Visual Appearance of Chiral Nematic Cellulose‐Based Photonic Films: Angular and Polarization Independent Color Response with a Twist

Hydroxypropyl cellulose (HPC) is a biocompatible cellulose derivative capable of self‐assembling into a lyotropic chiral nematic phase in aqueous solution. This liquid crystalline phase reflects right‐handed circular polarized light of a specific color as a function of the HPC weight fraction. Here, it is demonstrated that, by introducing a crosslinking agent, it is possible to drastically alter the visual appearance of the HPC mesophase in terms of the reflected color, the scattering distribution, and the polarization response, resulting in an exceptional matte appearance in solid‐state films. By exploiting the interplay between order and disorder, a robust and simple methodology toward the preparation of polarization and angular independent color is developed, which constitutes an important step toward the development of real‐world photonic colorants.     

Synthesis of Fluorinated Hyperbranched Polymers and Their Use as Additives in Cationic Photopolymerization

Summary: A fluorine containing hyperbranched polymer was synthesized by modifying an aromatic‐aliphatic hyperbranched polyester with a semifluorinated alcohol via a Mitsunobu reaction and was subsequently used as an additive in cationic photopolymerization of an epoxy resin. The remaining OH groups of the fluorinated hyperbranched polymer interact with the polymeric carbocation through a chain‐transfer mechanism inducing an increase in the final epoxy conversion. The fluorinated HBP induces modification of bulk and surface properties, with an increase in T_g and surface hydrophobicity already reached at very low concentration. The HBFP additive can, therefore, protect the coatings from aggressive solvents, increases hardness, and allows the preparation of a low energy surface coating.

Synthesis of fluorinated hyperbranched polyester.     

Opening Doors to Future Electrochemical Energy Devices: The Anion‐Conducting Polyketone Polyelectrolytes

The numerous potential benefits of incorporating anion‐exchange membranes (AEMs), in place of proton‐exchange membranes (PEMs), in energy storage and conversion technologies renders their development of fundamental importance for the continued evolution of alternative energy systems. However, the widespread implementation of AEMs is currently plagued by a range of problems including lower conductivity (with respect to PEMs), poor stability, and high cost. This study reports the conversion of polyketone, one of the world's most mass produced and cheap polymers, to a new highly tuneable polymer architecture, functionalized polyketone (FPK), that demonstrates a range of excellent properties rendering it a significant prospect for AEM materials. The thermal, processing, and ion‐conducting properties of FPK are governed by the amount and nature of the newly formed N‐substituted pyrrole pendant side groups. At 80 °C, the quarternized pyridyl FPK derivative (4MPyrFPK) yields ion‐conductivities of 8.6 and 10.5 mS cm^?1 in the iodide and hydroxide forms. In addition, the hydroxide form of 4MPyr‐FPK demonstrates remarkable stability toward the typically problematic alkaline conditions. No chemical decomposition is observed to the membrane after imbibing it in KOH solution for 72 h, and furthermore, the ion‐conductivity is demonstrated to remain constant for at least 30 d at 80 °C.     

Bio‐inspired Highly Scattering Networks via Polymer Phase Separation

A common strategy to optimize whiteness in living organisms consists in using 3D random networks with dense and polydisperse scattering elements constituted by relatively low refractive index materials. Inspired by these natural architectures, a fast and scalable method to produce highly scattering porous polymer films via phase separation is developed. By varying the molecular weight of the polymer, the morphology of the porous films is modified, and therefore their scattering properties are tuned. The achieved transport mean free paths are in the micrometer range, improving the scattering strength of analogous low refractive index systems, e.g., standard white paper, by an order of magnitude. The produced porous films show a broadband reflectivity of ≈75% while only 4 µm thick. In addition, the films are flexible and can be readily index‐matched with water (i.e., they become transparent when wet), allowing for various applications such as coatings with tunable transmittance and responsive paints.     

