The Surface Properties of Silicas

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ISBN: 9780471953326 | 0471953326
Cover: Hardcover
Copyright: 6/29/1998

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Silica is a major constituent of the world's crust and appears in various crystalline forms such as quartz. Natural and synthetic silicas serve as raw material for glasses and ceramics and are also used in technical applications such as optical waveguides. This book covers the different varieties of silica along with characterization of its crystalline or amorphous structure and its specific physicochemical properties.

Contributors

xvii

(2)

Foreword

xix

(2)

Preface

xxi

(2)

Acknowledgements

xxiii

Chapter 1 On the Silica Edge

(20)

Andre Pierre Legrand

1.1 Introduction

(1)

1.2 Main Crystalline Structures of Silica

(2)

1.2.1 Quartz

(1)

1.2.2 Tridymite

(1)

1.2.3 Cristobalite

(1)

1.2.4 Silica Glass

(1)

1.3 Origin of Silicas

(10)

1.3.1 Natural Minerals

(1)

1.3.2 Synthetic Silicas

(1)

1.3.2.1 Vapour Phase Process

(2)

1.3.2.2 Liquid Phase Process

(2)

1.3.2.3 Summary of the Main Denominations

(1)

1.3.2.4 Particle Size Considerations

(3)

1.4 Surface Models

(4)

1.5 Conclusion

(1)

References

(3)

Chapter 2 Texture, Morphology and Fractality of Silicas

(124)

2A Adsorption Properties of the Silica Surface

(60)

Yves Grillet

Philip L. Llewellyn

2A.1 Introduction

(2)

2A.2 Methods

(1)

2A.2.1 Methods Allowing the Characterization of the Initial State of the Silica: Controlled Transformation Rate Thermal Analysis (CRTA)

(2)

2A.2.2 Methods Allowing a Tracing of the Adsorption Isotherm, the Measurement of the Specific Surface Area and a Study of the Porosity

(1)

2A.2.2.1 The Adsorption Isotherm

(5)

2A.2.2.2 Measurement of the Specific Surface Area from the Gas Adsorption Isotherm

(1)

2A.2.2.3 Measurement of the Specific Surface Area of Silicas Immersed in Water

(1)

2A.2.2.4 Study of the Porosity and Determination of the Mesopore Distribution

(5)

2A.2.3 Methods Allowing a Study of the Superficial Heterogeneity of Silicas

(1)

2A.2.3.1 Indirect Isosteric Method

(1)

2A.2.3.2 Direct Microcalorimetric Method

(1)

2A.3 Experimental Results

(1)

2A.3.1 Different Types of Adsorption Isotherms Encountered

(1)

2A.3.1.1 The Case of Microporous Silicas

(6)

2A.3.1.2 The Case of Mesoporous Silicas

(4)

2A.3.1.3 The Case of Sheet Silicas

(1)

2A.3.2 Comparison of the Quantities of Nitrogen and Argon Adsorbed at the BET Monomolecular Layer; Influence of the Textural Nature of the Silica (Microporous or Mesoporous)

(5)

2A.3.3 Role of the Enthalpies of Adsorption, Immersion and the Activation Energies of Thermodesorption in the Characterization of Silica Surfaces

(1)

2A.3.3.1 Differential Enthalpies of Adsorption of Gases; The Case of Nitrogen and Argon at 77 K

(7)

2A.3.3.2 Enthalpies of Adsorption of Water Vapour and of Immersion in Water

(7)

2A.3.3.3 Thermodesorption of Water Adsorbed on Silicas--Dehydroxylation Activation Energies

(4)

2A.4 Conclusion

(1)

References

(6)

2B Fractal Characteristics of Silica Surfaces and Aggregates

(54)

Francoise Ehrburger-Dolle

2B.1 Introduction

(2)

2B.2 Survey of Fractal Geometry

(1)

2B.2.1 Definitions

(1)

2B.2.1.1 Box Counting

(2)

2B.2.1.2 Mass-Size Relation

(1)

