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1 INDEX A Abhesives definition 44 theory of action 45 Additivity of intermolecular forces and surface energy components Adherend definition of 41 roughness, effect on wetting by adhesive 42 Adhesion effect of water on 45 temperature dependence theory of adsorption theory of diffusion 189 theory of electrostatic Adhesion and chemical bonding at interface 45 Adhesion in lap joint, effect of poor wetting on Adhesion tension..162, 166, 170, 173, 177, 219, 310 Adhesive definition of 41 joint strength, maximum thermodynamic value.. 41 solidification, relation of WA 43 spreading, stress concentrations due to incomplete 43 viscosity, effect on wetting by adhesive 42 Adhesives art, relation to wetting 41 Adsorbed wetting agents, orientation and packing of interfacial energy Adsorption.. 160, 163, 165, 172 acid molecules from Decalin 290 behenic acid from Decalin 290 bromine ions on glass on copper 299 dodecyltrimethylammonium bromide on silica and glass 234 effect of moisture on fatty acid monolayers free energy of 108 on gold 298 heat of 110 on iron 297 on metals, direct measurement 295 on mica 297 multilayer, and angle of contact 62 potential theory of, and angle of contact 63 from solution, heat of immersion 96 solvent, rinsing from metal surfaces 271 techniques 295 of vapor and angle of contact 59 Advancing contact angles 5, 205, 206 Advancing and receding contact angles of liquid in a capillary tube 262 on polymeric solids 12 Alumina, adsorption isotherms 225 Amine 313 Angle of contact 57 See also Contact angle Autophobic liquids 334 contact angles of 25 definition of 23 Autophobic property, temperature effect on

2 382 INDEX Β Bangham and Razouk, contributions of 4 Behenic acid 281 Blodgett monolayer conversion of 270 counting rate to 269 Bonding, rate of 187 c Capacity of exchange at silica or glass surfaces 240 Capillarity 159 importance in adhesion.. 42 Capillary creep of adhesive, existence of a maximum 42 Capillary flow in microscratches 349, 373 Capillary pressure, maximum 187 Cassie and Baker equation.. 121, 128, 131 Cerotic acid 281 Chemisorption effect on adhesion 194 on glass and silica 232 of dodecyltrimethylammonium bromide effect of solution ph of substituted quaternary ammonium salts Coacervation 188 Coadsorbed film, model Coadsorption n-octadecane on metals stearic acid on metals Coatings, techniques for depositing 336 Composition of stearic acid-η-octadecane films, 0.5-hour adsorption Contact angle , 159, 171, 176, 204 advancing 112 apparent, of secondary film 362 calculation of advancing and receding 264 chain length dependence.. 56 on cut surfaces 55 definition of 2 effect of subsurface molecules 56 effect of surface roughness 156 effect of temperature equation for calculation of. 103 equilibrium 146 metastable 116 unstable 116 error due to surface roughness 6 on fluorocarbon wax surfaces 137, 138 gallium-mercury 156 hexadecane 151 hysteresis 54, 112, 136 effect of oxygen on relationship to equilibrium contact angle isoamyl xanthate on minerals 56 Langmuir s obs ervations f on 7 measurement 277 by interference patterns 343 on Teflon 256 methylene iodide 150 advantages of in studying 29 on perfluoro-octanoic acid 56 at monolayer-substrate boundary 376 on paraffin wax surfaces. 139 polyethylene, measurement on 256 receding 112 regularities among fluorinated materials 19 relation to critical line force 259 relation to surface tension 333 temperature dependence.. 54 variation with liquid variation with solid 145 water 148 on adamantane 55 on cycloparaffins 55 on hexadecyl alcohol on hexamethylethane on norcamphane 55 on paraffinic surfaces.. 54 on polyethylene 55 on tricyclodecane 55

