Self-Healing Transparent Poly(dimethyl)siloxane with Tunable Mechanical Properties: Toward Enhanced Aging Materials for Space Applications.

When exposed to the geostationary orbit, polymeric materials tend to degrade on their surface due to the appearance of cracks. Implementing the self-healing concept in polymers going to space is a new approach to enhancing the lifespan of materials that cannot be replaced once launched. In this study, the elaboration of autonomous self-healing transparent poly(dimethylsiloxane) (PDMS) materials resistant to proton particles is presented. The PDMS materials are functionalized with various compositions of urea and imine moieties, forming dynamic covalent and/or supramolecular networks. The hydrogen bonds induced by the urea ensure the formation of a supramolecular network, while the dynamic covalent imine bonds are capable of undergoing exchange reactions. Materials with a broad range of mechanical properties were obtained depending on the composition and structure of the PDMS networks. As coating applications in a spatial environment were mainly targeted, the surface properties of the polymer are essential. Thus, percentages of scratch recovery were determined by AFM. From these data, self-healing kinetics were extracted and rationalized based on the polymer structures. The obtained data were in good agreement with the relaxation times determined by rheology in stress relaxation experiments. Moreover, the accelerated aging of materials under proton irradiation, simulating a major part of the geostationary environment, revealed a strong limitation or disappearance of cracks while keeping the transparency of the PDMS. These promising results open routes to prepare new flexible autonomous polymeric materials for space applications.

Janus Effect of Lewis Acid Enables One-Step Block Copolymerization of Ethylene Oxide and N-Sulfonyl Aziridine.

One-step sequence-selective block copolymerization requires stringent catalytic control of monomers relative activity and enchainment order. It has been especially rare for An Bm -type block copolymers from simple binary monomer mixtures. Here, ethylene oxide (EO) and N-sulfonyl aziridine (Az) compose a valid pair provided with a bicomponent metal-free catalyst. Optimal Lewis acid/base ratio allows the two monomers to strictly block-copolymerize in a reverse order (EO-first) as compared with the conventional anionic route (Az-first). Livingness of the copolymerization facilitates one-pot synthesis of multiblock copolymers by addition of mixed monomers in batches. Calculation results reveal that a Janus effect of Lewis acid on the two monomers is key to enlarge the activity difference and reverse the enchainment order.

Large and Giant Unilamellar Vesicle(s) Obtained by Self-Assembly of Poly(dimethylsiloxane)-b-poly(ethylene oxide) Diblock Copolymers, Membrane Properties and Preliminary Investigation of their Ability to Form Hybrid Polymer/Lipid Vesicles.

In the emerging field of hybrid polymer/lipid vesicles, relatively few copolymers have been evaluated regarding their ability to form these structures and the resulting membrane properties have been scarcely studied. Here, we present the synthesis and self-assembly in solution of poly(dimethylsiloxane)-block-poly(ethylene oxide) diblock copolymers (PDMS-b-PEO). A library of different PDMS-b-PEO diblock copolymers was synthesized using ring-opening polymerization of hexamethylcyclotrisiloxane (D3) and further coupling with PEO chains via click chemistry. Self-assembly of the copolymers in water was studied using Dynamic Light Scattering (DLS), Static Light Scattering (SLS), Small Angle Neutron Scattering (SANS), and Cryo-Transmission Electron Microscopy (Cryo-TEM). Giant polymersomes obtained by electroformation present high toughness compared to those obtained from triblock copolymer in previous studies, for similar membrane thickness. Interestingly, these copolymers can be associated to phospholipids to form Giant Hybrid Unilamellar Vesicles (GHUV); preliminary investigations of their mechanical properties show that tough hybrid vesicles can be obtained.

The Effect of Hybridized Carbon Nanotubes, Silica Nanoparticles, and Core-Shell Rubber on Tensile, Fracture Mechanics and Electrical Properties of Epoxy Nanocomposites.