2B.2.2 Pore Size Distribution in Fractal Objects

(1)

2B.2.2.1 The Scaling Equations

(3)

2B.2.2.2 Analysis of the Limiting Cases D = 2 and D = 3

(1)

2B.2.2.3 Effects of Lower and Upper Cut-offs

(1)

2B.3 Experimental Determination of the Fractal Dimension of Silicas

(1)

2B.3.1 Introduction

(1)

2B.3.2 Electron, Tunnel and Atomic Force Microscopy

(1)

2B.3.2.1 Generalities

(2)

2B.3.2.2 Electron Microscopy

(1)

2B.3.2.3 Atomic Force Microscopy

(1)

2B.3.3 Molecular Accessibility and Particle Size Analysis

(1)

2B.3.3.1 Generalities

(2)

2B.3.3.2 Surface Fractal Dimension Determined by Molecular Accessibility

(3)

2B.3.3.3 Surface Fractal Dimension Determined by Particle Size Analysis

101

(1)

2B.3.4 Multilayer Adsorption

102

(1)

2B.3.4.1 Generalities

102

(1)

2B.3.4.2 Surface Fractal Dimension of Pyrogenic Silicas

103

(1)

2B.3.4.3 Surface Fractal Dimension of Aerogels, Xerogels and Precipitated Silicas

104

(1)

2B.3.5 Pore Size Distribution

105

(1)

2B.3.5.1 Capillary Condensation

105

(1)

2B.3.5.2 Nuclear Magnetic Resonance (NMR)

106

(2)

2B.3.5.3 Thermoporometry

108

(1)

2B.3.5.4 Mercury Porosimetry

109

(2)

2B.3.6 Scattering Techniques

111

(1)

2B.3.6.1 Generalities

111

(1)

2B.3.6.2 Pyrogenic Silicas

112

(3)

2B.3.6.3 Sols, Gels, Aerogels, Xerogels and Precipitated Silicas

115

(8)

2B.3.7 Electron Energy Transfer

123

(1)

2B.3.7.1 Generalities

123

(1)

2B.3.7.2 Experimental Results for Aerosil and Porous Silicas

124

(1)

2B.4 Relation between Fractal Dimension and Formation of Silicas

124

(1)

2B.4.1 Formation of Fractal Objects

124

(1)

2B.4.1.1 Aggregation and Deposition

125

(3)

2B.4.1.2 Diffusion, Invasion and Corrosion

128

(1)

2B.4.1.3 Mechanical Breakdown

128

(1)

2B.4.2 Formation of Silicas

129

(1)

2B.4.2.1 Pyrogenic Silicas

129

(1)

2B.4.2.2 Hydrogels

130

(2)

2B.4.2.3 Alcogels

132

(1)

2B.4.2.4 Aerogels, Xerogels and Precipitated Silicas

133

(3)

2B.5 Conclusion

136

(1)

Acknowledgements

137

(1)

References

137

(8)

Chapter 3 Hydroxyl Groups on Silica Surfaces

145

(168)

3A Vibrational Spectroscopies

147

(88)

Andre Burneau

Jean-Paul Gallas

3A.1 Introduction

147

(1)

3A.2 Infrared and Raman Spectroscopies

148

(1)

3A.2.1 Theory and Spectrochemical Notation

148

(1)

3A.2.1.1 Introduction

148

(1)

3A.2.1.2 The Harmonic Oscillator

149

(1)

3A.2.1.3 Diatomic Molecules; Anharmonicity

150

(1)

3A.2.1.4 Polyatomic Molecules

151

(3)

3A.2.1.5 Infrared Absorption

154

(2)

3A.2.1.6 Raman Scattering

156

(1)

3A.2.1.7 Application to Surface Studies

157

(1)

3A.2.2 Experimental Methods

158

(1)

3A.2.2.1 Fourier Transform Infrared (FTIR) Spectroscopy

158

(1)

3A.2.2.2 Transmission; Quantitative Analysis

158

(4)

