3 TRIBOLOGY SERIES Editor D. Dowson (Gt. Britain) Advisory Board W.J. Bartz (Germany) R. Bassani (Italy) B. Briscoe (Gt. Britain) H. Czichos (Germany) K. Friedrich (Germany) N. Gane (Australia) W.A. Glaeser (U.S.A.) H.E. Hintermann (Switzerland) K.C. Ludema (U.S.A.) T. Sakurai (Japan) W.O. Winer (U.S.A.) Vol. 6 VOl. 7 Vol. 8 VOl. 9 VOl. 10 VOl. 11 VOl. 12 Vol. 13 Vol. 14 Vol. 15 Vol. 16 Vol. 17 Vol. 18 VOl. 19 VOl. 20 VOl. 21 VOl. 22 Vol. 23 Vol. 24 Vol. 25 Vol. 26 Vol. 27 Vol. 28 Vol. 29 Friction and Wear of Polymers (Bartenev and Lavrentev) Microscopic Aspects of Adhesion and Lubrication (Georges, Editor) Industrial Tribology -The Practical Aspects of Friction, Lubrication and Wear (Jones and Scott, Editors) Mechanics and Chemistry in Lubrication (Dorinson and Ludema) Microstructure and Wear of Materials (Zum Gahr) Fluid Film Lubrication - Osborne Reynolds Centenary (Dowson et al., Editors) Interface Dynamics (Dowson et al., Editors) Tribology of Miniature Systems (Rymuza) Tribological Design of Machine Elements (Dowson et al., Editors) Encyclopedia of Tribology (Kajdas et al.) Tribology of Plastic Materials (Yamaguchi) Mechanics of Coatings (Dowson et al., Editors) Vehicle Tribology (Dowson et al., Editors) Rheology and Elastohydrodynamic Lubrication (Jacobson) Materials for Tribology (Glaeser) Wear Particles: From the Cradle to the Grave (Dowson et al., Editors) Hydrostatic Lubrication (Bassani and Piccigallo) Lubricants and Special Fluids (Stepina and Vesely) Engineering Tribology (Stachowiak and Batchelor) Thin Films in Tribology (Dowson et al., Editors) Engine Tribology (Taylor, Editor) Dissipative Processes in Tribology (Dowson et al., Editors) Coatings Tribology - Properties, Techniques and Applications in Surface Engineering (Holmberg and Matthew4 Friction Surface Phenomena (Shpenkov)
4 TRIBOLOGY SERIES, 29 EDITOR: D. DOWSON F R I CTI 0 N SURFACE PHENOMENA George P. Shpenkov University of Silesia Sosn o wiec, Po land ELSEVIER Amsterdam Lausanne New York Oxford Shannon Tokyo 1995
5 ELSEVIER SCIENCE B.V. Sara Burgerhartstraat 25 P.O. Box 21 1,1000 AE Amsterdam, The Netherlands ISBN Elsevier Science B.V. All rights reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, without the prior written permission of the publisher, Elsevier Science B.V., Copyright & Permissions Department, PO. Box 521, 1000 AM Amsterdam, The Netherlands. Special regulations for readers in the USA. - This publication has been registered with the Copyright Clearance Center Inc. (CCC), 222 Rosewood Drive, Danvers, MA Information can be obtained from the CCC about conditions under which photocopies of parts of this publication may be made in the U.S.A. All other copyright questions, including photocopying outside of the U.S.A., should be referred to the publisher. No responsibility is assumed by the publisher for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions or ideas contained in the material herein. This book is printed on acid-free paper Printed in The Netherlands
6 PREFACE The constantly growing interest in tribology, the science of friction, lubrication and wear, and particularly in the investigation of surface phenomena in the friction zone can be attributed to the recent remarkable increase in number of various friction pairs and to much stricter requirements for performance of machines, instruments and apparatuses where they are found. Analysis of the current state and development trends in tribology shows that a qualitatively new stage in the investigation of friction has begun. The characteristic feature of this stage is closer study of physicochemical processes of contact. This has resulted in the detection of a series of new friction phenomena prompting revision of the traditional methods of wear prevention. Making use of favorable friction phenomena (selective transfer, tribopolymerization, abnormally low friction in a vacuum, viscous flow of metals as result of hydrogen absorption at high temperature, etc.) plus wide introduction of new methods for combating harmful phenomena (e.g. hydrogen wear of metals, seizing etc.) could offer considerable potential economic benefits. This has been confirmed by further investigations on the physicochemistry of friction conducted after the first publication an author s book on this subject in Support gained, enabled the production of new lubricating materials, using selective transfer during sliding, and also theoretical study of this phenomenon. What does selective transfer and hydrogen wear of metals mean? Since the subject of the book is closely related to these