The paper investigates the effect of adding a combination of rigid nanoparticles and core-shell rubber nanoparticles on the tensile, fracture mechanics, electrical and thermo-mechanical properties of epoxy resins. SiO2 nanoparticles, multi-walled carbon nanotubes (MWCNT's), as rigid nanofillers, and core-shell rubber (CSR) nanoparticles, as soft nanofillers were used with bisphenol-A-based epoxy resin. Further, the rigid fillers were added systematically with core-shell rubber nanoparticles to investigate the commingled effect of rigid nanofillers and soft CSR nanoparticles. The resulting matrix will be broadly evaluated by standard methods to quantify tensile, fracture mechanics, electrical, and thermal properties. The results show that the electrical conductivity threshold is obtained at 0.075 wt. % for MWCNT-modified systems. For hybrid systems, the maximum increase of fracture toughness (218%) and fracture energy (900%) was obtained for a system containing 5 wt. % of CSR and 10 wt. % of SiO2. The analysis of the fracture surfaces revealed the information about existing toughening micro-mechanisms in the nanocomposites.

Improvement of the Thermal and Optical Performances of Protective Polydimethylsiloxane Space Coatings with Cellulose Nanocrystal Additives.

This work investigates the possibility of using cellulose nanocrystals (CNCs) as biobased nanoadditives in protective polydimethylsiloxane (PDMS) space coatings, to improve the thermal and optical performances of the material. CNCs produced from wood pulp were functionalized in different conditions with the objective to improve their dispersibility in the PDMS matrix, increase their thermal stability and provide photoactive functions. Polysiloxane, cinnamate, chloroacetate and trifluoroacetate moieties were accordingly anchored at the CNCs surface by silylation, using two different approaches, or acylation with different functional vinyl esters. The modified CNCs were thoroughly characterized by FT-IR spectroscopy, solid-state NMR spectroscopy and thermogravimetric analysis, before being incorporated into a PDMS space coating formulation in low concentration (0.5 to 4 wt %). The cross-linked PDMS films were subsequently investigated with regards to their mechanical behavior, thermal stability and optical properties after photoaging. Results revealed that the CNC additives could significantly improve the thermal stability of the PDMS coating, up to 140 °C, depending on the treatment and CNC concentration, without affecting the mechanical properties and transparency of the material. In addition, the PDMS films loaded with as low as 1 wt % halogenated nanoparticles, exhibited an improved UV-stability after irradiation in geostationary conditions.

The organocatalytic ring-opening polymerization of N-tosyl aziridines by an N-heterocyclic carbene.

The ring-opening polymerization of N-tosyl aziridines, in the presence of 1,3-bis(isopropyl)-4,5(dimethyl)imidazol-2-ylidene as an organocatalyst and an N-tosyl secondary amine as initiator mimicking the growing chain, provides the first metal-free route to well defined poly(aziridine)s (PAz) and related PAz-based block copolymers.

From Lignin-derived Aromatic Compounds to Novel Biobased Polymers.

Nowadays, the synthesis of (semi)aromatic polymers from lignin derivatives is of major interest, as aromatic compounds are key intermediates in the manufacture of polymers and lignin is the main source of aromatic biobased substrates. Phenols with a variety of chemical structures can be obtained from lignin deconstruction; among them, vanillin and ferulic acid are the main ones. Depending on the phenol substrates, different chemical modifications and polymerization pathways are developed, leading to (semi)aromatic polymers covering a wide range of thermomechanical properties. This review discusses the synthesis and properties of thermosets (vinyl ester resins, cyanate ester, epoxy, and benzoxazine resins) and thermoplastic polymers (polyesters, polyanhydrides, Schiff base polymers, polyacetals, polyoxalates, polycarbonates, acrylate polymers) prepared from vanillin, ferulic acid, guaiacol, syringaldehyde, or 4-hydroxybenzoic acid.