Inorganic Materials Chemistry C7780 1 Jiri Pinkas Office A12/224 Phone 549496493 Email: jpinkas@chemi.muni.cz Course grading: • 3 graded homeworks during semester • Short presentations on a selected topic concerning materials chemistry • Written final exam (100 pts, minimum 50 pts to pass) Grading weights: final test 75%, homeworks 15%, presentation 10%. Recommended Literature 2 SCHUBERT, U. a N. HÜSING. Synthesis of Inorganic Materials. Weinheim: Wiley-VCH CALLISTER, W.D.J. Materials Science and Engineering, An Introduction. John Wiley and Sons SMART, L. a E. MOORE. Solid state chemistry : an introduction. 2nd ed. London: Chapman & Hall Plinio Innocenzi, The Sol to Gel Transition, Springer International Publishing Mary Anne White, Physical Properties of Materials, 2nd Edition, CRC Press Ulrich Muller , Inorganic Structural Chemistry, 2nd Edition, Wiley 3 Materials in Human History Historical perspective: New materials bring advancement to societies • Stone age • Bronze age • Iron age • Silicon age Crescent Axes. The top Syrian, the bottom Egyptian. about 1900 BC 4 Materials in Human History 50 000 B.C. Iron oxide pigments Lascaux, Altamira 24 000 B.C. Ceramics – fat, bone ash, clay 3 500 B.C. Cu metallurgy Glass, Egypt and Mesopotamia 3 200 B.C. Bronze 1 600 B.C. Iron metallurgy, Hittites 1 300 B.C. Steel 1 000 B.C. Glass production, Greece, Syria 105 B.C. Paper, China 590 A.D. Gun powder, China 700 A.D. Porcelain, China 5 Materials in Human History - Metals 6 Materials in Human History - Ceramics 7 Development of Materials in Human History 8 Compounds vs. Materials * Chemical compounds single use (pharmaceuticals, fertilizers, fuels) * Materials - repeated or continual use - shaping Shaping of Materials 10 Shaping of (Nano)Materials Au concave cubes Cu2O nanoframes ZnO nanobeltsZnO nanopropellers ZnO nanorings 11 Materials Ceramics (oxides, carbides, nitrides, borides) Glasses (oxides, fluorides, chalcogenides, metallic) Metals, Alloys, Intermetallics Polymers - inorganic, organic, hybrid Semiconductors (Si, Ge, 13/15, 12/16 compounds) Composites, Inorganic-Organic Hybrid Materials Zeolites, Layer and Inclusion Materials Biomimetic Materials, hydroxyapatite Carbon-based Materials: Fullerenes, Fullerene Tubes, Graphene 12 Properties of Materials A property = a material trait, the kind and magnitude of response to a specific stimulus Properties Mechanical Electrical Thermal Magnetic Optical Deteriorative (corrosion) Catalytic Biocompatibility 13 Metals Ceramics Polymers Strong Strong Usually not strong Ductile Brittle Very ductile Electrical Conductor Electrical Insulator Electrical Insulator Heat Conductor Thermal Insulator Thermal Insulator Not transparent May be transparent Not transparent Shiny Heat Resistant Low Densities 14 Materials Science: Studies relationships between the structure and properties of materials Materials Engineering: Designing and engineering the structure of a material to produce a predetermined set of properties Processing Structure Properties Function 15 atomic bonding crystal structure microstructure properties final product Natural sciences Materials science Engineering ApplicationsBasic research F Materials Chemistry among Natural and Technical Sciences 16 Materials Chemistry Role of Materials Chemistry • Synthesis of new materials – new atom architecture • Preparation of high purity materials • Fabrication techniques for tailored morphologies (shapes and sizes) • Fabrication of functional materials Tento obrázek nyní nelze zobrazit. 17 Shapes of Natural and Synthetic Single Crystals Calcite CaCO3 Cu-Ag nanoalloy 18 Onion-Like Graphitic Particles 19 Functional Materials Dual-controlled nanoparticles exhibit AND logic function (a) Excitation with 448 nm light induces the dynamic wagging motion of the nanoimpellers, but the nanovalves remain shut and the contents are contained. (b) Addition of NaOH opens the nanovalves, but the static nanoimpellers are able to keep the contents contained. (c) Simultaneous excitation with 448 nm light AND addition of NaOH causes the contents to be released. CB[6] = cucurbit[6]uril 20 CB[6] = cucurbit[6]uril 21 Materials Chemistry Single crystals, defects, dopants, non-stoichiometry Monoliths Coatings Thin or thick films - singlecrystalline, polycrystalline, amorphous, epitaxial Fibers, Wires, Tubes Powders – primary particles, aggregates, agglomerates polycrystalline, amorphous, nanocrystalline (1-100 nm) Porous materials micropores (< 20 Å), mesopores (20-500 Å), macropores (> 500 Å) Micropatterns Nanostructures – spheres, hollow spheres, rods, wires, tubes, photonic crystals Self-assembly – supramolecular chemistry: rotaxenes, catenanes, cavitands, carcerands 22 Direct reactions of solids – „heat-and-beat“ Precursor methods Chimie douce, soft-chemistry methods, synthesis of novel metastable materials, such as open framework phases Ion-exchange methods, solution, melt Intercalation: chemical, electrochemical, pressure, exfoliation-reassembly Crystallization techniques, solutions, melts, glasses, gels, hydrothermal, molten salt, high P/T Vapor phase transport, synthesis, purification, crystal growth, doping Materials Chemistry Tool Box 23 Electrochemical synthesis, redox preparations, anodic oxidation, oxidative polymerization Preparation of thin films and superlattices, chemical, electrochemical, physical, self-assembling mono- and multilayers Growth of single crystals, vapor, liquid, solid phase chemical, electrochemical High pressure methods, hydrothermal, diamond anvils Combinatorial materials chemistry, creation and rapid evaluation of gigantic libraries of related materials Materials Chemistry Tool Box 24 Si3N4 Hexagonal a modification b modificationSi N Si N • Strong covalent bond (4.9 eV) • Hardness (a-monocrystal, Vickers 21 GPa) • Tensile Strength 1.5 GPa (b-whisker) • Young modulus 350 GPa • Decomposition temp. 1840 °C/1 atm N2 • Density 3.2 g cm-3 25 Si3N4 Ceramics 26 Microstructure of Materials SiC/Si3N4 nanocomposite Glass phase 27 Microstructure vs. Properties tens.str. tensile stress SiC inclusion Sliding of grains slowed down improved mechanical properties Si3N4tensile stressSi3N4 Sliding of grains 150 nm SiC inclusion Imaging at Nanoscale 28 a) 2D EDX map of a Au@Ag nanocube. Based on a tilt series of such 2D EDX maps the 3D reconstruction presented in (b) was obtained. The contrast in the 3D reconstruction is based on differences in chemical composition and it is clear that the core of the particle has an octahedral form. Atomic Scale Imaging 29 Atomic scale reconstruction of Au nanorods. a,b) Orthogonal slices through the atomic scale reconstruction of Au nanorods prepared using different surfactants. The side facets of these rods can be clearly recognized. c) Strain measurement along the major axis of the nanorod.