Quality assessment of bed sediments of the Po River (Italy)

Comprehensive and contemporary evaluations of physical, chemical and toxicological endpoints have been performed on bed sediments of the Po River, the major Italian watercourse. Two extensive sampling campaigns were conducted in summer and winter low-flow conditions. Composite sediment samples were collected from ten reaches of the main river: the first was located in the upper region (ambient control), and the others downstream of the confluences of nine principal tributaries. The two sampling programs were paralleled by contemporary investigations on the macroinvertebrate community. The particle-size composition along the Po River showed a relatively uniform distribution of fine sand, a progressive downstream decrease of coarse sands and a corresponding increase of fine materials. The levels of polychlorinated biphenyls (PCB), polycyclic aromatic hydrocarbons (PAH), extractable organo halides (EOX), Cd, Cr, Cu, Hg, Ni, Pb and Zn were determined in sediment fine particles (< 63 microm), and showed marked changes across the ten river reaches. Their longitudinal trends, as those of organic carbon and total nitrogen, were very similar and largely independent of the survey season. Sediment quality benchmarks were used to evaluate sediment chemistry, and, although the overall level of contamination was from moderate to low, the reaches located downstream of the tributaries Dora Riparia, Dora Baltea, Lambro and Oglio were considered to be at risk. Sediments were tested for toxicity on Oncorhynchus mykiss, Ceriodaphnia dubia, Raphidocelis subcapitata and Vibrio fischeri. The toxicity tests were conducted both with sediment extracts and whole samples. Sediment extracts showed toxic potentials that were consistent with the spatial distribution of contaminants. Whole-sediment toxicity showed moderate/low effects which also included false positives and negatives. Alterations of the macroinvertebrate community were found for many kilometers downstream of Dora Riparia, and with a seasonal dependence, also in other reaches of the Italian river. Principal component analysis (PCA) was used to describe the longitudinal and temporal changes of the Po River, and allowed the selection of the most useful and discriminating indicators.     

Output feedback stabilization of the angular velocity of a rigid body

The problem of stabilization of the angular velocity of a rigid body using only two control signals and partial state information is addressed. It is shown that if any two (out of three) states are measured the system is not asymptotically stabilizable with (continuous) dynamic output feedback. Nevertheless, we prove that practical stability is achievable if the measurable states fulfill a certain structural property, and that, under the same structural condition, a hybrid control law yielding exponential convergence can be constructed. Finally, we also study some geometric features of the Euler’s equations and the connection between local strong accessibility and local observability.     

Some considerations on the warping of marble façades: the example of Alvar Aalto’s Finland Hall in Helsinki

A scanning electron microscope study was performed on samples cored from the white-marble panels of Finland Hall’s façade which revealed considerable warping only a few years after the building’s completion. The analysis shows that granular decohesion is the most important sign of damage at the microstructural level. The presence of calcium sulphate is clearly recognisable on the façade’s surface, though it appears that chemical attack has failed to penetrate inside the material and, presumably, cannot thus be considered the only cause of decay. Following up on the results of other experimental observations that correlate warping with the degradation of bending strength, flexural tests were performed on four different qualities of white-marble, conditioned by thermal cycles in order to reproduce the damage process. The tests evidence that the four material types present very different resistance to thermal aggression: some varieties hold up very poorly, while others instead remain reliable in the long term.     

Combined heat and power plant effects on CO2 emission: Case study of the University of Perugia

In this work the CO₂ emissions due to the University of Perugia's energy needs have been evaluated. Perugia is a city set in the middle of Italy, in the ‘Umbria’ region, with a population of about 1400 000 people. The University of this city was founded in 1260 and nowadays consists of eleven Faculties with 30 000 students and about 1200 teachers. The energy needs of the University are mainly due to thermal and electrical users. In particular, the thermal consumption is strictly connected to building heating in the autumn–winter months. The reduction of CO₂ emissions is one of the main goals that developed countries have established to be achieved in the next few years, not only related to the Kyoto treated goals, but also for increasing economical and industrial production with a sustainable development concept. Carbon dioxide is not strictly a toxic substance, but makes a large contribution to the ‘greenhouse effect’ with negative repercussions for the environment. For these reasons the possibility of satisfying the University of Perugia's energy needs by the adoption of one, or more, cogeneration power plant fuelled by natural gas, opportunely located at the University, has been evaluated both in terms of energy production and of CO₂ emission reduction. This study also takes into account the experiences of the cogeneration power plant that is in operation at the Engineering Faculty of Perugia University. The results have been compared with the Regional Energetic Development Planning for evaluating the influence of the University's energy needs and emissions on the whole Region. Copyright © 2001 John Wiley & Sons, Ltd.     

Singular H∞ control for nonlinear systems

This paper presents a solution to the singular H_∞ control problem via state feedback for a class of nonlinear systems. It is shown that the problem of almost disturbance decoupling with stability plays a fundamental role in the solution of the considered problem. We also point out when the singular problem can be reduced to a regular one or solved via standard H_∞ technique. We must stress that the solution of the singular problem is obtained without making any approximation of it by means of regular problems. © 1997 John Wiley & Sons, Ltd.