Nanomaterials and Nanochemistry

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1 C. Br&hignac P. Houdy M. Lahmani (Eds.) Nanomaterials and Nanochemistry With 461 Figures and 26 Tables R 5 EUROPEAN MATERIALS RESEARCH SOCIETY ei Springer

2 Contents Part I Basic Principles and Fundamental Properties 1 Size Effects on Structure and Morphology of Free or Supported Nanoparticles C. Henry Size and Confinement Effects Introduction Fraction of Surface Atoms Specific Surface Energy and Surface Stress Effect on the Lattice Parameter Effect on the Phonon Density of States Nanoparticle Morphology Equilibrium Shape of a Macroscopic Crystal Equilibrium Shape of Nanometric Crystals Morphology of Supported Particles 17 References 32 2 Structure and Phase Transitions in Nanocrystals J.-C. Niepce, L. Pizzagalli Introduction Crystalline Phase Transitions in Nanocrystals Phase Transitions and Grain Size Dependence Elementary Thermodynamics of the Grain Size Dependence of Phase Transitions Influence of the Surface or Interface on Nanocrystals Modification of Transition Barriers Geometric Evolution of the Lattice in Nanocrystals Grain Size Dependence Theory Influence of the Nanocrystal Surface or Interface on the Lattice Parameter 50

3 XII Contents Is There a Continuous Variation of the Crystal State Within Nanocrystals? 51 References 53 3 Thermodynamics and Solid Liquid Transitions P. Labastie, F. Calvo Size Dependence of the Solid Liquid Transition From the Macroscopic to the Nanometric From Nanoparticles to Molecules Thermodynamics of Very Small Systems General Considerations Non-Equivalence of the Gibbs Ensembles Dynamically Coexisting Phases Stability of an Isolated Particle. Thermodynamic Equilibrium Evaporation: Consequences and Observation Statistical Theories of Evaporation Link with the Solid Liquid Transition. Numerical Results Experimental Investigation of Evaporation Beyond Unimolecular Evaporation Toward the Liquid Gas Transition 82 References 86 4 Modelling and Simulating the Dynamics of Nano-Objects A. Pimpinelli Introduction Free Clusters of Atoms. Molecular Dynamics Simulations Evolution of Free and Supported Nanoclusters Toward Equilibrium. Kinetic Monte Carlo Simulations 93 References 97 Part II Physical and Chemical Properties an the Nanoscale 5 Magnetism in Nanomaterials D. Givord Introduction Magnetism in Matter Magnetic Moment Magnetic Order Magnetocrystalline Anisotropy Magnetisation Process and Magnetic Materials Energy of the Demagnetising Field. Domains and Walls The Magnetisation Process Magnetic Materials 115

4 Contents XIII 5.4 Magnetism in Small Systems Magnetic Moments in Clusters Magnetic Order in Nanoparticles Magnetic Anisotropy in Clusters and Nanoparticles Magnetostatics and Magnetisation Processes in Nanoparticles Single-Domain Magnetic Particles Thermal Activation and Superparamagnetism Coherent Rotation in Nanoparticles From Thermal Activation to the Macroscopic Tunnel Effect Magnetism in Coupled Nanosystems Exchange-Coupled Nanocrystals. Ultrasoft Materials and Enhanced Remanence Coercivity in Nanocomposites Exchange Bias in Systems of Ferromagnetic Nanoparticles Coupled with an Antiferromagnetic Matrix 130 References Electronic Structure in Clusters and Nanoparticles F. Spiegelman Introduction Liquid-Drop Model Methods for Calculating Electronic Structure Born Oppenheimer Approximation. Surface Potential Ab Initio Calculation of Electronic Structure Density Functional Theory Charge Analysis Approximate and Semi-Empirical Descriptions Energy Bands and Densities of States Applications to Some Typical Examples Metallic Nanoparticles Molecular Clusters Tonic and Ionocovalent Clusters Covalent Systems Valence Changes Transitions with Size Transitions with Stoichiometry Nanotub es Prospects 185 References Optical Properties of Metallic Nanoparticles F. Valide Optical Response for Free Clusters and Composite Materials 198

