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KLIKNIJ ABY PRZEJŚĆ DO SPISU TREŚCI

KLIKNIJ ABY PRZEJŚĆ DO OPISU KSIĄŻKI

KLIKNIJ ABY ZOBACZYĆ INNE WYSTAWIANE PRZEZE MNIE PRZEDMIOTY ZNAJDUJĄCE SIĘ W TEJ SAMEJ KATEGORII

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PONIŻEJ ZNAJDZIESZ MINIATURY ZDJĘĆ SPRZEDAWANEGO PRZEDMIOTU, WYSTARCZY KLIKNĄĆ NA JEDNĄ Z NICH A ZOSTANIESZ PRZENIESIONY DO ODPOWIEDNIEGO ZDJĘCIA W WIĘKSZYM FORMACIE ZNAJDUJĄCEGO SIĘ NA DOLE STRONY (CZASAMI TRZEBA CHWILĘ POCZEKAĆ NA DOGRANIE ZDJĘCIA).

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Protective and Decorative Coatings
Prepared by a Staff of Specialists under the Editorship of
JOSEPH J. ÄIATTIELLO, Ph. D.
Vice-President and Technical Director Hilo Varnish Corporation
VOLUME IV
SPECIAL STUDIES
WETTING, GRINDING, COLOR, CONSISTENCY,
HIDING, ADHESION,
PERMEABILITY AND FILM STRUCTURE,
LIVERING, MICROSCOPY,
VACUUM TECHNOLOGY,
EMULSIONS,
AND ULTRAVIOLET ABSORPTION
OF DRYING OILS
NEW YORK: JOHN WILEY & SONS, INC. LONDON: CHAPMAN & HALL, LIMITED

Protective and Decorative Coatings
Prepared by a Staff of Specialists under the Editorship of
JOSEPH J. ÄIATTIELLO, Ph. D.
Vice-President and Technical Director Hilo Varnish Corporation
VOLUME IV
SPECIAL STUDIES
WETTING, GRINDING, COLOR, CONSISTENCY,
HIDING, ADHESION,
PERMEABILITY AND FILM STRUCTURE,
LIVERING, MICROSCOPY,
VACUUM TECHNOLOGY,
EMULSIONS,
AND ULTRAVIOLET ABSORPTION
OF DRYING OILS
NEW YORK: JOHN WILEY & SONS, INC. LONDON: CHAPMAN & HALL, LIMITED

PREFACE

This is the fourth volume of a set of books dealing with the protective and decorative coatings industry. It presents to the technologist the most important subjects concerned with pigmented coatings, both during and after manufacture, and in the dried film.
Of first importance is the practical application of wetting and grinding principles in pigment-vehicle systems. Next in importance is a thorough knowledge of the properties of the manufactured product, such as color, consistency, and hiding, and also of adhesion, permeability, and structure of the dried film. This knowledge is of specific value in the design and control of finished products to meet definite requirements.
Microscopy is coming into its own in the field of protective coatings. It is valuable for the examination of both pigments and paint films.
At this time, the paramount interest in emulsions and especially in emulsifiable paints necessitates a more extended discussion of emulsions than was given in previous volumes of this series.
The application of high-vacuum technology is vital in the segregation of drying oils into their relatively slower-drying and harder-drying constituents (the latter to serve as substitutes for tung oil, which is no longer available because of the war). Investigations in this field are important and should continue after the war.
Finally, the ultraviolet absorption studies of drying oils give us an insight into the chemical and structural changes that take place during the heat-bodying of drying oils. Knowledge of what these changes are accounts for the improved properties of the bodied oils.
The subjects presented in this volume of the series warrant continued investigation and clarification. It is hoped that their presentation will encourage others to initiate studies which may carry the industry further into the realm of science.
As editor of this book, I wish to express my sincere appreciation to the contributors, whose cooperation and sound advice have been invaluable In the preparation of this volume.
I feel particularly grateful to Carl J. Schumann, Lonnie W. Ryan, Lincoln T. Work, John F. Broeker, Vincent C. Vesce, Robert J. Moore,
Austin 0. Allen, John C. Moore, Raymond E. Kirk, Durant W. Robertson, Ralph H. Everett, William .1. Greco, John J. Bradley, Frank Brescia, William Howlett Gardner, Guido Henry, and Captains Arthur W. Van Heuckeroth and T. F. Cooke, Jr., for their advice and assistance.
For reviewing chapters of this volume of the series, I am indebted to Henry J. Stalzer, Dominick D. Razzano, Thomas J. Craig, William Wright, Clayton R. Cornthwaite, Kenneth J. Howe, William L. Schwalb, Burton Hannewald, Frank Munns, Majors E. L. Hobson and A. I. Totten, Jr., those mentioned in the previous paragraph, and the collaborators.
I wish to thank Miss Dorothy V. Duffy and Miss Rose Reynolds for typing much of the material and for other assistance.
To the American Chemical Society, the American Society for Testing Materials, the National Paint, Varnish and Lacquer Association, and other associations and business corporations, I make grateful acknowledgment for permission to use material previously published by them.