phenomena, appropriate definition of both are necessary. The term selective trunsfer (ST) is an adopted abbreviation for decreased wear and the coefficient of friction, which is a result of non-oxidized thin copper film formation induced by sliding. Conversely, the term hydrogen wear (HW) is an adopted abbreviation for increased wear of metals, a result of hydrogen absorption induced by sliding. Fundamental investigations of the ST mechanism are not as advanced as the traditional sections of friction theory. Selective transfer is the most pronounced manifestation of mechanochemistry and physicochemistry of the boundary friction process. The widely differing opinions on this subject indicate the complexity of
7 vi Preface the problem and are also the reason why it is not fully described in scientific literature. Progress in investigations on contact interactions of solids under friction, for example the study of new phenomena such as ST and HW, is only possible if based on advances in the physics of solids surfaces, contact phenomena and mechanics of damage, mechanochemistry, electrochemistry, materials technology, etc.. This book represents an attempt to fulfil this demand. In physics the most vital problem is the study of structural, electrophysical and physicochemical properties of real surfaces of solids subjected to mechanical and various physicochemical effects, including friction (i.e. the study of the surface) modified in various friction conditions. In chemistry most important is the investigation of adsorption and chemisorption of lubricants and the lubricant effect mechanism. A deep understanding of friction and wear processes requires first, investigation of the influence of the numerous effects accompanying the friction process, i.e. mechanical, electrical, hydroacoustic, physicochemical and other effects, their influence on physicochemical properties, structure of working surfaces etc. In the book as well as results of studies concerned with certain aspects of phenomena appearing in the process of influencing contacting surfaces, and with detecting the relations between the observed characteristics and behavior of investigated materials in the process of mechanical treatment and friction (with particular reference to selective transfer and hydrogen wear) are presented. The principle followed here is to combine varied experimental facts, physical concepts and investigation methods, which at first sight appear to be unrelated, and using this approach to determine general rules. Particular attention is paid to the quality of surface preparation and to surface properties, and to interaction between lubricants and the surfaces of real metals. A lubricant, in the broad sense, is taken to mean a third body (interlayer), differing in properties and composition, lying between the contacting surfaces. The lubricant, apart from its main function of reducing friction and wear, also promotes the formation of optimum roughness for the given pairs and conditions, influences the nature of submicrostructural changes and phase composition of working surfaces, separates and at the same time modifies the friction surfaces etc. Summarized in this book are results of investigations on certain surface phenomena observed during mechanical treatment and friction, mainly of metals used in friction assemblies, working under ST and subjected to hydrogen absorption. The nature of interaction in the systems metal-boundary lubricant medium-metal is studied. Theoretical concepts are formulated on the ST and HW mechanisms, one causing abnormally low the coefficient of friction and wear (ST), and the other catastrophic damage to surface layers under friction (HW). Some physical methods of friction investigation not yet published in the literature are briefly discussed, and application examples are given. Noteworthy are the
8 Preface vii methods of contact potential difference (CPD) and Mossbauer spectroscopy through conversion electrons and also discussion of new results, obtained with their help. In tribology and surface physics, the Mossbauer electron spectroscopy method is of particular importance due to its high sensitivity. This is a nondestructive selective method for the investigation of structure, phase composition, dynamics of the crystal lattice etc. of surface layers (which are most informative at a depth of nm). The first chapter presents interrelated fundamental characteristics of a solid and its surface, such as surface energy and surface tension, and the phenomena of contact interaction of solids surfaces with