Fabrication of hybrid proton-exchange membranes using a brandnew high temperature ionic liquid as charge transporting and clay modifier

The search for more compatibility between ionic liquids (ILs) and polymer matrices in proton-exchange membrane fuel cells (PEMFCs) is one of the ways in which IL leaking from proton-exchange membranes could be minimized. In this work, it is presented the synthesis of an aromatic high temperature ionic liquid (HTIL), which, incorporated into an aromatic matrix such as sulfonated polyether ether ketone (sPEEK), is expected to diminish the IL leaking that normally affects PEMFC. Phenylethylammonium trifluoromethane sulfonate (PhetaTfO) was successfully synthesized and characterized. Its melting point of 88°C makes it to classify as a HTIL and it was employed as modifier of natural Montmorillonite, forming the phenylethylammonium intercalated montmorillonite (MmtPheta) and thus, ternary membranes containing PhetaTfO, MmtPheta, and sPEEK were prepared and characterized. Immersion tests demonstrated a higher compatibility of PhetaTfO with matrix when compared to the reference DemaTfO, which was reflected in up to 30% lower IL loss by the synthesized IL than the DemaTfO; X-rays diffraction (XRD) patterns demonstrated that the modified clay was properly dispersed inside the membranes, while dynamic mechanical analyses (DMA) results indicated a strong plasticizer effect along the increase of PhetaTfO content inside the membrane, while at the same time, the conductivity increased in an exponential manner, which permitted to identify an empiric exponential equation to evaluate the effect of concentration on ionic conductivity. The maximum conductivity obtained at IL concentrations of around 38 wt% was 0.2 mS/cm. It could expect high ionic conductivities of 10 mS/cm when the concentration of this IL is 60%; nevertheless, in order to achieve that, crosslinking treatments should be done to give the membranes enough mechanical resistance.     

Synthesis and characterization of photopolymerizable hydrogels based on poly (ethylene glycol) for biomedical applications

Hydrogels are polymeric materials widely used in medicine due to their similarity with the biological components of the body. Hydrogels are biocompatible materials that have the potential to promote cell proliferation and tissue support because of their hydrophilic nature, porous structure, and elastic mechanical properties. In this work, we demonstrate the microwave-assisted synthesis of three molecular weight varieties of poly(ethylene glycol) dimethacrylate (PEGDMA) with different mechanical and thermal properties and the rapid photo of them using 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184) as UV photoinitiator. The effects of the poly(ethylene glycol) molecular weight and degree of acrylation on swelling, mechanical, and rheological properties of hydrogels were investigated. The biodegradability of the PEGDMA hydrogels, as well as the ability to grow and proliferate cells, was examined for its viability as a scaffold in tissue engineering. Altogether, the biomaterial hydrogel properties open the way for applications in the field of regenerative medicine for functional scaffolds and tissues.     

Synthesis of amphiphilic (meth)acrylates with oligo(ethylene glycol) and (or) oligo(propylene glycol) blocks by the esterification of (meth)acrylic acid

Thermoresponsive PEG-based (PEG stands polyethylene glycol) polymers are unique for use in medicine because of their low toxicity, good biocompatibility and biodegradability, but usually more hydrophobic and more toxic comonomers are used to adjust lower critical solution temperature (LCST). A convenient way to overcome this problem and to finely tune LCST is to use alkoxy oligo(ethylene glycol)- or alkoxy oligo(propylene glycol) (meth)acrylates as starting comonomers. Here we report on the conditions for the simple and affordable synthesis of methoxy oligo(propylene glycol) (meth)acrylate- and methoxy oligo(propylene glycol)-block-oligo(ethylene glycol) (meth)acrylate-based macromonomers with high yields (80%–98.7%) by the acid-catalyzed esterification of (meth)acrylic acid with alkoxy oligo(alkylene glycols) containing oligo(ethylene glycol) (OEG) and/or oligo(propylene glycol) (OPG) blocks. p-Toluene sulphonic acid (pTSA), alkyl(C₁₂–C₁₄)benzene sulfonic acid (ABSA) and H₂SO₄ were used as catalysts. It has been shown that pTSA and ABSA are practically the same in catalytic activity and are superior to sulfuric acid. The reaction orders with respect to catalyst was found to be close to 1 in all cases. It has been shown that the reaction is actually insensitive to the lengths of OEG and OPG blocks, as well as to the structure of the terminal alkyl group, while the esterification of acrylic acid (AA) proceeds much faster compared to methacrylic acid (MAA) one under the same conditions. The influence of temperature on the equilibrium conversions of alcohols was determined, which were found to be 89%–93% for the esterification of AA and 61%–86% for MAA in the temperature range of 60–120°C. A further increase in conversion was achieved by introducing an azeotropic agent (toluene), its optimal concentration was found to be 10%–15%.     