Joseph J. Mattiello
New York
January, 1944

CONTENTS

1. THE THEORETICAL AND PRACTICAL ASPECTS OF WETTING 1
Austin O. Allen, M.S.
Vice-President and Technical Director, Vita-Var Corporation Alexander Knoll, Ph.D.
Chief Chemist, Flake Laboratory, Metals Disintegrating Company Lonnie W. Ryan, M.S.
Technical Director, United Color and Pigment Corporation Charles A. Murray, Ph.D.
Reichhold Chemicals, Inc.
2. THEORY OF GRINDING . 80
Henry L. Beakes, B.Chem.
Director, Customer Service Department, Kentucky Color and Chemical Company
3. COLOR .95
M. Rea Paul
War Production Board
4. CONSISTENCY. 106
Henry Green, B.S.
Head of the Physical Department, Intcrchemical Corporation Laboratories
Louis A. Melsheimer, Ch. E.
United Color and Pigment Corporation
5. HIDING. .141
Earle Watson McMullen, M.S.
Director of Research, Eaglc-Picher Lead Company Everett J. Ritchie, M.S.
Paint Research Chemist, Eagle-Picher Lead Company
6. THE ADHESION OF DRIED COATINGS . . 173
Lincoln T. Work, Ph.D.
Director of Research and Development, Metal and Thermit Corporation
Gilbert M. Leigh, B.S.
Chemical Engineer, Metal and Thermit Corporation
7. ADSORPTION, PERMEABILITY, WATER RESISTANCE, AND
STRUCTURE OF ORGANIC SURFACE COATINGS 194
Henry Fleming Payne, M.S. Development Chemist, American Cyanamid Company

8. LIVERING OP PRINTING INKS .223
Herbert J. Wolfe, B.S.
V'ice-President in Charge of Research, Kienle and Company
9. MICROSCOPY IN THE PAINT AND VARNISH INDUSTRY 233
Roscoe H. Sawyer, M.S. R(search Division Head, E. 1. du Pont de Nemours and Company
10. HIGH-VACUUM TECHNOLOGY .259
Richard S. Morse, Ph.D. President, National Research Corporation
11. EMULSIONS.275
Georgk M. Sutheim, Ch. E. Chemist, Atlantic Calsomine Company, Inc.
12. ULTRAVIOLET ABSORPTION STUDIES OF DRYING OILS 362
J. Peter Kass, Ph.D.
Senior Chemist, Interchemical Corporation; formerly Senior Chemist, Northern Regional Research Laboratory, United States Department of Agriculture
INDEX .407