5 XIV Contents 7.2 Optical Response in the Quasi-Static Approximation: Nanospheres Dielectric Constant of a Metal: Nanometric Size Effect Surface Plasmon Resonance in the Quasi-Static Approximation: Nanospheres Surface Plasmon Resonance: Quantum Effects for Small Sizes (D < 5 nm) General Case for Nanospheres: The Mie Model Non-Spherical or Inhomogeneous Nanoparticles in the Quasi-Static Model Shape Effects: Ellipsoids Structure Effects: Core Shell System Optical Response of a Single Metal Nanoparticle Electromagnetic Field Enhancement: Applications Nonlinear Optical Response Time-Resolved Spectroscopy Local Enhancement of Raman Scattering: SERS Conclusion 224 References Mechanical and Nanomechanical Properties C. Tromas, M. Verdier, M. Fivel, P. Aubert, S. Labdi, Z.-Q. Feng, M. Zei, P. Joli Macroscopic Mechanical Properties Introduction Elastic Properties Hardness Ductility Numerical Modelling Nanomechanical Properties Experimentation Computer Modelling 254 References S up erplast icity T. Rouxel Introduction Mechanism Superplastic Nanostructured Materials Industrial Applications 277 References 280

6 Contents XV 10 Reactivity of Metal Nanoparticles J.-C. Bertolini, J.-L. Rousset Size Effects Structural Properties Electronic Pfoper-Hes Reactivity in Chemisorption and Catalysis of Monometallic Nanoparticles Support Effects Alloying Effects Effect of Surface Segregation Geometric Effects Electronic Effects Preparation and Implementation in the Laboratory and in Industry 299 References Inverse Systems Nanoporous Solids J. Patarin, 0. Spalla, F. Di Renzo Introduction Nomenclature: The Main Families of Porous Materials Zeolites and Related Microporous Solids. Definition and Structure Ordered Mesoporous Solids Disordered Nanoporous Solids 311 References Inverse Systems Confined Fluids: Phase Diagram and Metastability E. Charlaix, R. Denoyel Displacement of First Order Transitions: Evaporation and Condensation Adsorption Isotherms Capillary Condensation Capillary Pressure and the Kelvin Radius Non-Wetting Fluid Perfectly Wetting Fluid Hysteresis, Metastability and Nucleation Melting Solidification Modification of the Critical Temperature Ultraconfinement: Microporous Materials 331 References 334

7 XVI Contents 13 Supramolecular Chemistry: Applications and Prospects N. Solladie, J.-F. Nierengarten From Molecular to Supramolecular Chemistry Molecular Recognition Anionic Coordination Chemistry and Recognition of Anionic Substrates Multiple Recognition Applications Prospects 343 References Nanocomposites: The End of Compromise H. Van Damme Composites and Nanocomposites Introduction to Polymers Ideal Chains The Glass Transition Entropie Elasticity Nanofillers Clays Carbon Nanotubes Strengthening and Permeability Control: Models Strengthening: Increasing the Modulus Impermeability: Reducing the Diffusivity Strengthening and Permeability of Nanocomposites: Facts and Explanations Strengthening: Successes and Failures Impermeability Dimensional Stability Fire Resistance Conclusion 379 References 380 Part III Synthesis of Nanomaterials and Nanoparticles 15 Specific Features of Nanoscale Growth J. Livage, D. Roux Introduction Thermodynamics of Phase Transitions Dynamics of Phase Transitions Thermodynamics of Spinodal Decomposition Thermodynamics of Nucleation Growth Size Control Triggering the Phase Transition 391

8 Contents XVII 15.6 Application to Solid Nanoparticles Controlling Nucleation Controlling Growth Controlling Aggregation. Stability of Colloidal Dispersions Breaking Matter into Pieces 393 References Gas Phase Synthesis of Nanopowders Y. Champion Introduction The Need for Gas State Processing Main Stages of Gas Phase Synthesis Spontaneous Condensation of Nanoparticles: Homogeneous Nucleation Undesirable Post-Condensation Effects and Control of the Nanometric State Why Do These Effects Occur? Particle Growth by Gas Condensation Coalescent Coagulation Vapour Formation and the Production of Nanopowders Physical Processes Chemical Processing: Laser Pyrolysis Conclusion 426 References Synthesis of Nanocomposite Powders by Gas Solid Reaction and by Precipitation C. Laurent Introduction Synthesis of Nanocomposite Powders by Gas Solid Reactions Synthesis of Intergranular Nanocomposite and Nano Nano Composite Powders Synthesis of Intragranular and Hybrid Nanocomposite Powders Conclusion 438 References Colloidal Methods and Shape Anisotropy D. Ingert Introduction Surfactants Reverse Micelles: Spherical Nanoreactors Factors Affecting Shape Control Effect of the Colloidal Template an Shape Control 448

