Physical Chemistry and Acid-Base Properties of Surfaces

174 Pages·2015·5.64 MB·English

by  Jean-Charles Joud

9781848218437-Case.qxp_Layout 1 01/10/2015 16:02 Page 1
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FOCUS SERIES in MATERIALS SCIENCE
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The study of the wettability of surfaces is widely used in technological enearle
applications such as metal–polymer interfaces, water management in fuel viès J
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cells, the problems of adsorption in microelectronics as well as the e Bud
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applications of electrowettability. rth
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After a reminder of the properties of ideal and real surfaces, this book -L
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presents an analysis of the different components involved in the ro
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expression of interfacial tension, especially of the solid–liquid or ss
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iquid–vapor type.
Several methods for measuring wettability are then presented and
illustrated using examples leading to the determination of the different
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components of the substrate surface energy. h
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A review of the different experimental methods allowing us to determine s
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the acid-base properties of the surfaces is proposed, with emphasis put a
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on the most frequently used methods in the case of flat surfaces.
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Electrowettability and its different applications are then developed in h
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detail, thus highlighting the importance of electric charges on the solid–
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liquid interfacial tension.
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a Physical Chemistry and
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Acid-Base Properties
Jean-Charles Joud is Emeritus Professor at Grenoble(cid:0)INP Phelma, in i
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France and a specialist in the thermodynamics and physical chemistry of -B
surfaces. a
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Marie-Geneviève Barthés-Labrousse is CNRS Research Director at the
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Institut de Chimie Moléculaire et des Matériaux d’Orsay in France and a r
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specialist in surface reactivity. p
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www.iste.co.uk

Physical Chemistry and Acid-Base Properties of Surfaces

FOCUS SERIES
Series Editor Michel Pons
Physical Chemistry and
Acid-Base Properties
of Surfaces

Jean-Charles Joud
Marie-Geneviève Barthés-Labrousse
First published 2015 in Great Britain and the United States by ISTE Ltd and John Wiley & Sons, Inc.
Apart from any fair dealing for the purposes of research or private study, or criticism or review, as
permitted under the Copyright, Designs and Patents Act 1988, this publication may only be reproduced,
stored or transmitted, in any form or by any means, with the prior permission in writing of the publishers,
or in the case of reprographic reproduction in accordance with the terms and licenses issued by the
CLA. Enquiries concerning reproduction outside these terms should be sent to the publishers at the
undermentioned address:
ISTE Ltd John Wiley & Sons, Inc.
27-37 St George’s Road 111 River Street
London SW19 4EU Hoboken, NJ 07030
UK USA
www.iste.co.uk www.wiley.com

© ISTE Ltd 2015
The rights of Jean-Charles Joud and Marie-Geneviève Barthés-Labrousse to be identified as the authors
of this work have been asserted by them in accordance with the Copyright, Designs and Patents Act 1988.
Library of Congress Control Number: 2015952414

British Library Cataloguing-in-Publication Data
A CIP record for this book is available from the British Library
ISSN 2051-2481 (Print)
ISSN 2051-249X (Online)
ISBN 978-1-84821-843-7
Contents
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
vi Physical Chemistry and Acid-Base Properties of Surfaces
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
Contents vii
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