INDEX

Abrasion resistance, 205 Abrasion test, 191 Absorption, 195
Absorption spectrophotometry, .see Spee-trophotometry, ultraviolet absorption Adhesion, 3, 11, 38, 41
free energy of, see Work of adhesion work of, see Work of adhesion of dried coatings, 173-193 factors affecting, 174—178 test methods, 174, 178-191 base deformation, 186-189 conical mandrel, 187-188 elongation, 188 Erichsen, 188 mandrel, 186-187 impact, 189-191
Hart impact tester, 189 swinging pendulum test, 190-
191
miscellaneous, 191 abrasion test, 191 jet test, 191
stretching or gouging test, 182-180 Nettmann, 184 New York Production Club,
182-184
Rossmann, 184-186 tensile strength, 178-182
Courtney and Wakefield test,
180-181
Gardner-Parks, 181-182 New York Production Club,
179-180
Schmidt test, 178-179 of dried film, 205 Adhesion constant, 37 Adhesion tension, 2, 29, 33, 34, 35, 36, 37, 43, 44, 46, 48; see also Spreading pressure Adsorbate, 199
Adsorbed layer, 12, 46-47 Adsorption, 3, 8, 35, 39, 42-46, 194, 195-199, 287-291
absorption and surface area, 43, 45, 46, 195
chemical, 196, 198
chemosorption, 197
definition, 42, 195-197, 287
dipoles in, 196
electrical, 196-199
influence on surface tension, 42, 288
mechanical, 196, 198
negative, 42, 287, 288
oriented, 291
polar, 196-199
positive, 42, 287-288
preferential, 48
secondary valence forces in, 196
selective, 35
sorption, 195, 197 Alginate, 311
Alkalies, 299, 300, 301, 315, 319, 336, 341, 344
action in emulsion paint films, 336
buffered, 319, 341
free, in emulsion formulas, 300, 341, 344
in emulsion paint formulas, 341, 344
soaps as emulsifying agents, 299-301 Alkalinity of the underground, 337 Ammonium soap, 300-302, 336 Angle of contact, see Contact angle Anti-foaming agents, 339, 341 Antonoffs rule, 11
Bacterial activity, 320 Bartell-Osterhof equation, 35 Bartell's cell, 15, 33, 35, 36, 37, 38, 54 Bentonite, 281, 299
Bodying agents, 311, 320, 322, 339, 340 Breaking of emulsions, 318, 324, 327-329
Breaking of emulsions, definition, 327
description of, 328
desirable, 327
factors of influence on, 327
speed of, 329
undesirable, 327, 328 Brownian movement, 281, 327 Brushes, 337 Bubble attachment method, 13
Calcium tolerance, 301, 302, 305, 306,
308, 310, 319
by blocking the carboxyl group, 305 lack of, 301, 319 of emulsifying agents, 301, 302, 305,
308, 310 Capillarity, 7 Capillary rise, 6, 16, 285 Casein, 311, 312, 319
evaluation as emulsifying agent, 312 hydrolysis of, 319 Casein paint, 333, 334 Cataphoresis, 52 Cellulose, 202
Chemical constitution, 372-375; see also Ultraviolet absorption of drying oils and Spectrophotometry, ultraviolet absorption Chemical resistance, 205 Cholesterol, 313 Close packjng of particles in emulsions,
320-321
Clustering of emulsions, 327 Coalescence of emulsified particles, 322,
323
Cohesion, 3, 173
Cohesive forces, 283, 284, 286, 287 Colloidal clay, see Bentonite Color, 95-105 achromatic, 96 as paint, 97-98 brightness, 96 brilliance, 96 chromatic, 96
classification by hue, 96-97 colorimeters, 102-103 definition of, 95 dominant wavelength, 104 hue, 96 lightness, 96
Color, luminosity, 96 names, 101-102 object-color perception, 96 perception, 96 purity, 104 reflectance, 104 saturation, 96 sensation, 96 specification of, 98-99 spectral reflection, 96-97 spectral reflectivity, apparent, 104 spcctrophotqmeters, 102, 103-104 standard colors, 97-98 stimulus, 95 systems of, 102-104 tolerance of, 99-101 value, 96
