Inorganic Materials Chemistry C7780 1 Jiri Pinkas Office C12 / 224 Phone 549496493 Email: jpinkas@chemi.muni.cz • Lectures: PowerPoint presentations with recorded talk uploaded in the IS MU 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., HÜSING, N., Synthesis of Inorganic Materials. Weinheim: Wiley-VCH CALLISTER, W.D.J., Materials Science and Engineering, An Introduction. John Wiley and Sons SMART, L., MOORE, E., Solid state chemistry : an introduction. 2nd ed. London: Chapman & Hall INNOCENZI, Plinio, The Sol to Gel Transition, Springer International Publishing WHITE, Mary Anne, Physical Properties of Materials, 2nd Edition, CRC Press MUELLER, Ulrich, Inorganic Structural Chemistry, 2nd Edition, Wiley Recommended Literature 3 OZIN, G.A., ARSENAULT, A.C., CADEMARTIRI, L., Nanochemistry : a chemical approach to nanomaterials. 2nd ed. Cambridge: RSC Publishing, 2009. CADEMARTIRI, L., OZIN, G.A., Concepts of nanochemistry. Edited by Jean-Marie Lehn. Weinheim: Wiley-VCH, 2009. FAHLMAN, B. D. Materials Chemistry. Springer 2018. LOWELL, S., SHIELDS J. E., Martin A. THOMAS, M. A., THOMMES, M. Characterization of Porous Solids and Powders: Surface Area, Pore Size and Density. Springer 2004. MITTEMEIJER, E. J. Fundamentals of Materials Science. Springer 2011. 4 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 5 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 6 Materials in Human History - Metals 7 Materials in Human History - Ceramics 8 Development of Materials in Human History 9 Compounds vs. Materials * Chemical compounds single use (pharmaceuticals, fertilizers, fuels) * Materials - repeated or continual use - shaping Shaping of Macro and Micro Materials Ceramics Glasses Metals, Alloys Polymers Composites Semiconductors 11 Shaping of Nanomaterials Au concave cubes Cu2O nanoframes ZnO nanobeltsZnO nanopropellers ZnO nanorings 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 Classes of Materials Three Classical Classes of Materials 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 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 15 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 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 Core-shell NanobeltsNanowires 17 Size of Particles Nanoparticles 1 – 100 nm Traditional materials > 1 mm Cu 18 Shapes of Natural and Synthetic Single Crystals Calcite CaCO3 Cu-Ag nanoalloy 19 Onion-Like Particles MoS2Graphitic 20 CB[6] = cucurbit[6]uril Synthesis of porous SiO2 nanospheres Functional Materials Dynamic wagging motion by Z-E interconversion N N N N 448 nm 21 Functional Materials Dual-controlled nanoparticles exhibiting 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 = a + b) Simultaneous excitation with 448 nm light AND addition of NaOH causes the contents to be released CB[6] = cucurbit[6]uril E ⇄ Z 22 Functional Materials - Si3N4 Hexagonal  modification  modificationSi N Si N • Strong covalent bond (4.9 eV) • Hardness (a-monocrystal, Vickers 21 GPa) • Tensile Strength 1.5 GPa (-whisker) • Young modulus 350 GPa • Decomposition temp. 1840 °C/1 atm N2 • Density 3.2 g cm-3 23 Si3N4 Ceramics 24 Microstructure of Materials SiC/Si3N4 nanocomposite Glass phase 25 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 26 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 27 Self-Assembling Monolayers STM on HOPG 28 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 29 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 STEM - Imaging at Nanoscale 30 a) 2D EDX map of a Au@Ag nanocube. Based on a tilt series of 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. TEM - Atomic Scale Imaging 31 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.