each other, and with other phases in static. A brief description is given of the main aspects of a molecular-mechanical theory of friction, including analysis of the assumption of shear resistance positive gradient. Mechanical (deformation) properties of a double electrical layer are considered, and a mechanical model of a double electrical layer (DEL) is given and verified. Certain properties of solids, including friction coefficient, are determined by the value of surface tension, which in its turn varies with adsorption of surfactants contained in the lubricant. Also presented is the mechanism of adsorptive plasticization of surfaces, which has a great influence on the friction process during lubrication with surfactants. The chapter also gives the reader a general understanding of fundamental surface phenomena which provide the background of their dynamic interaction in mechanical treatment and under friction. The second chapter deals with the laws governing influence of mechanical effects on the surface. This is illustrated by hand polishing of surfaces with abrasive cloths of various grain sizes. Another highly sensitive recorded parameter is the electron work function (EWF). The experimentally obtained CPD dependence on quality of mechanical treatment of solids, which proved to be universal for the investigated materials, is discussed. An analysis is given of CPD kinetics after ceasing mechanical action in the friction process with adsorption of lubricant molecules. Results presented in this chapter also make it possible to distinguish a group of seven metals possessing a combination of properties, such that under defined friction conditions the ST of each may be predicted. Investigations were carried out on standard constructional metals and alloys under natural conditions (in air). The fundamentals of the ST-theory under friction are given in the third chapter, and the most characteristic physicochemical processes in ST are considered. The relation between metals resistance to wear during ST and the electron work function, influence of abrasive particles on the ST effect and other problems are analyzed. From this the electrochemical mechanism of the phenomenon may be determined. The fourth chapter is devoted to an analysis of the simultaneous effects of high pressure and shift deformation, taking place in the zones of actual surface
9 ... Vlll Preface contact under friction, on structural changes of the contacting surfaces and ambient conditions. The phenomenon of air ionization with perturbation of the boundary friction regime, is described. On the basis of latest results, one more possible mechanism of the servo vitae layer formation during ST is discussed. According to N.S. Enikolopyan et al, (Scientific Discovery. Diploma No 288, 1984) high pressures together with shift deformation, which are the necessary main components of the friction process, impart immense chemical and physical energy to the material, and in particular, promote solid monomers polymerization at abnormally high reaction velocities. According to the author, this offers great potential for utilization in tribology and tribotechnology, but this would need the cooperation of a wide group of tribologists to gain further knowledge of its internal mechanism. The main characteristics of the given phenomenon are given in this chapter, paying special attention to the frequency of processes occurring in the surface layers of friction bodies. The great possibilities of the Mossbauer electron spectroscopy method, widely used in physics for solving tribology problems are shown in the fifth chapter. Particular tribology problems described here are then solved by this method. These were the following; explaining the polishing mechanism and structure of modified surfaces, the phase composition of surface layers of friction metals, polishing effect, investigation of surface layers anisotropy resulting from specific treatment, etc. The sixth chapter is devoted to the influence of external electromotive force (EMF) sources on contact resistance and friction pairs wear, in which ST in the de-energized regime is possible. ST display, electrocapillary and electroplastic effect in current-conducting pairs, and also lubricant influence, are considered. Results of studies allowed certain recommendations to be made aimed at increasing reliability and longevity of lubricated sliding electrical contacts. The mechanism of hydrogen absorption and hydrogen wear under friction is dealt with in the final, seventh chapter. The calculation of temperature