Physical Chemistry and Acid-base Properties of Surfaces

The first part of this book looks at the consequence of chemical and topological defects existing on real surfaces, which explain the wettability of super hydrophilc and super hydrophobic surfaces. There follows an in-depth analysis of the acido-basicity of surfaces with, as an illustration, different wettability experiments on real materials.  The next chapter deals with various techniques enabling the measurement of acido basicity of the surfaces including IR and XPS technics.

The last part of the book presents an electrochemical point of view which explains the surface charges of the oxide at contact with water or other electrolyte solutions in the frame of Bronsted acido-basicity concept.  Various consequences are deduced from such analyses illustrated by original measurement of the point of zero charge or by understanding the basic principles of the electrowetting experiments.

Marie-Geneviève?Barthes, Research Director CNRS, Laboratoire ICMMO, France.

Introduction ix

Chapter 1. Wettability of an Ideal Surface: Overview 1

1.1. Wetting angle 1

1.2. Adhesion effect 4

1.3. Surface tension and free surface energy 5

Chapter 2. Real Surfaces 9

2.1. Wenzel’s model – topological defects 9

2.2. Cassie–Baxter model: chemical defects 11

2.3. Superhydrophilic surfaces 12

2.4. Superhydrophobic surfaces 16

2.5. Application 20

Chapter 3. Components of the Surface Energy 23

3.1. Overview 23

3.2. Molecular interactions and components of the energy 26

3.3. The hydrogen bond 28

3.4. Lewis acid-base interactions 28

3.5. The effective components of the interaction energy 31

3.6. Application 32

Chapter 4. The Acid-Base Component in the Work of Adhesion 37

4.1. Overview 37

4.2. Use of the acid-base component 38

4.3. The Owens–Wendt approximation 39

4.4. Van Oss–Good description 40

Chapter 5. Experimental Determination through Wettability Measurements 45

5.1. One liquid method 46

5.2. Two liquid method. Surfaces with high surface energy 48

5.3. Applications of the two liquid method 49

5.4. Comparison between Owens–Wendt and van Oss–Good methods 55

Chapter 6. Acid-Base Properties of Surfaces: Experimental Approaches 61

6.1. Overview 61

6.2. General methods 61

6.2.1. Wettability 61

6.2.2. Electrokinetic method 62

6.2.3. Scanning probe microscopies 68

6.2.4. Inverse gas chromatography at infinite dilution conditions 73

6.2.5. X-ray photoelectron spectroscopy (XPS) 78

6.2.6. Other methods 85

6.3. Local methods 86

6.3.1. Infrared spectroscopy 87

6.3.2. X-ray photoelectron spectroscopy (XPS) 91

6.3.3. Other methods 93

6.4. Application examples 94

6.4.1. Bonding ability of aluminum sheets 94

6.4.2. Mechanism of formation of the interphase in metal–polymer joints 96

6.4.3. Heterogeneous catalysis 98

Chapter 7. Oxide–Solution Interfaces: Surface Charges 99

7.1. Brønsted acidity and basicity 100

7.2. Point of zero charge (PZC) 101

7.3. The oxide–solution interface 103

7.4. Electrocapillarity in the oxide–solution interface 109

7.4.1. Evolution of the interfacial tension 110

Chapter 8. Electrocapillarity Applications 117

8.1. Study based on the pH of the oxide surfaces 117

8.2. Study of the stability of a liquid film on an oxide surface 123

8.2.1. Case of a flat surface 123

8.2.2. Case of a rough surface 125

8.3. Modification of the contact angle by an imposed potential (Electrowetting) 132

Conclusion 141

Bibliography 143

Index 153

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