visible spectrum, 95 Concentrated emulsions, 314, 320-322,
325, 328
Consistency, 1, 54, 64, 106-140 Bingham body, definition of, 111 control of, 136-138 filler's influence, 136 in emulsions, 137 interfacial tension, 137 particle size influence, 137 pigment volume influence, 137 pigment's influence, 136 vehicle influence, 136 definitions of, 107
in measuring, 110-112 dilatancy, definition of, 112 false body, definition of, 112 flocculation, 132 flow, laminar, 114
definition of, 112 plug, 114
streamline, definition of, 112 telescopic, definition of, 112 turbulence, definition of, 112 fluidity, apparent, definition of, 111
coefficient of, definition of, 111 force-flow curve, 112 friction in, 109 history of, 107-110 introduction to, 106-107 liquid (Newtonian), definition of, 111
Consistency, liquids, pure (Newtonian),
110
measurement of, 116-132 instruments used, 120-132 capillary types, 121-124 efflux types, 121-124 falling ball types, 127-129 miscellaneous types, 129-132 perforated plunger types, 124-126 rising bubble types, 124-126 rotational types, 124-126 mobility, definition of, 111
coefficient of, definition of, 111 plastic flow, 109, 110
definition of, 112 plasticity, 108-109 pseudoplastic, definition of, 110, 113
definition of, 111 rhe, unit of fluidity, definition of,
111
rheological measurement, 116-132 rheology, 108 rigidity, definition of, 110 "terms" used in, 110-112 thixotropic systems, 133-135 thixotropy, 113
definition of, 112, 133 viscosity, coefficient of, definition of,
111
effect on, 135-136 kinematic, definition of, 111 plastic, definition of, 110
coefficient of, definition of, 111 yield stress, 108 yield value, 109, 132
definition of, 110 Contact angle, 2, 4, 8-16, 33, 34, 38, 39,
46, 47, 49, 50, 51, 58, 64 and spreading, 17 and wetting, 9, 11, 12 classification, 8-9 definition of, 9 determination of, 12-16 equations, 10, 30, 34 values of, 11, 12
Creaming of emulsions, 324-327 definition of, 324
difference between breaking and, 324 direction of, 325 downward, 325
Creaming of emulsions, factors of influence on, 325-327 Brownian movement, 327 particle size, 327 specific gravity of constituents, 326,
327
viscosity of the external phase, 327 speed of, 325 Stokes' law, 325, 326 upward, 325-326
De-emulsification, 328
Dilatancy, 57, 58; see also Consistency Dilute emulsions, 314, 321, 322, 328 Dispersing agents, 62-65; see also Surface
active agents Dispersion, 1, 2, 39, 59, 61, 280, 322
coarse, 280, 281
colloid, 280
definition, 280
degree of, 322
molecular, 280
pigments, see Grinding, theory of Displacement cell, 15 Displacement pressure, 37, 38 Dissociation of emulsifying agents, 298,
307, 308
Distensibility, 205 Dual emulsions, 315 Duplex film, 19, 20 Duprć equation, 7, 18, 22, 24, 25, 46
Electric double layer, 7, 52
Electric structure of molecules, 289
Electrokinetic potential, 52
Electron microscope, see. Microscope,
electron
Electrophoresis, 52-53 Emersion, 26, 27 Emulsifiable paint, 331, 349, 357-358
formulation of, 351
use of, 357
Emulsification, 316-318; see also Formation of emulsions
intermittent agitation, 317
spontaneous, 317
temperature of, 317
time of, 317
work of, 316
Emulsifying agents, 275, 286, 291, 292-
313, 319, 323, 324, 338-340 adsorption at the interface, 292 amino compounds, 301-303 and interfacial film, 293 anion active, 298-307 balance of polar and non-polar groups
in, 293 calcium tolerance of, 301, 302, 305,
308, 310