3A.2.2.3 Diffuse Reflectance (DRIFT)

162

(1)

3A.2.2.4 Photoacoustic Spectroscopy (PAS)

163

(1)

3A.2.2.5 Raman

163

(1)

3A.3 Structure and Properties of Silica

164

(1)

3A.3.1 Introduction

164

(2)

3A.3.2 Overview of Silanol Spectra

166

(1)

3A.3.2.1 Stretching Vibration of Silanol Hydroxyl Groups

166

(4)

3A.3.2.2 Other Silanol Vibrations in an O(3)SiOH Unit

170

(2)

3A.3.3 Bulk Spectra of Silica; Relation with Surface

172

(1)

3A.3.3.1 Fundamental Spectra of Vitreous Silica

172

(1)

3A.3.3.2 Local Modes of An O(3)SiOSiO(3) Unit

173

(5)

3A.3.3.3 Surface Effects on Bulk Modes

178

(3)

3A.3.3.4 Overtones of Bulk Modes and Defect Bands

181

(1)

3A.3.3.5 Quantitative Determination of Silica

182

(1)

3A.3.4 Relation between the Silica Structure and the Preparation Process

183

(3)

3A.3.5 Physically Adsorbed Water

186

(1)

3A.3.5.1 Overall Assignment of Near-Infrared Spectra and Dehydration Conditions

187

(4)

3A.3.5.2 Sites of Water Adsorption

191

(5)

3A.3.5.3 States of Physisorbed Water

196

(7)

3A.3.5.4 Determination of Water Quantity

203

(1)

3A.3.6 Thermally Modified Silica

204

(1)

3A.3.6.1 uOH Region (3800-3000 cm^(-1))

204

(6)

3A.3.6.2 Regions 1000-100 cm^(-1) (uSi-OH, (XXX)OH, yOH) and 5000-3800 cm^(-1) (uOH + (XXX)OH, uOH + yOH)

210

(5)

3A.3.7 Bulk and Surface Silanols

215

(1)

3A.3.7.1 Characterization of Bulk Silanols

215

(2)

3A.3.7.2 Silanol Assessibility and Reagent Size

217

(3)

3A.3.7.3 Populations of the Various Silanols

220

(1)

3A.3.8 Silica-Adsorbate Interactions

221

(1)

3A.3.8.1 H-Bonding Interactions

221

(2)

3A.3.8.2 From H-Bonding to Protonation

223

(1)

3A.3.8.3 Aprotonic Surface Sites

224

(1)

3A.4 Conclusion

225

(2)

References

227

(8)

3B NMR Spectroscopies

235

(50)

Hubert Hommel

Andre Pierre Legrand

Claudine Doremieux

Jean-Baptiste d'Espinose de la Caillerie

3B.1 Nuclear Magnetic Resonance Methods

235

(1)

3B.1.1 Proton (1)H NMR Spectroscopy

236

(1)

3B.1.1.1 Static Measurement (Broad-Band NMR)

236

(2)

3B.1.2 Rare Spin Spectroscopy ((29)Si, (13)C)

238

(1)

3B.1.2.1 High-Power Decoupling

239

(1)

3B.1.2.2 Averaging the Chemical Shift Anisotropy (CSA); Magic Angle Spinning (MAS)

239

(1)

3B.1.2.3 Spin Temperature and Cross-Polarization (CP)

239

(3)

3B.1.2.4 Dipolar Dephasing (DD/CP/MAS)

242

(1)

3B.1.2.5 Model Compound Example

242

(2)

3B.1.3 Conclusion

244

(1)

3B.2 NMR Studies of the Structure of Silica

244

(1)

3B.2.1 (1)H Nuclear Magnetic Resonance

244

(1)

3B.2.2 Broad-Band and MAS Studies

245

(5)

3B.2.3 High-Resolution and Fast Chemical Exchange Studies

250

(1)

3B.2.4 High-Resolution (29)Si Spectroscopies

251

(1)

