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Preface i Units, Fundamental Constants, and Symbols iii
CHAPTER 1: THE REALM OF NANOSCIENCE AND MOLECULAR ENGINEERING 1
1.1 NANOSCIENCE AND MOLECULAR ENGINEERING 1
1.1.1 Trial-and-Error Approach and Deductive Rational Engineering 3
1.1.2 Combined Deductive Rational Engineering 5
1.1.3 Perception of our World - Apparent Unique Behaviors in Small Systems 6
1.2 PROPERTIES IN LOWER DIMENSIONALITIES 7
1.2.1 Flatland - The Uniqueness of Lower Dimensionality 8
1.3 MECHANICAL SYSTEM RESPONSES 9
1.3.1 Bulk Rheological Responses 9
1.3.2 Molecular Perspective of Mechanical Systems 11
1.4 DRIVING FORCES AND RESPONSES IN THERMAL TRANSPORT 15
1.4.1 Classical Thermal Transport 15
1.4.2 Thermal Conductivity Based on Classical Mechanics and Statistics 16
1.4.3 Size Effect on Thermal Energy Transfer 23
1.5 ELECTRONIC TRANSPORT OF LOWER DIMENSIONAL SYSTEMS 25
1.5.1 Drude Model Microscopic Model for Macroscopic Electron Transport 27
1.5.2 Characteristic Length Scales for Electron Transport 28
1.5.3 One-dimensional Electron Transport 31
1.6 ACOUSTIC TRANSPORT AND DIMENSIONALITY 35
1.7 CRITICAL MOLECULAR RESPONSE TIMES IN NANOCONSTRAINED SYSTEMS 37
1.7.1 Longitudinal Response to Stress: Maxwell Model 39
1.7.2 Shear Response to Stress 41
1.7.3 Dissipative Two-Dimensional Shear Response 44
1.8 MINIATURIZATION, SCALING, AND SYSTEM CONSTRAINTS 46
1.8.1 Phenomenological Shortcoming of the Scaling Analysis 47
1.8.1.1 Terminal Velocity of Liquid Droplets and Solid Particles 47
1.8.1.2 Interfacial Constraints and Nanocomposite Membrane Permeability 50
1.8.2 Dimensional Constraints and Thermal Conductivity 56
1.9 ORGANIZATION AND OUTLOOK FOR NANOSCIENCE AND NANOTECHNOLOGY 60
1.9.1 Classification of Nanoscience and Nanotechnology 60 STUDY PROBLEMS TO
CHAPTER 1 63
CHAPTER 2: INTERFACIAL AND SIZE-CONSTRAINT SYSTEMS 72
2.1 OVERVIEW 72
2.2 VAN DER WAALS MOLECULAR INTERACTIONS 73
2.2.1 Van der Waals Interactions in Gases 73
2.2.1 Van der Waals Interactions in Liquids 78
2.3 INTERFACIAL EFFECTS ON LIQUIDS AND VAN DER WAALS SOLIDS 82
2.3.1 Simplistic Perspective Bulk and Surface Binding Energy 84
2.3.2 Interfacial Effect on Van der Waals Liquid Structures 85
2.3.2.1 Molecular Perspective of the Bulk Cohesion Energy 89
2.3.2.2 Molecular Perspective of the Adhesion Energy 91
2.3.3 Free Surface Effects on Van der Waals Solids 96
2.4 INTERFACIAL EFFECTS ON SPIN-COATED POLYMER FILMS 102
2.4.1 Bulk Mechanical Response, Polymer Mobility, and the Glass Transition 102
2.4.2 Polymer Chain Entanglement and Melt Viscosity 104
2.4.3 Interfacial Constraint on the Glass Transition in Thin Films 108
2.5 SIZE AND INTERFACIAL CONSTRAINTS IN METAL NANOCLUSTERS 114
2.5.1 Size Effect on Cohesion Energy and Surface Energy in Quasicrystals 117
2.6 TWO-DIMENSIONAL SYSTEMS AND SURFACE ENERGY 121
2.6.1 Surface Energy of Graphite 122
2.6.2 Surface energy of graphite''s ultimate nanostructure Graphene 126 STUDY PROBLEMS TO
CHAPTER 2: 128
CHAPTER 3: CONSTRAINED CONDENSED FLUID MOLECULAR SYSTEMS 137
3.1 MOLECULES AND PHASE PROPERTIES 137
3.1.1 Molecules and Molecular Interactions 137
3.1.2 Molecular Interactions and Van der Waals Equation of State 139
3.1.3 Gas Bulk Critical and Molecular Properties 144
3.2 METASTABLE LIQUID PHENOMENA 151
3.2.1 Metastable Liquids and Cavitation 152
3.2.2 Homogeneous Nucleation Process of Vapor Bubbles 155
3.2.3 Free Energy of Bubble Nucleation 156
3.2.4 Probability of Bubble Nucleation and Liquid Tensile Strength 159
3.3 HYDRAULIC TRANSPORT IN CAPILLARIES AND BOUNDARY CONDITIONS 163
3.3.1 Bending Stresses on Vascular Plants and Drought Embolism 164
3.3.2 Water Transport - Darcy''s Law 167
3.3.3 Poiseuille Flow in Capillaries - Slip Boundary Condition 173
3.3.4 Molecular Conformations at Interfaces and Apparent Slip 181
3.3.5 Surface Roughness and Heterogeneous Slip 184
3.4 NANOCONDUIT FLOW - BOUNDARY LAYER MODEL AND NANOCAPILLARIES 188
3.4.1 Boundary Layer Model 188
3.4.2 Nanoconduit Flow through Carbon Nanotubes 193
3.5 MEMBRANE TRANSPORT 198
3.5.1 Osmosis 198
3.5.2 Water Purification and Desalination Reverse Osmosis 203
3.5.3 Transport Mechanisms through Solvent Swollen Polymer Membranes &n