distribution along the normal to the surface into the depth of a sample under friction, is presented. The phenomenon of metal passage to the viscous flow state under hydrogen saturation in the friction process, at temperatures much lower than melting temperatures, is also described. Propositions for HW prevention and the use of ST for this purpose are given. Current aspects of certain important practical tribology problems discussed in the book are stressed in the conclusion together with considerations of friction process control. Thus, the reader is offered a review of new ideas and methods in tribology to be used in tribotechnology. This book is a revised and supplemented version of the author s monograph Physicochemistry of Friction (University Publishers, Minsk, 1991). It is intended
10 Preface ix for scientific, engineering and technical workers but may also be of value to graduates and students dealing with tribology and tribotechnology. It is hoped that the problems solved by various physical considerations and methods will prove of interest to physicists. The book could also be useful for chemists specializing in lubrication. Those who have not yet needed to deal with the problems of tribology may begin to learn how complicated, interesting and diverse is the world of friction, and what knowledge it demands. In this way, the author hopes it may attract attention to the problems of tribology among those physicists and chemists who have not yet made their choice in science. While apologizing for the inadequacies of this book, the author would be grateful for all comments. It is my pleasure to express sincere thanks to Professor Douglas Godfrey for his friendly and valuable comments related to the translation of the seventh chapter. I also wish to thank Professor Nikolai Myshkin and his assistants for their correction of the entire English text. Many thanks to my son, Maxim, who has assisted me at all stages in the preparation of this manuscript. Sosnowiec, 1994 George P. Shpenkov
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12 CONTENTS Preface... v Chapter 1. INTERACTION OF SOLIDS Surface Energy and Surface Tension Double Electric Layer at the Phase Interface Mechanical Model of Double Electric Layer Friction; Positive Gradient Rule Adsorptional Softening of Surfaces Chapter 2. SURFACE STATE; ENERGY CHARACTERISTIC Measuring of Electron Work Function for Surface State Evaluation Correlation of Work Function and Metal Surface Treatment Kinetics of Electron Work Function of Machined Metal Surfaces Correlation of Work Function and Quality of Machining Different Metals Influence of Semiconductor Surface Treatment on Electron Work Function Kinetics of Contact Potential Difference in Adsorption of Lubricants Electron Work Function Variations of Solids in Sliding and the Method of Selecting Materials Chapter 3. PHYSICAL CHEMISTRY OF CONTACT INTERACTION AT SELECTIVE TRANSFER Selective Transfer Physical Nature of Metal Seizure Seizure Mechanism in Selective Transfer; Electrochemical Mechanism of Transfer... 80
13 xii Contents Boundary Layer Properties in Selective Transfer Relation Between Wear Resistance of Metals in Selective Transfer with Galvano-EMF in Statics Role of EMF in Selective Transfer at Low Sliding Speed Changes of Metal Electrode Potentials in Lubricants Favouring Selective Transfer Wear Resistance of Metals in Selective Transfer and Work Function Influence of Hydrogen on Selective Transfer Initiation of Selective Transfer by Powders Generalized Schematic Description of Selective Transfer Other Processes Responsible for Selective Transfer of Copper Development of the Concept of Selective Transfer An Example of the Selective Transfer Application; A New Multifunctional Additive Chapter4 THE ROLE OF HIGH PRESSURE AND SHEAR STRAIN IN FRICTION Local Excitation Level Gas Ionization in Sliding of Metals The Possible Mechanism of the Servovite Layers Formation Phenomena at the Interface Under High Pressure and Shear Strain Periodicity of Processes in Surface Layers During Friction A Theoretical Approach to a Description of the Periodicity of Triboparameters Structural Changes of Surface Layers in Friction Chapter 5. STRUCTURAL AND PHASE CHANGES STUDIED BY MOSSBAUER SPECTROSCOPY Mossbauer Electron Spectroscopy Capability The Mechanism of Polishing Anisotropy of Surface Properties after Machming Crystalline Lattice Deformation of Stainless Steel Surface Layer by Grinding Influence of Lubricants and Lubricant-Coolants on Surface Layer Structure and Phase Composition Surface Modification by Nonabrasive Antifriction Finishing Role of Original Surface State in Structural and Phase Changes at Machining
