Polymerization in magnetic field: XVIII. Influence of surfactant nature on the synthesis and thermal properties of poly(methyl methacrylate) and poly[(methyl methacrylate)‐co‐(epoxypropyl methacrylate)]

BACKGROUND: The possibility to use β‐cyclodextrin as biodegradable tensioactive and an electromagnetic field in order to improve the kinetic parameters of radical emulsion polymerization is of interest. Thus, the influence of different surfactants—sodium lauryl sulfate (SLS) and β‐cyclodextrin (CD)—on the pathway of emulsion polymerization of methyl methacrylate (MMA) and emulsion copolymerization of MMA with 2,3‐epoxypropyl methacrylate (GMA) performed with or without the presence of a continuous electromagnetic field (MF) was studied. RESULTS: The presence of the MF leads to a considerable increase of the conversion during the first part of the reaction if the classic surfactant (SLS) is used. The reactions performed without MF and with CD exhibit a decrease of the conversion and of the polymerization rate as compared with the variants using SLS. The swelling rate and the maximum degree of swelling vary with the surfactant nature and with the reaction conditions and MF presence. Data from thermogravimetry and differential scanning calorimetry evidence the dependences between the polymer characteristics and the preparation conditions. CONCLUSION: This research underlines the coupling possibilities of the influence of a MF—growth of the reaction rate and conversion explained through radical pairs mechanism—with a combination of the ‘cage’ effect and ‘conformational control’ afforded by CD. The presence of MF and CD during the syntheses leads to an increase of T_g and an increase of PMMA and P(MMA‐co‐GMA) thermal stability. Copyright © 2007 Society of Chemical Industry     

Co-pyrolysis of pine cone with synthetic polymers

Biomass from pine cone (Pinus pinea L.) was co-pyrolyzed with synthetic polymers (PE, PP and PS) in order to investigate the effect of biomass and plastic nature on the product yields and quality of pyrolysis oils and chars. The pyrolysis temperature was of 500 °C and it was selected based on results from thermogravimetric analysis of the studied samples. Co-pyrolysis products namely gases, aqueous and tar fraction coming from biomass, oils from synthetic polymers and residual char were collected and analyzed. Due to the synergistic effect in the pyrolysis of the biomass/polymer mixtures, higher amounts of liquid products were obtained compared to theoretical ones. To investigate the effect of biomass content on the co-pyrolysis, the co-pyrolysis of pure cellulose as model natural polymer for biomass with polymer mixture was also carried out. In the presence of cellulose, degradation reaction leading to more gas formation and less char yield was more advanced than in the case of co-pyrolysis with pine cone. Co-pyrolysis gave polar oxygenated compounds distributed between tar and aqueous phase and hydrocarbon oils with composition depending on the type of synthetic polyolefin. Co-pyrolysis chars had higher calorific values compared to pyrolysis of biomass alone.     

Supramolecular and nanochemistry

The following contributions describe various research activities of the Department of Chemistry, University of Basel in the area of nanochemistry and supramolecular chemistry.     

Triple tangent flank milling of ruled surfaces

This paper presents a positioning strategy for flank milling ruled surfaces. It is a modification of a positioning method developed by Bedi et al. [Comput Aided Des 35 (2003) 293]. A cylindrical cutting tool is initially positioned tangential to the two boundary curves on a ruled surface. Optimization is used to move these tangential points to different curves on the ruled surface to reduce the error. A second optimization step is used to additionally make the tool tangent to a rule line, further reducing the error and resulting in a tool position, where the tool is positioned tangential to two guiding rails and one rule line. The resulting surface has 88% less under cutting than the method of Bedi et al.     

Landscape externalities from onshore wind power

The expansion of renewable energy is a central element of the German Federal Government's climate and energy policy. The target for 2020 is to produce 30% of the electricity from renewable energies. Wind power has been selected to be a major contributor to this change. Replacing old wind turbines by modern ones and building new turbines on land will be crucial in meeting this target. However, the expansion of onshore wind power is not universally accepted. In several regions of Germany residents are protesting against setting up new wind turbines. To determine the negative effects two choice experiments were applied in Westsachsen and Nordhessen, Germany. In both regions the externalities of wind power generation until 2020 based on today's state of technology were measured. The results show that negative landscape externalities would result from expanding wind power generation. Using latent class models three different groups of respondents experiencing different degrees of externalities were identified.     

