Synthesis and characterization of polystyrene-blockpoly(vinylbenzoic acid): a promising compound for manipulating photoresponsive properties at the nanoscale

"Published online: 27 January 2015"Using reversible addition-fragmentation chain transfer (RAFT) polymerization, the effect of PSt macroRAFT and 4VBA ratio on the synthesis of a carboxylic acid functional block copolymer (PSt-b-P4VBA) was studied. PSt macroRAFT polymer was initially prepared followed by the insertion of 4-vinylbenzoic acid (4VBA) monomer. The chemical structure of the diblock copolymer was confirmed by NMR and FTIR. The effect of PSt macroRAFT and 4VBA ratio on copolymerization yield and on molecular weight distribution was assessed by gel permeation chromatography. The rate of polymerization did not change as the 4VBA/PSt macroRAFT ratio increased, indicating an ideal amount of 4VBA insertion. An optimal ratio of [PSt macroRAFT]:[AIBN]:[4VBA] was 1.2:1:180. DSC and XRD confirmed the amorphous structure of homo and copolymer. Thermal stability was higher for PSt-b-P4VBA forming activated porous carbon char by dehydration, carbonization and oxidation. SEM and STEM observations showed a morphological evolution between PSt macroRAFT and the correspondent copolymer.The authors acknowledge the n-STeP-Nanostructured systems for Tailored Performance, with reference NORTE-07-0124-FEDER-000039, supported by the Programa Operacional Regional do Norte (ON.2), PEst-C/CTM/LA0025/2013 (Strategic Project-LA 25-2013-2014)

Impact of Fuel Production Technologies on Energy Consumption and GHG Emissions from Diesel and Electric–Hydrogen Hybrid Buses in Rio de Janeiro, Brazil

In view of the GHG reduction targets to be met, Brazilian researchers are looking for cleaner alternatives to energy sources. These alternatives are primarily to be applied in the transport sector, which presents high energy consumption, as well as high CO2 emissions. In this sense, this research developed an LCI study considering two bus alternatives for the city of Rio de Janeiro: diesel-powered internal combustion buses (ICEB) and a hydrogen-powered polymer fuel cell hybrid bus (FCHB). For the FCHB, three hydrogen production methods were also included: water electrolysis (WE), ethanol steam reforming (ESR) and natural gas steam reforming (NGSR). The research was aimed at estimating energy consumption, including the percentage of energy that is renewable, as well as CO2 emissions. The results show diesel as the energy source with the highest emissions as well as the highest fossil energy consumption. Regarding the alternatives for hydrogen production, water electrolysis stood out with the lowest emissions

pH-Switchable Stratification of Colloidal Coatings: Surfaces “On Demand”

Stratified coatings are used to provide properties at a surface, such as hardness or refractive index, which are different from underlying layers. Although time-savings are offered by self-assembly approaches, there have been no methods yet reported to offer stratification on demand. Here, we demonstrate a strategy to create self-assembled stratified coatings, which can be switched to homogenous structures when required. We use blends of large and small colloidal polymer particle dispersions in water that self-assemble during drying because of an osmotic pressure gradient that leads to a downward velocity of larger particles. Our confocal fluorescent microscopy images reveal a distinct surface layer created by the small particles. When the pH of the initial dispersion is raised, the hydrophilic shells of the small particles swell substantially, and the stratification is switched off. Brownian dynamics simulations explain the suppression of stratifi-cation when the small particles are swollen as a result of reduced particle mobility, a drop in the pressure gradient, and less time available before particle jamming. Our strategy paves the way for applications in antireflection films and pro-tective coatings in which the required surface composition can be achieved on demand, simply by adjusting the pH prior to deposition

Dynamic Stratification in Drying Films of Colloidal Mixtures

In simulations and experiments, we study the drying of films containing mixtures of large and small colloidal particles in water. During drying, the mixture stratifies into a layer of the larger particles at the bottom with a layer of the smaller particles on top. We developed a model to show that a gradient in osmotic pressure, which develops dynamically during drying, is responsible for the segregation mechanism behind stratification.Comment: Accepted for publication in Physical Review Letters. Supplementary Material added as Appendi