3B.2.5 Study by CP/MAS NMR

251

(3)

3B.2.6 Simple MAS Experiments

254

(3)

3B.2.7 Quantitative Measurements of f(g) and f(s)

257

(3)

3B.2.8 The Case of Pyrogenic Silica

260

(5)

3B.2.9 Models for the Surface

265

(5)

3B.2.10 (1)H NMR and Particularly CRAMPS

270

(5)

3B.2.11 N-Quantum Coherence

275

(1)

3B.2.12 Correlation of (1)H and (29)Si Resonances

276

(2)

3B.2.13 Dissolution of Silica

278

(3)

3B.3 Conclusion

281

(1)

References

281

(4)

3C Chemical Reactivity

285

(21)

Alain Vidal

Eugene Papirer

3C.1 Introduction

285

(1)

3C.2 Chemical Modification as a Tool for Silica Surface Characterization

286

(13)

3C.3 Chemical Modification as a Tool for Changing the Surface Properties of Silicas

299

(1)

3C.3.1 Reduction of a Silica Surface

300

(1)

3C.3.2 Grafting of Organic Molecules

300

(3)

3C.3.3 Grafting of Polymers

303

(1)

3C.3.3.1 Grafting `onto'

303

(1)

3C.3.3.2 Grafting `from'

304

(1)

3C.4 Conclusion

305

(1)

References

306

(7)

Chapter 4 Surface Characteristics of Silicas

313

(102)

4A Surface Energy of Silicas

315

(50)

Eugene Papirer

Henri Balard

4A.1 Introduction

315

(2)

4A.2 Measurement of the Surface Energy of Silicas

317

(1)

4A.2.1 Surface Energy Determination by Adsorption Measurements

318

(1)

4A.2.1.1 Adsorption of Hydrocarbons

318

(1)

4A.2.1.2 Adsorption of Water

319

(2)

4A.2.2 Wetting Experiments

321

(1)

4A.2.2.1 Contact Angle Measurements

321

(1)

4A.2.2.2 Thin-Layer Wicking

321

(2)

4A.2.3 Inverse Gas Chromatography (IGC)

323

(1)

4A.2.3.1 Infinite Dilution Conditions

323

(3)

4A.2.3.2 Finite Concentration Conditions

326

(1)

4A.3 Dispersive Component of the Surface Energy of Silicas

327

(1)

4A.3.1 Non-modified Silicas

327

(1)

4A.3.1.1 Amorphous, Wet Silica Surfaces

327

(2)

4A.3.1.2 Amorphous Dry Silicas

329

(1)

4A.3.1.3 Lamellar Silicas (Morphology Index)

330

(2)

4A.3.2 Modified Silicas

332

(1)

4A.3.2.1 Thermally Modified Silicas

332

(2)

4A.3.2.2 Chemically Modified Silicas

334

(1)

4A.4 Specific Component of the Surface Energy of Silicas

335

(1)

4A.4.1 The Polar Component Approach

336

(1)

4A.4.2 The Acid-Base Approach

337

(1)

4A.4.2.1 Gutmann's Acidity Scale

337

(3)

4A.4.2.2 Van Oss Scale

340

(1)

4A.4.3 Relation between Specific Component of Surface Energy and Surface Chemistry

341

(1)

4A.4.3.1 Relation with the Silanol Group Content

341

(1)

4A.4.3.2 Relation with Silica Surface Modification

342

(2)

4A.5 Surface Energetic Heterogeneity

344

(1)

4A.5.1 General Considerations

344

(3)

4A.5.1.1 Physical Model of the Adsorption of a Heterogeneous Surface

347

(2)

4A.5.1.2 Resolution Methods of the Fredholm Integral Equation

349

(3)

4A.5.2 Methods of Acquisition

352

(1)

4A.5.3 Adsorption Energy Distribution Functions Measured on Silicas

353

(5)

4A.6 Application of the Acid/Base and Surface Energy Concepts

358

(1)

