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Poly[sulfur-random-1,3-diisopropenylbenzene (DIB)] copolymers synthesized via inverse vulcanization form electrochemically active polymers used as cathodes for high-energy density Li–S batteries, capable of enhanced capacity retention (1005 mAh/g at 100 cycles) and lifetimes of over 500 cycles. In this prospective, we demonstrate how analytical electron microscopy can be employed as a powerful tool to explore the origins of the enhanced capacity retention. We analyze morphological and compositional features when the copolymers, with DIB contents up to 50% by mass, are blended with carbon nanoparticles. Replacing the elemental sulfur with the copolymers improves the compatibility and interfacial contact between active sulfur compounds and conductive carbons. There also appears to be improvements of the cathode mechanical stability that leads to less cracking but preserving porosity. This compatibilization scheme through stabilized organosulfur copolymers represents an alternative strategy to the nanoscale encapsulation schemes which are often used to improve the cycle life in high-energy density Li–S batteries.
Processible poly(methylsilsesquioxane)s (PMSSQs) were prepared in THF solution under nitrogen atmosphere in the presence of HCl catalyst. It was found that various reaction parameters such as concentration, temperature, reaction time, the amount of water, and the amount of acid catalyst could affect the molecular weight and the amount of functional end groups of PMSSQ samples. Thin films prepared from our PMSSQ samples by spin-coating followed by curing to 420°C exhibited a much better crack resistance than those presented in the literature, while the dielectric constant remained practically the same, i.e., ca. 2.7.
We introduce a method to build up organic/organic and organic/inorganic multilayer films composed of cationic poly(allylamine hydrochloride) (PAH) and negatively charged poly(sodium 4-styrenesulfonate) (PSS) or inorganic cadmium sulfide (CdS) nanoparticles using a spinning process. Since the deposition of each layer is made at a high spinning speed, the adsorption time for the formation of a homogeneous thin layer takes only 8 to 15 seconds. The adsorbed film thickness per bilayer can be easily controlled from about 5Å to 40Å by varying the spinning speed (Ω) and the mole concentration of polyelectrolytes. We also demonstrated with X-ray reflectivity that the alternating organic/inorganic ultrathin films fabricated by the spin SA process retain highly ordered internal structure in comparison with those prepared by the conventional SA process.
Mesoporous organosilicas based on a bridged organosilicate have been synthesized using a triblock PEO-PLGA-PEO copolymer containing more hydrophobic poly(DL-lactic acid-coglycolic acid) block and the structural difference between mesoporous organosilicas prepared from PEO-PLGA-PEO and PEO-PPO-PEO block templates is discussed.
A new approach to create layer-by-layer assembled multilayer ultrathin films with welldefined micropatterns in a short process time is introduced. To achieve such micropatterns with high line resolution in organic multilayer films, microfluidic channels were combined with the convective self-assembly process employing both hydrogen bonding and electrostatic intermolecular interactions. The channels were initially filled with polymer solution by capillary pressure and the residual solution was then removed by spinning process. The micropatterns with distinct line boundaries were obtained and the small ridges were also observed at the edges of the patterned lines. Spin self-assembled vertical heterostructural multilayer patterning using (PVP/PAA)5 micropatterns, which were prepared with microfluidic channels, as a template was also investigated.
The BMIM+NO3-/Ag metal nanocomposite membranes were utilized for separation of propylene/propane mixtures. The selectivity of propylene/propane and the mixed gas permeance increased to 10 and 1.3 GPU, respectively. It is anticipated that the interactions between NO3- of BMIM+NO3- and the surface of silver nanoparticles causes the Ag surface to be partially positively charged, resulting in the reversible complexation with propylene and consequently facilitated propylene transport. The surface positive charge was confirmed from the increase in the binding energy of the d5/2 orbital of the silver nanoparticles by x-ray photoelectron spectroscopy. It increased from 368.26 for the neat silver nanoparticles to 368.47 eV for BMIM+NO3-/Ag metal composite. The positively charged surface of silver nanoparticles can be utilized as a new durable olefin carrier for facilitated transport.
Polysilsesquioxanes (PSSQs) with the empirical formula (RSiO3/2)n have become very important as low-dielectric insulators for copper interconnects in the next-generation logic devices, but the detailed structure-property relationships were completely lacking. We have investigated the microstructure and functional properties of PSSQs with varying alkyl substituents and also PSSQ copolymers. As a result, significant advances have been made in the scientific understanding of PSSQ structures and significant improvements of key properties such as the crack resistance, mechanical modulus and hardness, and incorporation of nanometer-sized (<4 nm) porosity for ultra-low dielectric constants (<2.0).
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