cation-active, 298, 299, 307-309 chemistry of, 297-313 classification, 297-299 chemical, 298-299 physical, 297
combinations of, 296, 338-340 definition of, 292 dissociation of, 298, 307, 308 equilibrium of polar and non-polar
portion in, 297 esters and ethers, 309-311 hydrophilic, 310 hydrophobic, 310 evaluation of, 301, 302, 305, 310, 339-
340
finely dispersed solids as, 298, 299 formation in situ, 300, 342, 344 hydrolysis of, 319, 320 hydrophilic, 294 hydrophobic, 294 in emulsion paint, 338-340 influence on type of emulsion formed,
314
list of, 350-356
natural or modified-natural, 298, SUSIS
non-dissociating, 298, 299 non-ionic, 298, 299 non-polar portion in, 296 orientation at the interface, 292, 293 phase reversal, 329 polar portion in, 297 reduction of interfacial tension by, 316 requirements on, 295-296 selectivity, 296
soaps, 299-301; see also Soaps alkali, 300 metallic, 301 solid, 295, 298, 313 special claims on the properties of, 296
Emulsifying agents, stability of, 296, 319 structure of, 296-297 sulfated compounds, 299, 303-305 alcohols, 304 oils, 304
sulfonated compounds, 299, 306-307 aliphatic, 305 aromatic, 306 synthesis of, 297, 299-310 use in emulsion paint formulations,
338-340, 344
volatile, 300-303, 307, 336, 340; sec also Ammonium soap and Mor-pholine
Emulsion paint, 331-349 advantages, 332 characteristics of, 331 classification, 331 evaluation of, 332 oil in water type, 332-347; see also
Emulsion paint O/W shortcomings, 332 water in oil type, 347-349; see also
Emulsion paint W/O Emulsion paint O/W, 332-347 compared with water paint, 332 description of, 336 drying of, 334
emulsifying agents in, 338-340 exterior, 337, 342, 346 formulation, 338-346; see also Formulation of emulsion paint hydrophobic film formed by, 333-336 interior, 337, 342, 346 properties of film, 336 reduction with water, 337 washability, 338 water resistance, 334, 336, 338 weather resistance, 338 wet abrasion test, 334 Emulsion paint W/O, 331, 347-349 as textile coatings, 348 drying of, 348 durability, 348 emulsifying agents in, 348 Emulsions, 275-361 addition to water paint, 333 adsorption as a factor in, 287-289;
see also Adsorption breaking of, 324, 327-329
Emulsions, coarse, 275, 327, 328 continuous phase of, 276 creaming of, see Creaming of emulsions definition of, 275 description of, 275 determination of type, 278 discontinuous phase of, 276 dual, 315 -emulsifying agents in, see Emulsifying
agents
external phase of, 276 fine, 275
formation of, see Formation of emulsions
internal phase of, 276 oil in water, 277 oil phase of, 276 O/W, 277
paint, see Emulsion paint particle size as a factor in, 281-283, 322, 323, 327; see also Particle size phase reversal, 329-330 phase-volume ratio, 314, 315, 320-322, 328, 329; see also Phase-volume ratio
phases of, 276
physical chemistry of, 283-291 polarity as a factor in, 289-291; see
also Polarity references to, 358
stability of, see Stability of emulsions structure of, 278
surface tension as a factor in, 283-286 temperature of, 286, 317, 322 two types of, 277 water in oil, 277 water phase of, 276 W/O, 277
Energy of cohesion, 3 of emersion, 28, 32 of immersion, 23, 24, 29, 31, 32 of separation, 28 Enthalpy, 26, 27 Entropy, 31
External phase of emulsions, 276 [zasłonięte] 327
False body in paints, 347; see also Consistency Fick's diffusion law, 203
Film pressure, 19-21, 50
Film structure, see Physical structure of
film Films, 19, 26, 35, 49, 50, 51, 293-295,
