Use of amphiphilic triblock copolymers to direct the organization of polymerizing silica species has resulted in the preparation of well-ordered hexagonal mesoporous silica structures (SBA-15) with uniform pore sizes up to approximately 300 angstroms. The SBA-15 materials are synthesized in acidic media to produce highly ordered, two-dimensional hexagonal (space group p6mm) silica-block copolymer mesophases. Calcination at 500°C gives porous structures with unusually large interlattice d spacings of 74.5 to 320 angstroms between the (100) planes, pore sizes from 46 to 300 angstroms, pore volume fractions up to 0.85, and silica wall thicknesses of 31 to 64 angstroms. SBA-15 can be readily prepared over a wide range of uniform pore sizes and pore wall thicknesses at low temperature (35° to 80°C), using a variety of poly(alkylene oxide) triblock copolymers and by the addition of cosolvent organic molecules. The block copolymer species can be recovered for reuse by solvent extraction with ethanol or removed by heating at 140°C for 3 hours, in both cases, yielding a product that is thermally stable in boiling water.

Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores

Images and force measurements taken by an atomic‐force microscope (AFM) depend greatly on the properties of the spring and tip used to probe the sample’s surface. In this article, we describe a simple, nondestructive procedure for measuring the force constant, resonant frequency, and quality factor of an AFM cantilever spring and the effective radius of curvature of an AFM tip. Our procedure uses the AFM itself and does not require additional equipment.

Calibration of atomic‐force microscope tips

http://experimentationlab.berkeley.edu/sites/default/files/AFMImages/butt_AFM.pdf

Force measurements with the atomic force microscope: Technique, interpretation and applications