3 INDEX 383 Contact time 209 Contamination 205 Copper, coadsorption of stearic acid and n-octadecane on 268 Creep of oils. See Spreading, spontaneous Critical line force calculated from equilibrium contact angle calculation in capillary tubes 254 defined 251 Critical low energy surfaces, effect of constitution on f s vo 48 Critical micelle concentration, relation to cos θ vs. r L V plots 33 Critical surface tension of abhesive surfaces aqueous solutions of nonmicelle-forming compounds 33 chlorocarbon surfaces definition of 12 effect of relative humidity on 48 effects of temperature on. 48 fluorocarbon surfaces. 21, 147 of halocarbon surfaces halogenated poly ethylenes. 16 of hydrocarbon surfaces 22, 147 need for research on temperature effect nitrated hydrocarbon surfaces 22 of polyacrylamide 327 of polyacrylamide containing fluorocarbon additives 329 of polymeric solids 20 of polymethacrylic ester of perfluoro-octanol 20 of poly (methyl methacrylate) containing fluorocarbon additives 325 of poly (methyl methacrylate) surface 324 of polystyrene surface of poly(vinylidene chloride) copolymer 326 containing fluorocarbon additives 326 of poly (vinyl alcohol) relation to principle of independent surface action 22 of starch polymer 20 vs. surface constitution table of 21 of wetting 104, 304, 334 of polyethylene 254 of Teflon 254 Crystallinity of polymers.. 82 Crystallization rate phenomena 173, 176 D debruyne, adhesion rule of 189, 198 Defect structure of solid surface 86 Degree of surface coverage. 290 Dewetting glass and silica 232 silica by chemisorption of dodecyltrimethylammonium bromide 240 Diffusion, surface 373 Dipole moment 76 Dipoles oriented 85 rotating 85 Dispersion energies 92 Dispersion force 75, 99 contribution to surface tension 100 in graphite surfaces in high energy solids in mercury 102 in relation to y c 48 theory of 83 in water 102 between wax and polar organic liquids 107 Distinction between WA and WA* 4 Dopes 311 Double layers, heats of immersion 97 Draining of oil films, equation for 361

4 384 INDEX Drops, movement on tilted plates 253 Dupre' equation 3 Dynamic contact angles E Electron diffraction pattern of evaporated metal films. 269 of polished metal surfaces 269 Electrostatic fields 92 Ellipsometric measurement of oil films 359 Energy barriers 119,122 composite surface 130 noncomposite surface Epilame 333, 335, 336 Equation of Cassie and Baxter 121, 128, 131 Equilibrium contact angle effect of vapor pressure on 12 F Fatty acid monolayers, adsorption of 275 Film pressure , 164, 166, 170, 172, 175, 177 Fluorinated liquids, contact angles of 106 Fluorinated polymers barriers for spreadingoil drops 337 effect of temperature on with low critical surface tension of wetting 336 Fluorocarbon surfaces Fluorocarbons, interactions of, at interfaces 105 G Gallium 211 Gallium-mercury interfacial tension 218 Glass 211 chemisorption and dewetting 232 Graphite, heats of immersion 109 H Heat of immersion 108 alumina 226 combining with other techniques 91 curves 89 classification 89 new types 90 double layer formation in hexane 230 hydrophilic character interaction energies oxides 95 polarity of solids 92 problems 90 relation to adhesion 46 site heterogeneities 93 solution adsorption 96 surfactants 94 titania 227 Heterogeneities of sites Hexane, adsorption isotherms on alumina 230 on quartz 230 on titania 230 High energy solid surfaces. 108 High energy surfaces definition of 11 wetting of 23 Hydrogen bonds 82 Hysteresis , 205, 217, 219 in capillary tubes 262 of contact angles , 250 I Immersion, free energy of Immiscible liquids. 159, 164, 169 Incorporation of solvent Interfacial discontinuity Interfacial energy, conditions for neglect of 35 Interfacial hydrostatics. 160, 161 Interfacial monolayers, tension and pressure in. 101 Interference microscopy of spreading films 358 Ionization energy 3, 83 Iron, coadsorption of stearic acid and n-octadecane on 268 J Jeffrey T s equation 361 Κ Kel-F polymer, wetting of.. 15

5 INDEX 385 Langmuir's principle of independent surface action 7 Liquid-liquid interfaces, structure of 100 Liquid vs. solid state in relation to angle of contact 62 London dispersion forces Low energy surfaces, definition of 11 Lubricants, control of spreading of 378 Lubrication conditions for fine instruments 332 M Macadam, oil-bound 315 Marangoni effect 349, 374 Meniscus shape 214 Mercury 204, 211 interface between, and polar organic liquids. 106 Mercury-water interfacial tension 102 Metal, effect on composition of coadsorbed films Metal films, adsorption on Metal-metal systems 75 Metals, coadsorption of stearic acid and n-octadecane on 268 Methanol, adsorption isotherms on alumina 229 on quartz 229 on titania 229 Methyl groups, attraction for water 55 Methylene groups, attraction for water 55 Methyline groups, attraction for water 55 Mobile drop effect 347 Molar volumes 76 Mold-release agents, definition of 44 Molecular forces, Laplace treatment of 1 Monolayers 275 adsorbed by metals 300 of ψ - alkanoic acid, properties of 18 barium dinonylnaphthalene sulfonate, spreading on 272, 377 octadecylamine 75 perfluorodecanoate 364 Movement of liquid in capillary tube 253 Multilayers 290 adsorbed on metal surfaces 272, 273 Nonspreading on glass, silica, and sapphire 25 clock oils 332, 333 oils 341 Nylon wettability 302 n-octadecane adsorbed on films , 272 coadsorption with stearic acid 268 Oleophobic additive 334 films, Langmuir T s orientation of 7 monolayers, critical temperature of wetting Optimum joint strength, conditions for 46 Organic liquid-air interfaces, surface activity 317 Oxides, solid, thermodynamics of wetting Oxygen 204 Parting agents, definition of. 44 Peel strength 182 Perchloropentadienoic acid monolayer, wetting of.. 14 Perfluoro fatty acid monolayers, wettability of.. 17 Perfluorolauric acid monolayer surface free energy 77

