Anisotropic Lithium Ion Conductivity in Single‐Ion Diblock Copolymer Electrolyte Thin Films

Well‐defined single‐ion diblock copolymers consisting of a Li‐ion conductive poly(styrenesulfonyllithium(trifluoromethylsulfonyl)imide) (PSLiTFSI) block associated with a glassy polystyrene (PS) block have been synthesized via reversible addition fragmentation chain transfer polymerization. Conductivity anisotropy ratio up to 1000 has been achieved from PS‐b‐PSLiTFSI thin films by comparing Li‐ion conductivities of out‐of‐plane (aligned) and in‐plane (antialigned) cylinder morphologies at 40 °C. Blending of PS‐b‐PSLiTFSI thin films with poly(ethylene oxide) homopolymer (hPEO) enables a substantial improvement of Li‐ion transport within aligned cylindrical domains, since hPEO, preferentially located in PSLiTFSI domains, is an excellent lithium‐solvating material. Results are also compared with unblended and blended PSLiTFSI homopolymer (hPSLiTFSI) homologues, which reveals that ionic conductivity is improved when thin films are nanostructured.

     

Nano-organization of amylose-b-polystyrene block copolymer films doped with bipyridine

This paper discusses the self-assembly of rod-coil amylose-b-polystyrene (Mal-b-PS) block copolymer thick and thin films. The nano-organization falls in an interdomain spacing d of about 10 nm, much smaller than flexible-flexible petrol block copolymer systems. Additionally, hydrogen-bonding interactions between carbohydrate rods (amylose) and 4',4-bipyridine (bipy) molecules induces phase transitions. Indeed, adding bipy in maltooctadecaose-block-polystyrene (Mal18-b-PS) copolymers results, at room temperature, in the formation of a lamellar phase having Mal18 bipy-rich nanodomains instead of hexagonal close-packed (HCP) of cylinders made of Mal18, whereas a coexistence of Mal7bipy-rich cylindrical and spherical nanodomains are formed from maltoheptaose-b-polystyrene (Mal7-b-PS) copolymers instead of a poorly organized array of Mal7-based cylinders. On heating, the Mal7bipy-b-PS system shows more rich phase behavior as compared to the Mal7-b-PS one due to weakening of hydrogen bonding with temperature. Such a system is of great interest in developing active layers in light-emitting diodes (LEDs) or in photovoltaic cells to realize devices with an optimal structure, that is, having large interface area and domain size with similar exciton diffusion length (10 nm).     

Fluorescent Vesicles Consisting of Galactose‐based Amphiphilic Copolymers with a π‐Conjugated Sequence Self‐assembled in Water

Fluorescent vesicles considered as a mimic of natural primitive cells are prepared from poly(3‐hexylthiophene)‐block‐poly(3‐O‐methacryloyl‐D‐galactopyranose) P3HT‐b‐PMAGP copolymers. The unique characteristic of such vesicular nanostructures is their architecture, which comprises a hydrophobic π‐conjugated P3HT wall stabilized by a hydrophilic PMAGP interface featuring glucose units. The results of this work offer a very efficient and straightforward method for engineering well‐controlled fluorescent nanoparticles (without the addition of dyes), which provide an excellent support to the study of carbohydrate‐protein interactions.

     

Self-assembled block polymer templates as high resolution lithographic masks

Diblock copolymer thin films have recently received more attention due to their ability to organize into nanometric structures under thermal annealing. This phenomenon was studied for an asymmetric poly(styrene-block-methyl methacrylate) (PS-b-PMMA) diblock copolymer with PMMA weight fraction of 0.3 and MW = 67,100 g mol⁻¹. First, the surface chemistry of the substrate was modified to favor the formation of vertical PMMA cylinders surrounded by a PS matrix. We have also found that the mean pore area of cylinders increases with their coordination number. Finally, these films were used as a deposition or etching mask to produce well-organized arrays of holes, dots and nanopillars.     

Synthesis of Carbon Nanohorns by Inductively Coupled Plasma

We demonstrate a new pathway for the synthesis of carbon nanohorns (CNHs) in a reactor by using inductively coupled plasma (ICP) and gaseous precursors. Thermal plasma synthesis allows the formation of different carbon allotropes such as carbon nanoflakes, hybrid forms of flakes and nanotubules, CNHs embryos, seed-like CNHs and onion-like polyhedral graphitic nanocapsules. In this study, pressure has the greatest impact on the selectivity of carbon nanostructures: pressure below 53.3 kPa favors the growth of carbon nanoflakes and higher pressures, 66.7 kPa and above, promotes the formation of CNHs. The ratio between methane and hydrogen as well as the global concentration of CH₄?+?H₂ inside the plasma flame are also crucial to the reaction. CNHs are formed preferentially by injection of a 1:2 ratio of H₂ to CH₄ at 82.7 kPa with a production rate of 20 g/h. The synthesis pathway is easily scalable and could be made continuous, which offers an interesting alternative compared to methods based on laser-, arc- or induction-based vaporization of graphite rods.

Graphical Abstract

     

Impact of Tween 60 on physicochemical properties and stability of Pistacia lentiscus fruit oil-in-water emulsion at a semi-low temperature

This study shows the effects of the Tween 60 emulsifier at different concentrations on the aqueous emulsion containing 5% of Pistacia lentiscus fruit oil. The rheological behavior and the droplet size distribution of cosmetic oil-in-water emulsions were investigated. This investigation was carried out by analyzing the shear flow and dynamic oscillatory followed by microscopic analysis and physical stability study for 24?hours and 4 months. During the period of 4 months, the emulsions were stored in a refrigerator at a semi-low temperature 12?°C. The physical stability test showed that the sample not emulsified yielded a creaming process after a short aging time. Flow curves of emulsions prepared with TW 60 exhibited a non-linear relationship between the shear stress σ and shear rate γ ?, which implies that the Herschel–Bulkley rheological model was the appropriate model for the shear flow. The increase of emulsifier quantities leading to an increase in the internal structure coherence, whereas the excess quantity affects the structure. Therefore, the optimal quantity proposed was 3.47%. Furthermore, the storage time at a semi-low temperature performed the stability and maintain the structure of emulsions.     

Hexagonal-to-cubic phase transformation in composite thin films induced by FePt nanoparticles located at PS/PEO interfaces

The organization process of asymmetric poly(styrene-block-ethylene oxide) (PS-b-PEO) copolymer thin films blended with FePt nanoparticles is studied. In a first step, it is shown that FePt nanoparticles stabilized by oleic acid ligands are distributed within the PS matrix phase, whereas the same particles partially covered with short dopamine-terminated-methoxy poly(ethylene oxide) (mPEO-Dopa) are located at PS/PEO interfaces. The swelling of PS domains, induced by FePt_oleic acid nanoparticles during the solvent annealing process, results in formation of a disordered microstructure in comparison to the well-organized hexagonally close-packed (HCP) cylinder phase formed in the neat PS-b-PEO copolymer. The evolution of the microstructure of PS-b-PEO/FePt_mPEO-Dopa composite has been investigated for different solvent annealing treatments. Under high-humidity conditions during the vapor annealing process, the addition of FePt nanoparticles results in formation of spheres in the film split into terraces. The upper and lower terraces are occupied by spheres organized in an unusual square and HCP phases, respectively. Under low-humidity conditions, undulated PEO cylinders oriented parallel to substrate are formed in the presence of FePt nanoparticles. In this case, we observe that most of the nanoparticles accumulate within the core of topological defects, which induces a low nanoparticle concentration at the PS/PEO interfaces and so stabilizes an intermediate undulated cylinder phase.