14 Contents... Xlll Chapter 6. INFLUENCE OF EXTERNAL ELECTROMOTIVE FORCES ON CONTACT RESISTANCE AND WEAR Electrical Contacts Contact Electrical Resistance Contact Resistance of Sliding Electrical Contacts in Experiment Wear of Sliding Electrical Contacts Electrocapillary and Electroplastic Effects Electroplastic Effect in Sliding Pairs Initiation of Selective Transfer by Electric Current Practical Recommendations Problems of Improving Design of Standard Current Collectors Chapter 7. HYDROGENATION DURING SLIDING AND HYDROGEN WEAR MECHANISM Introduction; Hydrogen Embrittlement and Hydrogen Wear of Metals Sources of Hydrogen and Factors Influencing Absorption Hydrogen Evolution and Absorption During Sliding of Solids Hydrogenation of Metals During Sliding Against High Friction Plastics Mechanism of High Temperature Hydrogenation of Metals During Sliding Against High Friction Plastics The Influence of Hydrogen Absorption on the Work Function of Metals and Alloys The Mechanism of Hydrogen Wear Preventing Hydrogen Wear in Various Kinds of Sliding Assemblies Examples of the Use of Selective Transfer to Prevent Hydrogen Wear Magnetic Field Influence on Hydrogen Behavior Conclusion References Subject Index
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16 Chapter 1 INTERACTION OF SOLIDS 1.1. Surface Energy and Surface Tension The interaction of solids in friction proceeds on their surfaces. Any surface can be considered as an imperfection of a three-dimensional crystal structure. The break of the lattice periodicity causes a change in the coordination number of the surface atoms, and rehybridization of their bonds. As a result, the atomic arrangement and spacing alter. Here, Z, > Z, is usually the case, where Z, is the coordination number in the crystal volume and Z, is the same on the surface. Generally, equilibrium chemical bonds on the surface and in the adjacent region differ from those in the bulk. A disrupted surface structure and an ordered structure in the bulk have no sharp boundary, therefore, a certain transition layer can exist. Two-dimensional structures appear on the crystal surface with atomic spacing different from those in the bulk. The difference in molecular interactions is responsible for an excess of the energy at the interface, which is the surface energy. Thus, molecules at the phase interface, unlike molecules in the bulk, are subjected to the forces, the resultant of which is directed into the solid. Naturally, a part of the substance located at the interface has some specific features, distinct from those of the substance in the bulk. Besides, on the surface and in the near-surface layers phase transitions occur. This fact specifies a number of phenomena, referred to as surface phenomena, like catalysis, adsorption, capillary forces, electronic and molecular processes on the semiconductor surface, the Rehbinder effect, adhesion, etc. The special properties of the surface have the greatest influence upon the behavior of semiconductor devices with sizes commensurable with the thickness of the surface layer. When considering the effect of mechanical treatment and the interaction of solids in friction from a physicochemical standpoint, the energy parameters should be considered which characterize a solid and its surface, primarily, the surface energy and the surface tension. Surface energy. The surface energy depends on the nature and structure of a solid and has a definite value corresponding to the surface thermodynamic equilibrium and its saturated vapor [ 11. The surface energy distribution is anisotropic. Thus, theoretical calculation of
17 2 Chapter 1 the model of a 360-atomic lattice for Ca, Ag, Al, Pb, Cu, and Ni has revealed that, in all the above-listed metals, planes (111) have the minimum surface energy o and planes (110) have the maximum. The problem of theoretical prediction of the surface energy is more intricate than to predict the atomic bond energy. Discontinuity of the metal lattice leads to a modulation of the volume density of conductivity electrons. Near the boundary, at distances of an order of the atomic size, the density falls from the bulk value to zero. A task of the metal surface theory is to adequately identify the character of the electron density fall. In the solid state theory, this problem is solved with the theory of heterogeneous electron systems (the self-consistent theory of normal state of heterogeneous electron gas ), specifically, with the