9 XVIII Contents Effect of Anions on Nanocrystal Growth Effect of Molecular Adsorption on Nanocrystalline Growth Conclusion 452 References Mechanical Milling E. Gaffet, G. Le Car Introduction Mechanosynthesis Mechanical Activation Ball Mills Mechanisms Reducing Cristallite Sizes Parameters Relevant to Mechanical Alloying and Activation Mechanics of Mechanical Alloying Materials and Their Applications Mechanical Alloying Mechanical Activation Shaping and Densifying Nanomaterials Standard Processes Mechanically-Activated Field-Activated Pressure-Assisted Synthesis (MAFAPAS) Severe Plastic Deformation (SPD) High-Pressure Torsion (HPT) Equal Channel Angular Pressing (ECAP) Bulk Mechanical Alloying Synthesis of Nanocomposites by Extrusion, Drawing, and Embossing 468 References Supercritical Fluids A. Taleb Definition Physicochemical Properties Solubility Viscosity Diffusion Thermal Conductivity Applications Purification and Extraction Synthesis 480 References 484

10 Contents XIX Part IV Fabrication of Nanostructured Bulk Materials and Nanoporous Materials 21 Bulk Nanostructured Materials Obtained by Powder Sintering F. Bernard, J.-C. Niepce Sintering Definition The Physical Phenomena of Sintering Different Sintering Conditions Preserving Nanostructure During Sintering Spark Plasma Sintering (SPS) Basic Principle Advantages of the SPS Process Illustrations in the Field of Nanomaterials 493 References Self-Assemblr of Nanomaterials at Macroscopic Scales A. Courty Fabrication of Nanomaterials D and 3D Nanomaterial Structures Depositing Nanomaterials an a Solid Substrate Forces Inducing Self-Organisation Crystal Structure of 2D and 3D Nanomaterials Conclusion 513 References Assemblies of Magnetic Nanoparticles J. Richardi Magnetic Properties of Nanoparticle Assemblies Structure of Magnetic Nanoparticle Assemblies Deposited Without Field Structure of Magnetic Nanoparticle Assemblies Deposited with Field Perpendicular Field Parallel Field 526 References Nanostructured Coatings J. -P. Riviere Methodology for Malring Superhard Nanostructured Coatings Multilayers with Nanometric Period Nanocomposites Methods of Synthesis General Principles 536

11 XX Contents Plasma-Activated Chemical Vapour Deposition (PACVD) Physical Vapour Deposition by Sputtering and Cathodic Arc PVD by Ion Beam Sputtering 544 References Dispersion in Solids D. Babonneau Chemical Methods Synthesis of Doped Glasses Sol Gel Method Physical Methods Ion Implantation Vapour Deposition and Sputtering Methods Pulsed Laser Deposition Low Energy Cluster Beam Deposition (LECBD) 563 References Nanoporous Media J. Patarin, 0. Spalla, F. Di Renzo Introduction Synthesis of Crystalline Microporous Solids Methods of Synthesis The Crystallisation Process Exemplified by Zeolites Main Organic Structure-Directing Agents Used to Synthesise Crystalline Microporous Solids Role of Inorganic Cations and Organic Species Organic Species and the Template Effect Porosity of Zeolites and Related Solids Applications of Zeolitic Materials Synthesis of Ordered Mesoporous Solids Methods of Synthesis Definition and Role of the Surfactant Mechanisms for the Formation of MCM-41 Phase Characteristics of Mesoporous Silicas Obtained in the Presence of Amphiphilic Molecules Structural Characterisation of Nanoporous Solids by X-Ray and Neutron Scattering Conclusion 593 References Molecular Imprinting V. Dufaud, L. Bonneviot Introduction Fundamental Considerations General Principles 598