4A.6.1 Adsorption of Polymers on Silica

358

(2)

4A.6.2 Consequences of Filler-Elastomer Interactions Studied with Model Compounds

360

(1)

4A.6.3 Surface Properties and Possible Implications in Biological Responses

360

(1)

4A.7 Conclusion

361

(1)

References

361

(4)

4B Surface Group Ionization on Silicas

365

(46)

Alain Foissy

Jacques Persello

4B.1 Introduction

365

(1)

4B.2 Surface Acidic Properties of Silica

366

(1)

4B.2.1 Silica Materials; Bulk Properties and Impurities

366

(1)

4B.2.2 Surface Structure

367

(2)

4B.2.3 Theoretical Determination of Proton Association Constants

369

(4)

4B.3 Description of the Electrochemical Interface

373

(1)

4B.3.1 Definition of Interfacial Parameters

373

(3)

4B.3.2 Evaluation of Interfacial Parameters

376

(3)

4B.4 Practical Determination of Electrochemical Properties

379

(1)

4B.4.1 Surface Charge Titration

379

(1)

4B.4.1.1 General Procedure

379

(6)

4B.4.1.2 Titration Experiments

385

(4)

4B.4.2 Evaluation of Interfacial Parameters

389

(1)

4B.4.2.1 Surface Ionization Constant

389

(3)

4B.4.2.2 Interfacial Capacity

392

(2)

4B.4.2.3 Electrical Charge Balance

394

(1)

4B.4.3 Specific Interaction of Counter Ions

395

(1)

4B.4.3.1 Monovalent Ions

396

(3)

4B.4.3.2 Divalent Ions

399

(4)

4B.5 Enthalpy of Surface Ionization

403

(1)

4B.5.1 Adsorption of Protons

403

(5)

4B.5.2 Adsorption of Counter Ions

408

(2)

4B.6 Conclusion

410

(1)

References

411

(4)

Chapter 5 Health Effects of Silica

415

(50)

Bice Fubini

5.1 Introduction

415

(4)

5.1.1 An Historical Overview of Silica Pathogenicity

415

(2)

5.1.2 Investigations on Silica Toxicology: Epidemiology, in vivo Tests, in vitro Tests, acellular Tests

417

(1)

5.1.2.1 Epidemiology Studies

418

(1)

5.1.2.2 In vivo Tests

418

(1)

5.1.2.3 In vitro Tests

419

(1)

5.1.2.4 Acellular Tests

419

(1)

5.2 Diseases Associated with Silica Exposure

419

(1)

5.2.1 Chronic Silicosis (Nodular Pulmonary Fibrosis)

419

(1)

5.2.2 Acute Silicosis (Alveolar Proteinosis)

419

(1)

5.2.3 Increased Susceptibility to Mycobacterial and Fungal Infections

420

(1)

5.2.4 Lung Cancer (Bronchogenic Carcinoma)

420

(1)

5.2.5 Increased Incidence of Autoimmune Diseases

420

(1)

5.3 Occupational Risks

420

(1)

5.4 Interaction between Silica and Biological Matter

420

(6)

5.4.1 Biological Response to Silica Particles

420

(2)

5.4.2 Adsorption of Endogenous Matter

422

(1)

5.4.2.1 Proteins

422

(1)

5.4.2.2 Phospholipids

423

(1)

5.4.2.3 Metal Ions

424

(1)

5.4.3 Fate of a Silica Particle in the Lung

424

(1)

5.4.3.1 Interaction with Phospholipids on the Wall Lining Layer

424

(1)

5.4.3.2 Phagocytosis by Alveolar Macrophages

425

(1)

5.4.3.3 Interaction with Epithelial Cells

425

(1)

5.4.3.4 Translocation to the Interstitium

425

(1)

5.4.3.5 Clearance

426

(1)

5.5 Toxicity of the Various Silica Polymorphs

426

(4)

5.5.1 Crystalline Polymorphs

426

(1)

