Symposium A Advanced Materials: From Fundamentals to Applications INVITED LECTURES 1. Potassium hydroxide 2. Potassium hydride 3. Potassium carbonate 4. Sodium hydroxide 5. Sodium hydride 6. Sodium carbonate 7. Calcium hydroxide 8. Calcium carbonate 9. Calcium sulphate 10. Calcium nitrate 11. Calcium chloride 12. Barium hydroxide 13. Barium carbonate 14. Barium sulphate 15. Barium nitrate 16. Barium chloride 17. Aluminium sulphate 18. Aluminium nitrate 19. Aluminium chloride 20. Alum 21. Potassium silicate 22. Potassium silicate 23. Potassium calcium silicate 24. Potassium barium silicate 25. Silicon fluoride 26. Ammonium potassium 27. Ethylene chloride compound Chemical symbols used by Dalton, 19th century ← Previous page: Distilling apparatus from John French’s The art of distillation, London 1651 Symposium A: Advanced Materials A - IL 1 Binuclear Complexes as Tectons in Designing Supramolecular Solid-State Architectures Marius Andruh University of Bucharest, Faculty of Chemistry, Inorganic Chemistry Laboratory Str. Dumbrava Rosie nr. 23, 020464-Bucharest, Romania [email protected] We are currently developing a research project on the use of homo- and heterobinuclear complexes as building-blocks in designing both oligonuclear species and high-dimensionality coordination polymers with interesting magnetic properties. The building-blocks are stable binuclear complexes, where the metal ions are held together by compartmental ligands, or alkoxo- bridged copper(II) complexes. The binuclear nodes are connected through appropriate exo- - 3- III bidentate ligands, or through metal-containing anions (e. g. [Cr(NH3)2(NCS)4] , [M(CN)6] , M = Fe , CrIII). A rich variety of 3d-3d and 3d-4f heterometallic complexes, with interesting architectures and topologies of the spin carriers, has been obtained1. A particular case is the one concerning the 3d-4f binuclear nodes. The building principle is based on the employment of symmetrical (dicarboxylato anions, bis(4-pyridyl) derivatives) or of unsymmetrical spacers (e. g. the isonicotinate anion), which act selectively with the different (3d, 4f) metal ions. Following this strategy we were able to obtain coordination polymers containing three different spin carriers (2p-3d-4f; 3d-3d’-4f). The magnetic properties of the newly synthesized compounds have been investigated and will be discussed. Acknowledgements I am grateful for the contributions to this work to my coworkers Violeta Tudor, Ruxandra Gheorghe, Augustin M. Madalan, Geanina Marin, Andrei Cucos. References: 1. A. M. Madalan, H. W. Roesky, M. Andruh, M. Noltemeyer, N. Stanica, Chem. Commun., 2002, 1638; R. Gheorghe, M. Andruh, A. Müller, M. Schmidtmann, Inorg. Chem., 2002, 41, 5314; V. Tudor, G. Marin, V. Kravtsov, Y. A. Simonov, J. Lipkowski, M. Brezeanu, M. Andruh, Inorg. Chim. Acta, 2003, 353, 35; R. Ghorghe, M. Andruh, J. P. Costes, B. Donnadieu, Chem. Commun., 2003, 2778. 3 A - IL 2 ICOSECS 4 - Chemical Sciences in Changing Times: Visions, Challenges and Solutions Interphase in Fiber Reinforced Composites: Characterization and Design Gordana Bogoeva-Gaceva Faculty of Technology and Metallurgy, University Sts. Cyril and Methodius Skopje, Macedonia The properties of fiber reinforced composite materials largely depend on the nature and properties of interphase region. Interfacial phenomena control stress transfer to, and distribution between, the fibers and also govern mechanisms of damage accumulation and propagation. Recently the interphase is treated as a three-dimensional entity, extending further than the atomic dimensions of the boundary. The existence of an interphase, whose properties are different from those of the bulk matrix, is related to several factors, such as: specific adsorption and wetting behavior of fibers, chemical and physical interactions between the matrix and the fiber, specific polymer morphology and an existence of transcrystalline interface (in semicrystalline thermoplastic composites), etc. The nature and properties of the interface are unique to each fiber/matrix system, however, certain common features apply, and will be discussed in this paper. Interfacial analysis encompasses both chemical and mechanical characterization of the interfacial region. Different approaches to the characterization are developed, involving wetting studies, surface spectroscopies, microthermal analysis, differntial csanning calorimetry, atomic force microscopy, micromechanical tests, etc., in an attempt to describe and optimize the boundary region. However, the question of interfacial optimization is a complex one without simple answers, owing to the complexity of the chemical and physical nature of the interface and the variety of roles it is called on to perform. The possibilities of controlling interfacial strength by means of target-oriented variation of strength, structure and thickness of the interphase, created between differently treated (sized, plasma treated, untreated) glass and carbon fibers and thermoplastic and thermoset matrices, are discussed in this paper. In order to correlate the mechanical response with the characteristics of the interface, micro- and macromechanical methods were applied to investigate glass and carbon fiber composites with thermoplastic and thermoset matrices. 