12 Contents XXI Role of Complexation Sites During the Imprinting Process Structure and Properties of the Polymer Matrix Procedures and Methods for Molecular Imprinting Imprinted Organic Polymers Imprinted Inorganic Matrices Applications Separating a Mixture of Herbicides Synthesis of a-aspartame Chiral Separation of Amino Acids by Ligand Exchange at a Metal Site Specific Elimination of Lanthanides and Actinides in a Highly Radioactive Efiluent Recent Challenges and Progress 612 References 613 Part V Applications of Nanomaterials 28 Electronics and Electromagnetism J.-C. Nece, D. Givord Multilayer Ceramic Capacitors What Is a Multilayer Ceramic Capacitor? Market Requirements Constraints Laid Down by these Requirements BaTiO3 Ceramic Dielectrics with Nanograins: The Favoured Solution Magnetic Recording General Operation Recording Materials. Longitudinal and Perpendicular Recording Write Heads Read Heads Disk Drive Motor 630 References Optics P. Maestro, M. Chagny, P.-P. Jobert, H. Van Damme, S. Berthier Cosmetics Introduction Nano-Titanium Oxides in Cosmetics: Solar Skin Protection Conclusion Nanophosphors Introduction Phosphors: General Considerations Operating Principle 638

13 XXII Contents Industrial Applications Conclusion Surface Nanoengineering What Is the Surface Area of a Town? Superhydrophobic Surfaces Self-Cleaning and Superhydrophilic Surfaces When Concrete Cleans the Air We Breathe Photonic Crystals The Colourful World of Birds and Insects Photonic Crystals and Photonic Band Gaps Guides and Cavities From Colloidal Crystals to Photonic Crystals 654 References Mechanics P. Maestro, E. Gaffet, G. Le Ca6r, A. Mocellin, E. Reynaud, T. Rouxel, M. Soulard, J. Patarin, L. Thilly, F. Lecouturier Silica Precipitates for High-Performance Tyres Fabrication of Silica Precipitates Tyres and Other Applications Ceramic Metal Composite Welding Supports Ceramics Reactive Mechanical Alloying and High-Energy Ball Milling Improving Properties Reinforced Amorphous Matrices Not All Materials Are Ordered Incorporating Nanoparticles into Amorphous Matrices Prospects The Long Road Nanoporous Solids as Molecular Springs, Shock Absorbers and Bumpers Introduction Basic Idea Pressure Volume Diagram Stored Energy and Restored Energy Causes of Irreversibility Behaviour of the Solid and Liquid Practical Applications High Field Coils Specifications for Generating High Pulsed Magnetic Fields Synthesis of Reinforced Copper Matrix Conductors Geometry and Microstructure 687 of Cu/Nb Nanofilamentary Conductors 688

14 Contents XXIII Physical Properties of Cu/Nb Nanofilamentary Conductors Conclusion 693 References Biology and the Environment P. Maestro, P. Couvreur, D. Roux, D. Givord, J.-A. Dalmon, J.-C. Bertolini, F.J. Cadete Santos Aires Inorganic Catalysts for Diesel Engines Nanotechnology and New Medicines Introduction Artificial Carriers: Liposomes and Nanoparticles Conclusion Magnetic Nanoparticles and Biomedical Applications Magnetotactic Bacteria Homing Pigeons Magnetic Separation Magnetic Nanoparticles as MRI Contrast Agents Magnetic Nanoparticles and Treatment of Tumours Zeolitic Membranes for Separation Processes and Catalytic Reactors Introduction Microporous Membranes Zeolitic Membranes: Synthesis and Characterisation Application to Gas Separation Application to a Catalytic Reactor Metal Nanoparticles and Catalysis Synthesis and Characterisation of Pd/Si 3N4 Catalysts Total Oxidation of Methane: Implementation in the Laboratory Application to Radiant Panels (Infrared Energy Emission) 713 References 715 Index 717

: NT2113 CHEMISTRY OF NANOMATERIALS : CHEMISTRY OF NANOMATERIALS

DEPARTMENT OF PHYSICS AND NANOTECHNOLOGY FACULTY OF ENGINEERING AND TECHNOLOGY COURSE PLAN Course Code : NT2113 CHEMISTRY OF NANOMATERIALS Course Title Semester : III Course Time : JULY- NOV 2017 Location