments in water followed by dynamic light scattering and transmission electron microscopy analyses. The efficiency to stabilize PLA nanoparticles was investigated in function of the stars structure.

[4+2] thermoreversible Diels-Alder cycloaddition has been used to crosslink star-shaped poly(e-caprolactone) in order to produce networks based on strong carbon-carbon covalent bondings. Depending on the nature of the Diels-Alder reactants, these bonds can be thermoreversibly broken, allowing re-processing of the polymer matrix.

This paper describes the synthesis of a novel amphiphilic AB 2 triarm star-shaped copolymer with A = non-toxic and biocompatible hydrophilic poly(ethylene oxide) (PEO) and B = biodegradable and hydrophobic poly(e-caprolactone) (PCL). A series of AB 2 triarm star-shaped copolymers with different molecular-weights for the PCL block were successfully synthesized by a three-step procedure. α-Methoxy-ω-epoxy-poly(ethylene oxide) (PEO-epoxide) was first synthesized by the nucleophilic substitution of α-methoxy-ω-hydroxy-poly(ethylene oxide) (MPEO) on epichlorohydrin. In a second step, the α-methoxy-ω,ω′-dihydroxy-poly(ethylene oxide) (PEO(OH) 2 ) macroinitiator was prepared by the selective hydrolysis of the ω-epoxy end-group of the PEO-epoxide chain. Finally, PEO(OH) 2 was used as a macroinitiator for the ring-opening polymerization (ROP) of e-caprolactone (eCL) catalyzed by tin octoaote (Sn(Oct) 2 ). PEO-epoxide, PEO(OH) 2 and the AB 2 triarm star-shaped copolymers were assessed by 1 H NMR spectroscopy, size exclusion chromatography (SEC) and MALDI-TOF. The behavior of the AB 2 triarm star-shaped copolymer in aqueous solution was studied by dynamic light scattering (DLS) and transmission electron microscopy (TEM).

Biodegradability makes aliphatic polyesters valuable candidates for biomaterials and environmentally friendly thermoplastics. Nevertheless, their chemical modification, which is mandatory for a series of potential applications, is usually a problem because it must be carried out under very mild conditions in order to prevent degradation by hydrolysis and/or transesterification from occurring. In this review, the copper(I)-catalyzed azide-alkyne cycloaddition, which is a click reaction, is shown to be very efficient to bypass these problems and to tailor the macromolecular architecture and functionality of those polyesters without facing undesired degradation reactions.

Copper-mediated azide–alkyne Huisgen's 1,3-dipolar cycloaddition is a “click” reaction that was successfully used to prepare pH-responsive, amphiphilic and biodegradable networks. Indeed, this reaction proved to be very efficient in the “one pot” grafting of amino alkyne onto azide containing poly(ɛ-caprolactone) and the cross-linking of these chains by α,ω-dialkynyl poly(ethylene oxide). The pH-controlled release of guests hosted during the cross-linking step was illustrated with an entrapped model dye.

International audience; Silver sintering is an attractive alternative to soldering in power electronics, as it offers higher electrical and thermal performance. Furthermore, sintered attaches can operate at a higher temperature. In this paper, we investigate the use of silver sintering for the bonding of passive components, and for the manufacturing of so-called 3D-modules. It is shown that this technique is well suited, as it makes it possible to operate at very high temperature (up to 310 °C demonstrated), and as it simplifies the assembly process (several identical sintering steps can be performed successively without problem).

In previous works, poly(D,L-lactide-co-ɛCL-poly(ethylene glycol) (poly(D,L-La-co-αPEGɛCL) amphiphilic graft-copolymers were successfully synthesized according to a copper azide-alkyne cycloaddition (CuAAC) strategy. This paper aims at reporting on the behavior of this amphiphilic copolymer in water, which was not studied in the previous paper. Moreover, the ability of the copolymer to stabilize a PLA nanoparticles aqueous suspension is presented. For this purpose, dynamic light scattering (DLS) and transmission electron microscopy (TEM) are proposed to characterize the nanoparticles in solution. Otherwise, the strategy developed for the synthesis of the amphiphilic copolymers was adapted and extended to the synthesis of PLA-based degradable hydrogel, potentially applicable as drug-loaded degradable polymer implant.