pH sensitive phosphate crosslinked films of starch-carboxymethyl cellulose

This work aims to develop hydrogel films of starch and carboxymethyl cellulose (CMC) crosslinked with sodium trimetaphosphate (STMP) and to characterize some of their properties. Starch and STMP (S/T), starch and CMC (S/C), and mixed (S/T/C) films were prepared by casting. The degree of substitution, morphology, swelling degree, FTIR, mechanical properties, and sorption isotherms were studied. Reticulated samples (S/T and S/T/C) showed the same degree of substitution (0.050 ± 0.001). All films presented homogeneous morphology, but the mixed film showed greater roughness. Crosslinking increased the swelling capacity of the mixed hydrogel at pH 7, although it remained decreased concerning the S/T hydrogel. However, this property was sensitive to pH variations. The mixed film (S/T/C) showed greater mechanical resistance. The casting process was efficient to produce hydrogel films of starch/CMC crosslinked with STMP and the general results demonstrated the advantages of the mixed hydrogel.     

Mechanical characterization and modeling stress relaxation behavior of acrylic–polyurethane-based graft-interpenetrating polymer networks

The stress relaxation behavior of acrylic–polyurethane (PU)-based graft-interpenetrating polymer networks (IPNs) was characterized via dynamic mechanical analysis (DMA) and modeled using finite element method (FEM) analysis. Stress relaxation of glassy IPN specimens was experimentally studied under flexural testing, while rubbery IPN specimens were tested in tension. The effects of varying the styrene content in the acrylic copolymer phase, compatibility of the two phases in IPNs, and changing the concentration of acrylic copolymer and PU were studied. A higher percentage of styrene content resulted in higher homogeneity of IPN specimens, and decrease in initial modulus for acrylic copolymer specimens. Additionally, glassy IPN specimens with 90% styrene shows resistance to relaxation as high as acrylic copolymer samples. Experimental results were used to develop a numerical model to study stress relaxation response of specimens. While polymer systems have been studied computationally, numerical modeling of IPN systems is still in its infancy. A three-dimensional FEM model was developed using the Generalized Maxwell model and four-term Prony series constants, which were extracted from the stress relaxation experiments. With four terms in the Prony series, a good match was observed between experimental observations and results from the FEM model.     

Recommending multimedia visiting paths in cultural heritage applications

The valorization and promotion of worldwide Cultural Heritage by the adoption of Information and Communication Technologies represent nowadays some of the most important research issues with a large variety of potential applications. This challenge is particularly perceived in the Italian scenario, where the artistic patrimony is one of the most diverse and rich of the world, able to attract millions of visitors every year to monuments, archaeological sites and museums. In this paper, we present a general recommendation framework able to uniformly manage heterogeneous multimedia data coming from several web repositories and to provide context-aware recommendation techniques supporting intelligent multimedia services for the users—i.e. dynamic visiting paths for a given environment. Specific applications of our system within the cultural heritage domain are proposed by means of real case studies in the mobile environment related both to an outdoor and indoor scenario, together with some results on user’s satisfaction and system accuracy.     

Visual search tree profiling

Understanding how the search space is explored for a given constraint problem – and how it changes for different models, solvers or search strategies – is crucial for efficient solving. Yet programmers often have to rely on the crude aggregate measures of the search that are provided by solvers, or on visualisation tools that can show the search tree, but do not offer sophisticated ways to navigate and analyse it, particularly for large trees. We present an architecture for profiling a constraint programming search that is based on a lightweight instrumentation of the solver. The architecture combines a visualisation of the search tree with various tools for convenient navigation and analysis of the search. These include identifying repeated subtrees, high-level abstraction and navigation of the tree, and the comparison of two search trees. The resulting system is akin to a traditional program profiler, which helps the user to focus on the parts of the execution where an improvement to their program would have the greatest effect.     

Semantic weaving of configuration fragments into a consistent system configuration

Configuration fragments developed separately and focusing on different aspects, such as availability, security or performance of a system need to be integrated into a consistent system configuration to avoid system malfunctions. The main challenges of such integration are due to the overlapping entities and the integration relations between the entities of the different configuration fragments. In this paper we propose a model based approach for a consistent integration of configuration fragments into a system configuration. We use and extend the model weaving technique to capture the semantics of the relations between the entities of the configuration fragments. Moreover, we generate automatically the constraints corresponding to these semantic relations to complete the target system configuration profile. These constraints can be used to guard the configuration consistency during runtime modifications.