density functional method (DFM) . The DFM is also employed in calculating other characteristics of the metal surface, in particular, the electron work function and the surface energy 0. In most cases, the calculations are based on the simplest gel model, when the metal lattice is replaced by a homogeneous positive background. The calculations make it clear a double electric layer (DEL) forms near the background boundary with the size of an order of an atom. Since the electron density n(x) does not fall abruptly to zero at the boundary, the electron gas extends outward, thereby reducing the kinetic energy of the electrons and increasing the potential energy that restricts further diffusion of the electron density. On the basis of the DFM and the minimum energy principle of the normal state, for relatively simple models of a solid, a considerable advance has been made in explaining numerous experimental data on the surface energy and the EWF as well as in solving many other problems of the surface physics . Alongside with the development of theoretical predictions, many empirical or semiempirical equations are suggested to relate the surface energy to some physical constants of metals . Thus, for example, a method of crystal cracking in a certain crystallographic direction is used for measuring 0. The equation relating the surface energy to mechanical characteristics of the metal, such as the Young modulus E, appears as o=(6fzl2)/(e~ t:), where F is the force required for propagation of a crack; L is the length of the crack opening; a is the specimen width, and 2t, is the thickness of the specimens. A number of studies proposes a simple calculation, yielding approximate values which, however, satisfactorily represent correlations in o for various metals. As an illustration of a fairly acceptable empirical formula relating o to the basic
18 Interaction of Solids 3 characteristic of a solid, namely, EWF, we may present the equation derived by S.N. Zadumkin for planes (h,k,l) may be presented: where k,=1.15 for Zv=8 and k,=1.08 for Zv=12; n is the number of valence electrons; and V,, is the specific molar volume. Surface tension. A general thermodynamic approach to equilibrium of a surface layer with two neighboring volume phases gives the following expression for the total surface layer energy where T=dU/dS is the layer temperature (the intensity factor); is the layer entropy (the capacitance factor); s is the phase interface area; Y = (8 u 18 ~)s,~~,... is the intensity factor similar to pressure in the volume phase du/dv=-p, which is called the layer surface tension (the dimensions of y are J/m2 or N/m); pi=dll/dni is the chemical potential of the component i in the layer (the intensity factor); and nj is the excess of the components i in the surface layer. The surface tension y enters into expressions for the excess free surface energy of the layer ds) defined in accordance with equation ( 1.1) as i The surface tension is governed by the nature of contacting phases. In surfactant adsorption the Rehbinder effect manifests itself in a variety of forms [4.5]. They include a reduction of the surface potential causing metal softening; origination and subsequent propagation of cracks resulting in the fracture of solids; dramatic fall of the interfacial energy inducing a spontaneous dispersion accompanied by generation of particles of colloidal sizes. The effects stem for the most part from a decrease in the free surface energy of a solid at the boundary with the medium. In adsorption of surfactants (specifically, of diphilic molecules), the surface tension of the liquid phase diminishes appreciably. Because the surface tension and the free surface energy for a single-component liquid are numerically equal, any reduction of the surface tension entails an equivalent reduction of the free surface energy. It ensues from Gibbs fundamental equation (1.2) for the interfacial layer that the interfacial surface tension y is defined as the free surface energy