Nanostructured materials: basic concepts and microstructure☆

CHAPTER 1. INTRODUCTION TO KARST. 1.1 Definitions. 1.2 The Relationship Between Karst And General Geomorphology And Hydrogeology. 1.3 The Global Distribution Of Karst. 1.4 The Growth Of Ideas. 1.5 Aims Of The Book. 1.6 Karst Terminology. CHAPTER 2. THE KARST ROCKS. 2.1 Carbonate Rocks And Minerals. 2.2 Limestone Compositions And Depositional Facies. 2.3 Limestone Diagenesis And The Formation Of Dolomite. 2.4 The Evaporite Rocks. 2.5. Quartzites And Siliceous Sandstones. 2.6 Effects Of Lithologic Properties Upon Karst Development. 2.7 Interbedded Clastic Rocks. 2.8 Bedding Planes, Joints, Faults And Fracture Traces. 2.9 Fold Topography. 2.10 Paleokarst Unconformities. CHAPTER 3. DISSOLUTION: CHEMICAL AND KINETIC BEHAVIOUR OF THE KARST ROCKS. 3.1 Introduction. 3.2 Aqueous Solutions And Chemical Equilibria. 3.3 The Dissolution Of Anhydrite, Gypsum And Salt. 3.4 The Dissolution Of Silica. 3.5 Bicarbonate Equilibria And The Dissolution Of Carbonate Rocks In Normal Meteoric Waters. 3.6 The S-O-H System And The Dissolution Of Carbonate Rocks. 3.7 Chemical Complications In Carbonate Dissolution. 3.8 Biokarst Processes. 3.9 Measurements In The Field And Lab Computer Programs. 3.10 Dissolution And Precipitation Kinetics Of Karst Rocks. CHAPTER 4. DISTRIBUTION AND RATE OF KARST DENUDATION. 4.1 Global Variations In The Solutional Denudation Of Carbonate Terrains. 4.2 Measurement And Calculation Of Solutional Denudation Rates. 4.3 Solution Rates In Gypsum, Salt And Other Non-Carbonate Rocks. 4.4 Interpretation Of Measurements. CHAPTER 5. KARST HYDROLOGY. 5.1 Basic Hydrological Concepts, Terms And Definitions. 5.2 Controls On The Development Of Karst Hydrologic Systems. 5.3 Energy Supply And Flow Network Development. 5.4 Development Of The Water Table And Phreatic Zones. 5.5 Development Of The Vadose Zone. 5.6 Classification And Characteristics Of Karst Aquifers. 5.7 Applicability Of Darcy's Law To Karst. 5.8 The Fresh Water/Salt Water Interface. CHAPTER 6. ANALYSIS OF KARST DRAINAGE SYSTEMS. 6.1 The 'Grey Box' Nature Of Karst. 6.2 Surface Exploration And Survey Techniques. 6.3 Investigating Recharge And Percolation In The Vadose Zone. 6.4 Borehole Analysis. 6.5 Spring Hydrograph Analysis. 6.6 Polje Hydrograph Analysis. 6.7 Spring Chemograph Interpretation. 6.8 Storage Volumes And Flow Routing Under Different States Of The Hydrograph. 6.9 Interpreting The Organisation Of A Karst Aquifer. 6.10 Water Tracing Techniques. 6.11 Computer Modelling Of Karst Aquifers. CHAPTER 7. SPELEOGENESIS: THE DEVELOPMENT OF CAVE SYSTEMS. 7.1 Classifying Cave Systems. 7.2 Building The Plan Patterns Of Unconfined Caves. 7.3 Unconfined Cave Development In Length And Depth. 7.4 System Modifications Occurring Within A Single Phase. 7.5 Multi-Phase Cave Systems. 7.6 Meteoric Water Caves Developed Where There Is Confined Circulation Or Basal Injection Of Water. 7.7 Hypogene Caves: (A) Hydrothermal Caves Associated Chiefly With Co2. 7.8 Hypogene Caves: (B) Caves Formed By Waters Containing H2s. 7.9 Sea Coast Eogenetic Caves. 7.10 Passage Cross-Sections And Smaller Features Of Erosional Morphology. 7.11 Condensation, Condensation Corrosion, And Weathering In Caves. 7.12 Breakdown In Caves. CHAPTER 8. CAVE INTERIOR DEPOSITS. 8.1 Introduction. 8.2 Clastic Sediments. 8.3 Calcite, Aragonite And Other Carbonate Precipitates. 8.4 Other Cave Minerals. 8.5 Ice In Caves. 8.6 Dating Of Calcite Speleothems And Other Cave Deposits. 8.7 Paleo-Environmental Analysis Of Calcite Speleothems. 8.8 Mass Flux Through A Cave System: The Example Of Friar's Hole, W.Va. CHAPTER 9. KARST LANDFORM DEVELOPMENT IN HUMID REGIONS. 9.1 Coupled Hydrological And Geochemical Systems. 9.2 Small Scale Solution Sculpture - Microkarren And Karren. 9.3 Dolines - The 'Diagnostic' Karst Landform? 9.4 The Origin And Development Of Solution Dolines. 9.5 The Origin Of Collapse And Subsidence Depressions. 9.6 Polygonal Karst. 9.7 Morphometric Analysis Of Solution Dolines. 9.8 Landforms Associated With Allogenic Inputs. 9.9 Karst Poljes. 9.10 Corrosional Plains And Shifts In Baselevel. 9.11 Residual Hills On Karst Plains. 9.12 Depositional And Constructional Karst Features. 9.13 Special Features Of Evaporite Terrains. 9.14 Karstic Features Of Quartzose And Other Rocks. 9.15 Sequences Of Carbonate Karst Evolution In Humid Terrains. CHAPTER 10.THE INFLUENCE OF CLIMATE, CLIMATIC CHANGE AND OTHER ENVIRONMENTAL FACTORS ON KARST DEVELOPMENT. 10.1 The Precepts Of Climatic Geomorphology. 10.2 The Hot Arid Extreme. 10.3 The Cold Extreme: 1 Karst Development In Glaciated Terrains. 10.4 The Cold Extreme: 2 Karst Development In Permafrozen Terrains. 10.5 Sea Level Changes, Tectonic Movement And Implications For Coastal Karst Development. 10.6 Polycyclic, Polygenetic And Exhumed Karsts. CHAPTER 11. KARST WATER RESOURCES MANAGEMENT. 11.1 Water Resources And Sustainable Yields. 11.2 Determination Of Available Water Resources. 11.3 Karst Hydrogeological Mapping. 11.4 Human Impacts On Karst Water. 11.5 Groundwater Vulnerability, Protection, And Risk Mapping. 11.6 Dam Building, Leakages, Failures And Impacts. CHAPTER 12. HUMAN IMPACTS AND ENVIRONMENTAL REHABILITATION. 12.1 The Inherent Vulnerability Of Karst Systems. 12.2 Deforestation, Agricultural Impacts And Rocky Desertification. 12.3 Sinkholes Induced By De-Watering, Surcharging, Solution Mining And Other Practices On Karst. 12.4 Problems Of Construction On And In The Karst Rocks - Expect The Unexpected! 12.5 Industrial Exploitation Of Karst Rocks And Minerals. 12.6 Restoration Of Karstlands And Rehabilitation Of Limestone Quarries. 12.7 Sustainable Management Of Karst. 12.8 Scientific, Cultural And Recreational Values Of Karstlands.