6 386 INDEX Perfluorolauric acid monolayer, continued wettability of 17 ph, influence of 206 Platinum, coadsorption of stearic acid and n-octadecane on 268 Polarity of solids 92 Polarizability 76 Polyacrylamide, wettability of 327 Polydimethylsiloxane monolayer retracted 147 packing of methyl groups. 149 Polyethylene adhesion of, to epoxy tensile strength and relation to joint strength of wettability of 13 Polyhexafluoropropylene, surface free energy Polymer crystal structure morphology and wettability 306 Polymer wettability 302 Poly(methyl methacrylate), wettability of Polymethylsiloxane liquids, causes of spreading Polystyrene, wettability of Polytetrafluoroethylene, wetting by homologous series of liquids 12 Polytrifluoroethylene, surface free energy 77 Poly(trifluoromonochloro)- ethylene, surface free energy 77 Polyvinyl chloride), wettability of 14 Poly (vinyl fluoride) wetting of 15 Poly(vinylidene chloride) copolymer, wettability of 325 Poly(vinylidine chloride), wettability of 14 Poly(vinylidine fluoride), wetting of 15 Potential energy function Potential functions 85 Pressure differential across liquid in a capillary tube 251 Principle of independent surface action, exceptions to 22 Progressively fluorinated acids, retracted monolayer 147 fatty acids, synthesis by Brace 22 Q Quaternary ammonium salts, effect of solution ph on chemisorption of 235 Quartz, adsorption isotherms 225 R Radiation detection of combined H and C Radiostearic acid, adsorption of on metals Radiotracer adsorption technique 296 Reactivity and adsorption of metals 300 Readvancing contact angle Receding contact angles... 5, 206 Refractive index, polarizability from 78 Regular interfaces 74 Relaxation 184, 208 Replicas 280 Resistance to movement of liquid-solid-vapor boundary line 250 Retracted films condition for solvent inclusion 29 metastability of films including solvent 29 Retracted monolayers advancing vs. receding contact angles 10 effect of varying solvent.. 10 orientation of 8 relation to Langmuir- Blodgett films 9 structural requirements for 8 Retraction from aqueous solutions 9 Retraction method choice of solvent for... 27

7 INDEX 387 Retraction method, continued discovery of 8 explanation of 26 generalization of 26 Retraction process, effect of temperature on 9 Reversible work of liquid adhesion effect of surface tension in plastics 39 estimation for monolayercoated surfaces 40 maximum in 38 method of estimation Road aggregates 310 wettability of 310 Rough surface composite 119, 124 idealized 112 noncomposite 119, 123 preparation 138 sinusoidal 112 Roughness of adherend, effect on joint strength 44 effect of on adhesion Rutile, heats of immersion. 109 Selective adsorption 188 Self-healing of adsorbed films 330 Shadow-casting 280 Silica aqueous solutions of dodecy ltr imethy lam - monium bromide adhesion tension of effect of ph on adhesion tension of 243 chemisorption and dewetting 232 Silicone films to prevent spreading 351, 352 Silver, coadsorption of stearic acid and n-octadecane on 268 Solid-liquid interfacial tension... 20, 158, 173, 175 Solid surfaces, chemical structure of 52 Solid-vapor interfacial tension 158, 162 Solubility effects in interfacial tension 75 Solubility parameters, recent work of Gardon in relation to yc 48 Solvent inclusion in films formation by retraction.. 28 work of Bartell and Ruch. 28 Solvent purity 270 Speed dependence 209 Spreading , 163, 168, , 181 of aliphatic hydrocarbons. 369 of alkyl aromatic hydrocarbons 370 anomalous 347 behavior of additive oils 344, 346, 348 coefficient , 218 condition of Cooper and Nuttall 4 condition of Harkins... 5 effect of scratches on 371, 373 effect of temperature difference on 370 nonreciprocity of 193 of polymeric liquids pressure 75 of adsorbed layers on solids 103 in metal-metal systems 77 values of f s y o for metallic surfaces values of f S Vo for nonmetallic surfaces. 37 of water on graphite of water on mercury and graphite 104 primary film 356, 360, 363, 373 secondary film 356, 373 spontaneous 355 vapor effect on 368 Spray coating, control of spreading in 379 Spreadability οηα-α on fused silica 24 on metals 24 Static contact angles 203 Stearic acid 281