4 Symposium A: Advanced Materials A - IL 3 New Insight into the Role of Extra-Framework Cations in Zeolite Materials Chemistry V. Dondur 1Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16 P.O. Box 137, 11000 Belgrade, Serbia and Montenegro, [email protected] An approach to preparation for a novel material is sometimes found in the developments of new structural elements, new arrangements or combinations of them, and new preparation technique as a total system. Microporous systems are becoming increasingly important as the host material for new arrangement of the guest materials. Properties of porous materials are intimately related to their framework topological features and chemical compositions. Currently, the most important porous materials are zeolites. Zeolites are micropurous aluminosilicate materials made up of 4- 3- (SiO4) and (AlO4) tetrahedral arranged in defined manner to give the material with an open framework structure of cavities and pores. Each aluminum atom in the framework carries a net negative charge which is balanced by a charge-balancing cation. Within zeolites, the cation exchange density is controlled by the framework Si/Al ratio. Presence of all these charged constituents produces a highly polar environment within the cavities of zeolites. Alumosilicate framework exerts a strong, localized electrostatic field that can alter the properties of charge- balancing cations. Therefore, the behavior of the cations inside the zeolite is often different then that of cations adsorbed, precipitated or exchanged into other porous solids. By considering cations as being located within specific sites in each or the many zeolite topologies, one can envision the oxide ions in the framework providing ligand centers which also impose some steric constraint around the cation. Thus, each zeolite offers its own unique crystal field, perhaps exerting multiple crystal field effects on different cation sites. In that manner, zeolites can serve as a host providing a high level of dispersion of cations, while offering multiple sites to environments. Being in these sites, cations are often coordinatively unsaturated. Differences in coordination around the cations in exchange sites could give to cation-zeolite system unusual and unexpected properties and shape selectivity associated with pores size. This paper reviews the results of investigation of the influence of extra-framework cations, their nature and amounts, on different zeolite’s features: magnetic and adsorption properties and the possibilities of phase transformations. Different zeolite topologies (SOD, LTA, FAU and ZSM5) with alkaline, alkaline earth, transition metal or large organic cations, were considered. As a result of alkaline cations incorporation into low pore sized zeolite SOD, the change of magnetic properties of this structure was noticed. High temperature transformation of zeolites modified by alkaline and alkaline-earth cations were performed. The obtained new phases were investigated using XRD, NMR, IR, Raman and thermal analysis methods. The influence of the presence of extra-framework cations and included salts on the mechanism of high temperature transformation into new ceramic materials was evidenced. The adsorption and catalytic possibilities of alkaline, alkaline earth, and transition metal cation-exchanged zeolites were investigated using microcalorimetric and spectroscopic (MAS and IR) methods. The cations were recognized as active sites for adsorption and forming of carbonyl-like, nitrosyl-like and amino complexes. Quantitative and energetic aspects of these reactions were studied by means of adsorption microcalorimetry and TPD/MAS. Additionally, the specific interactions of incorporated large organic cations with external zeolite surface active sites were studied. The adsorption of insecticides and pesticides on some modified zeolite structures was found. On the others, catalytic decomposition of these organic compounds happened, indicating the possibility of usage of modified zeolites in wastewater treatment. 5 A - IL 4 ICOSECS 4 - Chemical Sciences in Changing Times: Visions, Challenges and Solutions Tailoring the Properties of Highly Uniform Metallic Particles Dan V. Goia Clarkson University/Center for Advanced