Does thermal control improve visual satisfaction? Interactions between occupants’ self-perceived control,visual, thermal,and overall satisfaction

Occupants’ satisfaction had been researched independently related to thermal and visual stimuli for many decades showing among others the influence of self-perceived control. Few studies revealed interactions between thermal and visual stimuli affecting occupant satisfaction. In addition, studies including interactions between thermal and visual stimuli are lacking different control scenarios. This study focused on the effects of thermal and visual factors, their interaction, seasonal influences, and the degree of self-perceived control on overall, thermal, and visual satisfaction. A repeated-measures laboratory study with 61 participants running over two years and a total of 986 participant sessions was conducted. Mixed model analyses with overall satisfaction as outcome variable revealed that thermal satisfaction and visual satisfaction are the most important predictors for overall satisfaction with the indoor environment. Self-perceived thermal control served as moderator between thermal satisfaction and overall satisfaction. Season had slight influence on overall satisfaction. Random effects explained the highest amount of variance, indicating that intra- and interindividual differences in the ratings of satisfaction are more prevalent than study condition. Future building design and operation plans aiming at a high level of occupant satisfaction should consider personal control opportunities and take into account the moderating effect of control opportunities in multimodal interactions.     

Heuristic Methods for Minimum-Cost Pipeline Network Design – a Node Valency Transfer Metaheuristic

Designing low-cost network layouts is an essential step in planning linked infrastructure. For the case of capacitated trees, such as oil or gas pipeline networks, the cost is usually a function of both pipeline diameter (i.e. ability to carry flow or transferred capacity) and pipeline length. Even for the case of incompressible, steady flow, minimizing cost becomes particularly difficult as network topology itself dictates local flow material balances, rendering the optimization space non-linear. The combinatorial nature of potential trees requires the use of graph optimization heuristics to achieve good solutions in reasonable time. In this work we perform a comparison of known literature network optimization heuristics and metaheuristics for finding minimum-cost capacitated trees without Steiner nodes, and propose novel algorithms, including a metaheuristic based on transferring edges of high valency nodes. Our metaheuristic achieves performance above similar algorithms studied, especially for larger graphs, usually producing a significantly higher proportion of optimal solutions, while remaining in line with time-complexity of algorithms found in the literature. Data points for graph node positions and capacities are first randomly generated, and secondly obtained from the German emissions trading CO₂ source registry. As political will for applications and storage for hard-to-abate industry CO₂ emissions is growing, efficient network design methods become relevant for new large-scale CO₂ pipeline networks.

     

A DNA-Micropatterned Surface for Propagating Biomolecular Signals by Positional on-off Assembly of Catalytic Nanocompartments

Signal transduction is pivotal for the transfer of information between and within living cells. The composition and spatial organization of specified compartments are key to propagating soluble signals. Here, a high-throughput platform mimicking multistep signal transduction which is based on a geometrically defined array of immobilized catalytic nanocompartments (CNCs) that consist of distinct polymeric nanoassemblies encapsulating enzymes and DNA or enzymes alone is presented. The dual role of single entities or tandem CNCs in providing confined but communicating spaces for complex metabolic reactions and in protecting encapsulated compounds from denaturation is explored. To support a controlled spatial organization of CNCs, CNCs are patterned by means of DNA hybridization to a microprinted glass surface. Specifically, CNC-functionalized DNA microarrays are produced where individual reaction compartments are kept in close proximity by a distinct geometrical arrangement to promote effective communication. Besides a remarkable versatility and robustness, the most prominent feature of this platform is the reversibility of DNA-mediated CNC-anchoring which renders it reusable. Micropatterns of polymer-based nanocompartment assemblies offer an ideal scaffold for the development of the next generation responsive and communicative soft-matter analytical devices for applications in catalysis and medicine.     

Chemical oxidation of residual carbon from ZnAl2O4 powders prepared by combustion synthesis

The removal of carbon residue from ZnAl₂O₄ nanopowders by annealing at 500–800 °C leads to a decrease of specific surface area from 228.1 m²/g to 47.6 m²/g. At the same time, the average crystallite size increased from 5.1 nm to 14.9 nm. In order to overcome these drawbacks, a new solution for removing the carbon residue has been suggested: chemical oxidation using hydrogen peroxide. In terms of carbon removal, a H₂O₂ treatment for 8 h at 107 °C proved to be equivalent to a heat treatment of 1 h at 600 °C. The benefits of chemical oxidation over thermal oxidation were obvious. The specific surface area was much larger (188.1 m²/g) in the case of the powder treated with H₂O₂. The average crystallite size (5.8 nm) of ZnAl₂O₄ powder treated with H₂O₂ was smaller than the crystallite size (8.2 nm) of the ZnAl₂O₄ powder annealed at 600 °C.