8 388 INDEX Stearic acid, continued adsorbed on films , 272 coadsorption of solvent with n-octadecane Stress concentration 184 near occlusions 43 Stress propagation in interface, effect of surface voids 44 Subscript system of Boyd and Livingston 4 Surface active agents in nonaqueous systems organophilic -organophobic balance 36, 318 partially fluorinated compounds 318 Surface activity of fluorocarbon additives in polyacrylamide in poly (methyl methacrylate) 325 in polystyrene 321 in poly(vinylidene chloride) copolymer 326 fluorochemicals in nonaqueous liquids 36 at organic liquid-air interfaces 317 of polymer-air interface. 318 silicones in nonaqueous liquids 36 Surface cleaning 304 Surface contamination, effect on nonspreading Surface energy perfluorolauric acid monolayer 81 polyhexafluoropropylene.. 81 polytetrafluoroethylene.. 81 poly (trif luoromonochloro) - ethylene 81 Surface entropy 84 Surface forces, localization of 6 Surface free energy... 74, 181 Surface heterogeneity and angle of contact 69 Surface hydrolysis of 2-ethylhexanoates on silica, glass, and sapphire 25 Surface poisoning by hydrolytic products 25 Surface polarity 82 Surface potentials, pure and mixed monolayers on metals 29 Surface roughness , 272 and angle of contact 58 and contact angle hysteresis 266 and critical line force effect on contact angle Surface tension of bare solid 175, 177 gradient by adsorption gradient by evaporation of hydrocarbons, table lowering, survey of Fischer and Gans, conventional agents 30 of polymeric liquids, table 358 by temperature difference 378 temperature effect on in water, effect of conventional wetting agents 31 Surface wicking 117, 142 Surfactants, packing on Graphon 94 Teflon, heats of immersion. 109 Textile fibers and fabrics, surface treatment with fluorochemicals 19 Three-phase interline.. 208, 209 Thermodynamic treatment of capillary phenomena... 3 Threshold, concentration, for adhesion tension 313 Titania, adsorption isotherms 225 Vapor adsorption and f i 38 s vo on low energy surfaces. 38 on polytetrafluoroethylene 38 Vapor-deposited metal films 296 Velocity of liquid movement in a capillary tube

9 INDEX 389 Viscoelastic response 184 W Water adsorption, essentially hydrophobic surfaces.. 95 Waxes, resins, early work of Bartell and Zuidema on 20 Wenzel's equation. 116, 127, 131 and the roughness factor. 5 Wenzel's ratio 115 Wettability comparison of hydrocarbon and fluorocarbon surfaces 17 comparison of monolayers and solid polymers effect of progressive fluorination of co-ch3 group 18 by heats of immersion by higher boiling liquids.. 24 and moisture sorption of polyethylene by aqueous solutions 31 of polytetrafluoroethylene by aqueous solutions Wetting action of "wetting agents" 30 adhesion, applications of research on 47 agents, new method of comparison 35 agents for nonaqueous systems 36 balance 311 criterion 182 definition of 180 heats of immersion 94 of poly(ethylene terephthalate) 20 of polyhexafluoropropylene 20 of poly (hexamethy lene adipamide) 20 and polymer surface chemistry 306 and polymer surface crystallinity 306 of polystyrene 20 properties 275 and separation of polymer crystal planes 309 by solutions, aqueous and nonaqueous 30 spreading, and adhesion, future research on thermodynamics of 222 Work of adhesion 304 Y Young-Dupré equation... 58, 305 thermodynamic value of.. 59 verification of 66 Young's equation.. 52, 115, 158, 159, 161, 163, 168, 177, 202, 205 complications in use of.. 3 early treatment 2 Sumner's and latter treatments of 3