Karst Hydrogeology and Geomorphology

The spring constant of microfabricated cantilevers used in scanning force microscopy (SFM) can be determined by measuring their resonant frequencies before and after adding small end masses These masses adhere naturally and can be easily removed before using the cantilever for SFM, making the method nondestructive The observed variability in spring constant—almost an order of magnitude for a single type of cantilever—necessitates calibration of individual cantilevers in work where precise knowledge of forces is required Measurements also revealed that the spring constant scales with the cube of the unloaded resonant frequency, providing a simple way to estimate the spring constant for less precise work

A nondestructive method for determining the spring constant of cantilevers for scanning force microscopy

Living organisms construct various forms of laminated nanocomposites through directed nucleation and growth of inorganics at self-assembled organic templates at temperatures below 100°C and in aqueous solutions. Recent research has focused on the use of functionalized organic surfaces to form continuous thin films of single-phase ceramics. Continuous thin films of mesostructured silicates have also been formed on hydrophobic and hydrophilic surfaces through a two-step mechanism. First, under acidic conditions, surfactant micellar structures are self-assembled at the solid/liquid interface, and second, inorganic precursors condense to form an inorganic-organic nanocomposite. Epitaxial coordination of adsorbed surfactant tubules is observed on mica and graphite substrates, whereas a random arrangement is observed on amorphous silica. The ability to process ceramic-organic nanocomposite films by these methods provides new technological opportunities.

https://science.sciencemag.org/content/sci/273/5277/892.full.pdf

Biomimetic Pathways for Assembling Inorganic Thin Films

Interactions between surfactant solutions and solid surfaces play a key role in technologically important processes such as colloidal stabilization, ore flotation, and soil removal; however, the interfacial aggregation of surfactant molecules is not yet well understood. Direct images of surfactant aggregates at solid surfaces in aqueous solutions were obtained with atomic force microscopy. The resulting structures for quaternary ammonium surfactants (above the critical micelle concentration) are consistent with half-cylinders on crystalline hydrophobic substrates, full cylinders on mica, and spheres on amorphous silica. These structures-surprisingly different from earlier models-appear to result from a compromise between the natural free curvature as defined by intermolecular interactions and the constraints imposed by specific surfactant-surface interactions. Such interfacial aggregates can potentially be used to pattern surfaces at nanometer-length scales.

https://science.sciencemag.org/content/sci/270/5241/1480.full.pdf

Molecular Organization of Surfactants at Solid-Liquid Interfaces

The morphology of ionic surfactant molecules adsorbed from aqueous solution onto hydrophobic substrates has been determined by atomic force microscopy. Near the critical micelle concentration (cmc), noncontact imaging using double-layer repulsion between the tip and sample shows parallel, epitaxially oriented stripes spaced apart by about twice the surfactant length. This represents the first direct imaging of «hemimicelles», liquid-crystalline aggregates of amphiphilic molecules (analogous to bulk micelles) which form at interfaces. The striped pattern is indicative of hemicylindrical hemimicelles, which is further corroborated by images of the monolayer adsorbate (in contact mode) below the cmc

Direct Visualization of Surfactant Hemimicelles by Force Microscopy of the Electrical Double-Layer

The atomic force microscope (AFM) was used to image an electrode surface at atomic resolution while the electrode was under potential control in a fluid electrolyte. A new level of subtlety was observed for each step of a complete electrochemical cycle that started with an Au(111) surface onto which bulk Cu was electrodeposited. The Cu was stripped down to an underpotential-deposited monolayer and finally returned to a bare Au(111) surface. The images revealed that the underpotential-deposited monolayer has different structures in different electrolytes. Specifically, for a perchloric acid electrolyte the Cu atoms are in a close-packed lattice with a spacing of 0.29 ± 0.02 nanometer (nm). For a sulfate electrolyte they are in a more open lattice with a spacing of 0.49 ± 0.02 nm. As the deposited Cu layer grew thicker, the Cu atoms converged to a (111)-oriented layer with a lattice spacing of 0.26 ± 0.02 nm for both electrolytes. A terrace pattern was observed during dissolution of bulk Cu. Images were obtained of an atomically resolved Cu monolayer in one region and an atomically resolved Au substrate in another in which a 30° rotation of the Cu monolayer lattice from the Au lattice is clearly visible.

https://science.sciencemag.org/content/sci/251/4990/183.full.pdf

S. Manne

Papers

A nondestructive method for determining the spring constant of cantilevers for scanning force microscopy

Biomimetic Pathways for Assembling Inorganic Thin Films

Molecular Organization of Surfactants at Solid-Liquid Interfaces

Direct Visualization of Surfactant Hemimicelles by Force Microscopy of the Electrical Double-Layer

Atomic-Resolution Electrochemistry with the Atomic Force Microscope: Copper Deposition on Gold