19 4 Chapter I o( ) of a unit surface area at constant temperature and composition of the layer: For solids, such identity does not hold true and the relation between the two quantities is as follows: y=o+s(do/ds),, where s is the surface area. The difference between the surface energy o and the surface tension y is that the first is the work needed for the unit surface area formation and the second is the work required for increasing the available surface by the same magnitude. For liquids, it is as a rule, do/ds=o, since a uniform density of the liquid film establishes in the surface layer nearly instantaneously, following the film deformation (no matter how much mercury may spread, its physical characteristics remain unchanged). When the solid surface is under tension, the average atomic spacing in the surface layer varies and, accordingly, the conditions of atomic interaction alter (with a tensile-stressed solid metal, the surface area properties also change simultaneously) . The surface layer may be considered in the first approximation as surface phases of variable composition, with the properties being functions of the distance from the interface. Generally, the surface phase has the following thermodynamics. A change in the total internal energy of the system AU due to the increment As of a new surface phase from the side of one of the two bordering phases is AU=V-U,, where V is the total internal energy of the new surface phase and U, is the total internal energy of the part of volume V. In conformity with equation (1. l), the expression for AU has the form: where Ns is the particle number in the surface phase and N, is the particle number in the part of volume V. A surface identification of the total internal energy of the system is U,=AU/(~)=T(Ss-S,)/(~)+C1(Ns-N,)/(As)+y=T~+CLT+y. Here,,$=(SS-S,)/(As) is the surface densification of entropy and T=(N -N,)/(As) is the surface densification of the substance, or adsorption. The surface densification of the free energy of the system (the specific free surface energy) is defined as o,=u,-ts;=~r+y. (1.3) From (1.3) follows o,q. Then, as the surface phase is generated, the work is spent not only on creating the surface but also on varying the substance density
20 Interaction of Solids 5 in the surface layer. Hence the reduction of the surface tension cannot be treated as a fall of the free surface energy. Thus, for plane (111) of NaCl crystals, 0,=0.187 N/m, whereas ypo.562 N/m. The surface tension y is one of the most important characteristics. Many properties of solids are dependent on the surface tension, among them adsorption wettability, adhesion, electron emission (photo-, thermal, exoelectron, and other types), mechanical properties (hardness, creep, friction coefficient, and others), electrochemical phenomena, etc. Thus, the surfactant adsorption causes a change in the surface tension. For example, argon adsorption on the clean surface of a glass rod results in its elongation, equivalent to heating by 523 K. Solids have heterogeneous surfaces characterized by the presence of areas with different energy and, therefore, with different surface tension (a composition heterogeneity, different crystallographic orientations of individual crystals and crystal lattice imperfections). Adsorption molecules tend to cluster in active centers. In this connection, studies of adsorption have revealed a strong influence of the pretreatment and the state of the surface on the adsorption on metals Adsorption of surface-active organic and inorganic ions is also influenced by the metal nature. Ions, highly surface-active on one metal, are low-active or inactive at all on another. For example, hydroxyl ions, which are surfaceinactive on mercury even at large ph of solution, are well-adsorbed on iron. Naphthalene molecules, representing two condensed benzene rings, have a flat arrangement on iron, nickel and lead surfaces and a vertical arrangement on a copper surface. Decylamine molecules adsorb on lead, copper, and nickel by hydrocarbon tails of molecules, and an NH, group is directed into the solution. The decylamine molecules are oriented to the iron surface by an NH, group. Nonetheless, the mechanism of different orientations of decylamine molecules on metals with identical chemical characteristics (like iron and nickel) has not been fully understood . The surface tension of solids depends on the electric potential jump at the interface. It exists at the solid-liquid interface, if both phases are somewhat conducting. Any change in the interfacial electric potential is accompanied by alteration in the character of phenomena occurring on the solid surface . So, changes in the potential of a gold electrode in aqueous solutions cause its elongation and changes in the potential of a high-porous carbon electrode electrode results in its deformation . Studies in correlation of the surface tension y and the potential cp  allowed to ascertain of the fundamental difference between y and the reversible surface generation work o for a solid electrode, which was first noticed by Gibbs.
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