5.5.1.1 Quartz

426

(1)

5.5.1.2 Tridymite

427

(1)

5.5.1.3 Cristobalite

427

(1)

5.5.1.4 Coesite

427

(1)

5.5.1.5 Stishovite

427

(1)

5.5.1.6 Silica Frame Zeolites: An Open Field of Investigation

428

(1)

5.5.2 Amorphous Silicas

428

(1)

5.5.2.1 Silica Glass

428

(1)

5.5.2.2 Precipitated Silicas

429

(1)

5.5.2.3 Pyrogenic Silicas

429

(1)

5.5.2.4 Diatomite Earths

429

(1)

5.6 Micromorphology of Silica Particles

430

(5)

5.6.1 Form of the Particles

430

(1)

5.6.2 State of the Surface

431

(1)

5.6.2.1 Mechanical Fracture

431

(3)

5.6.2.2 Crystallinity of Outmost Layers

434

(1)

5.6.2.3 Chemical Etching

435

(1)

5.6.3 Density

435

(1)

5.7 Surface Functionalities Implicated in the Toxicity of Silica

435

(13)

5.7.1 Surface Properties and the Mechanism of Toxicity

435

(1)

5.7.1.1 Hydrogen Bonding

435

(1)

5.7.1.2 Surface Charges

436

(1)

5.7.1.3 Hydrophilicity/Hydrophobicity

436

(1)

5.7.1.4 Freshly Fractured Surfaces

436

(3)

5.7.1.5 Free Radical Release

439

(1)

5.7.2 Chemical Functionalities and Biological Effects Elicited

440

(1)

5.7.2.1 Silanols

440

(1)

5.7.2.2 Siloxanes

441

(1)

5.7.2.3 Dangling Bonds

442

(1)

5.7.2.4 Peroxobridges, Superoxide Anions, Sylilperoxide Radicals

442

(1)

5.7.2.5 Surface Charges

442

(1)

5.7.3 Interaction with Cells and Tissues

442

(1)

5.7.3.1 Membranolysis

442

(2)

5.7.3.2 Cytotoxicity to Macrophages and Macrophage-like Cells

444

(2)

5.7.3.3 Lipid Peroxidation

446

(1)

5.7.3.4 DNA Damage

447

(1)

5.8 Modifications of the Surface that Decrease the Toxic Potential of a Silica Dust

448

(3)

5.8.1 Polymer Coating

448

(1)

5.8.2 Aluminium Salts

449

(1)

5.8.3 Tetrandrine

450

(1)

5.8.4 Thermal Treatments

450

(1)

5.8.5 Functionalization of the Surface

451

(1)

5.9 Chemical Causes of Silicosis: An Overview

451

(7)

5.9.1 Recent Studies Employing Well-Defined Samples Differing in Crystallinity and Surface Properties

451

(1)

5.9.1.1 Biological Response to Different Silica Polymorphs and the Effect of Functionalization of the Quartz Surface

452

(1)

5.9.1.2 Effect of Thermal Treatments on the Pathogenicity of Different Silica Polymorphs

453

(1)

5.9.1.3 Effect of Morphology, Crystallinity and Contaminants on the Biological Response to Quartz Dusts

454

(1)

5.9.1.4 Effect of the Origin of the Sample on the Fibrogenic Response

455

(1)

5.9.1.5 Effect of Acid Washing on Some Biological Responses to Quartz

456

(1)

5.9.2 Hypothesis on the Molecular Mechanisms of Silica Pathogenicity Consistent with Recent Experimental Data

456

(1)

5.9.2.1 Prolonged Reactions and Chronic Silicosis

457

(1)

5.9.2.2 Fresh Surfaces and Acute Silicosis

457

(1)

5.9.2.3 Genome Modifications and Cancer

458

(1)

Acknowledgements

458

(1)

References

458

(7)

Index

465

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The Surface Properties of Silicas

Summary

Author Biography

Table of Contents

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Summary

Author Biography

Table of Contents

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