Recent progress in the synthesis of aliphatic polyesters, substituted by pendent functional groups, has been reviewed. Two main strategies have to be distinguished. The first route consists of the ring-opening polymerization of e-caprolactone substituted by various functional groups, protected if needed, in α- or γ-position. In a second strategy, the functional groups are grafted onto preformed polyesters chains in α-position of the carbonyl groups. α-chloro-e-caprolactone is quite an interesting monomer because, after polymerization, the activated chloride can be easily derivatized by atom transfer radical addition and click chemistry, respectively. Similarly, γ-acrylic-e-caprolactone is precursor of (co)polyesters well-suited to derivatization of the pendent double bonds by Michael addition.

8 pages; International audience; Although they can operate at elevated junction temperature, silicon carbide power devices can in some cases fail, even at low ambient temperature. This destruction mechanism, called the thermal run-away, is described in the paper. Then, the sensitivity of normally-on SiC JFETs (SiCED) to this mechanism is evaluated using a model based on experimental measurements performed over a wide temperature range (from -50°C to 300°C). It is shown that above a certain current level, run-away can occur. An experimental test bench is used to validate the modelling and explore the safe-operating area of these devices. The measurements confirm the sensitivity of the device to thermal run-away. Mitigation techniques are discussed.

A chemically cross-linked but remarkably (re)processable shape-memory polymer (SMP) is designed by cross-linking poly(ε-caprolactone) (PCL) stars via the efficient triazolinedione click chemistry, based on the very fast and reversible Alder-ene reaction of 1,2,4-triazoline-3,5-dione (TAD) with indole compounds. Typically, a six-arm star-shaped PCL functionalized by indole moieties at the chain ends is melt-blended with a bisfunctional TAD, directly resulting in a cross-linked PCL-based SMP without the need of post-curing treatment. As demonstrated by the stress relaxation measurement, the labile character of the TAD-indole adducts under stress allows for the solid-state plasticity reprocessing of the permanent shape at will by compression molding of the raw cross-linked material, while keeping excellent shape-memory properties.

A new concept to build shape memory polymers (SMP) combining outstanding fixity and recovery ratios (both above 99% after only one training cycle) typical of chemically crosslinked SMPs with reprocessability restricted to physically crosslinked SMPs is demonstrated by covalently bonding, through thermoreversible Diels-Alder (DA) adducts, star-shaped poly(e-caprolactones) (PCL) end-functionalized by furan and maleimide moieties. A PCL network is easily prepared by melt-blending complementary end-functional star polymers in retro DA regime, then by curing at lower temperature to favour the DA cycloaddition. Such covalent network can be reprocessed when heated again at the retro DA temperature. The resulting SMP shows still excellent shape memory properties attesting for its good recyclability.

Chitosan is a nontoxic, biodegradable, and biocompatible polysaccharide of β(1-4)-linked d-glucosamine and N-acetyl-d-glucosamine. This derivative of natural chitin presents remarkable properties that have paved the way for the introduction of chitosan in the biomedical and pharmaceutical fields. Nevertheless, the properties of chitosan, such as its poor solubility in water or in organic solvents, can limit its utilization for a specific application. An elegant way to improve or to impart new properties to chitosan is the chemical modification of the chain, generally by grafting of functional groups, without modification of the initial skeleton in order to conserve the original properties. The functionalization is carried out on the primary amine group, generally by quaternization, or on the hydroxyl group. This review aims to provide an overview of chitosan and chitosan derivatives used for drug delivery, with a special emphasis on chemical modifications of chitosan to achieve specific biomedical purpose. The synthesis of the main chitosan derivatives will be reviewed. The applications of chitosan and these chitosan derivatives will be illustrated.