321, 323, 325, 328, 333-336 adsorbed, 26 duplex, 19, 20 emulsion paint, 333-336 hydrophilic, 334, 336 hydrophobic, 333-336 irreversible, 336 reversible, 336 in emulsions, 293-295, 321, 323, 325,
328
interfacial, 294, 295 mixed, 51
monomolecular, 50, 52, 55 non-duplex, 19
protective, 321, 323, 325, 327, 328, 335 references to, 50 Floating, 53, 62 Flocculation, 39, 40, 47, 53, 54, 55, 57,
58, 60, 64, 114 force of, 60 of a pigment, 135 Flotation, 14, 53 Flow, 1, 53, 60 laminar, see Consistency plastic, see Consistency streamline, see Consistency telescopic, see Consistency turbulence, see Consistency Fluidity, apparent, see Consistency
coefficient, see Consistency Foams, 281, 341
anti-foaming agents, 341 reduction of, 341 Formation of emulsifying agents in situ,
300, 342, 344 of emulsions, 313-318 influence of constituents, 315 of phase-volume ratio, 314 of the emulsifying agent, 314 order of incorporating ingredients,
315 formulation of emulsion paint O/W,
338-347
exterior paste paint, 346 interior paste paint, 346 oil phase, 342-343
Formulation of emulsion pamt O/W, pigmentation, 345, 346
table of ingredients, 339
vehicles, 343, 344, 345
water phase, 338-342 Free energy, 6, 21, 22, 26, 29, 32, 35
of adhesion, 3, 21; see also Work of adhesion
of emersion, 29
of immersion, 24, 29, 32, 34, 35
of interfaces, 5, 6
of phase transfer, 29
of surfaces, 5, 6, 17, 22 Freezing of emulsions, 324
Gibbs heat function, 30 Gloss, 1, 2 loss of, 2 Grinding, 1, 60 theory of, 80-94
corollary, 90-94
dispersion, 88-89
function of grinding, 80—82
liquid functions, 80—82
mill setting, 85
mixing, 82-83
particle size, 89-90
pigments functions, 80-82
roller mill, 83-85
technique, 86-88
vehicle functions, 80—82
wetting, 88-89 Gums, water-soluble, 311, 320
Haftspannung, 29
Heat of wetting, 2, 7, 23-29, 41, 54, 55
Heat function, 30, 31
Heterogeneity, 278
Heterogeneous systems, 279
emulsion paint as, 331
emulsions as, 279
Hiding, 141-172; see also Hiding power and Opacity of paint films
complete, 142
dry, 167-169; see also Hiding, wet
maximum, 142
mechanism of, 142-143
particle size, 142, 143
refractive index influence, 142
Hiding, wet, 167-169; see also Hiding, dry Hiding power, 149-170; see also Hiding
and Opacity of paint films color, effect on, 148-149 control of, 149-152 absolute pigment, 149 anomalies, 150
fineness of grind, effect on, 151 grind fineness, effect on, 151 particle shape, effect on, 151-152 particle size, effect on, 151-152 pigment, actual values, 149 pigment combination choice, 149-
150
vehicles choice, 150-151 definition of, 152 films, multiple versus single, 168 measurement of, 152-168 absolute hiding, 153 Baltimore Production Club, 155,
165, 167
brightening power, 156 Bruce, 159 brush out and weigh, 153, 154, 155,
157, 158, 161
contrast obliterating power, 157 contrast ratio, 157, 158 cryptometer methods, 160—161
Pfund's, 160
Sward's, 160
Doctor Blade methods, 159-160 dry hiding, 167 evaluation, 154 Gardner method, 155 Hallett methods, 157-158 Haslam method, 156 Jacobsen and Reynolds, 158 Kraemer and Schupf, 161 McMullen, Ritchie, and Bullard,
161-167
photometrically, 159 Pfund, 160, 161 practical test, 153 recommendation, general, 169-170 relative hiding, 153 roller coating, 154, 161 sample preparation, 153-154 Sawyer, 158 spin and weigh or measure, 153, 155,
156, 159
Hiding power, measurement of, spray
and weigh or measure, 153, 161 Sward's cryptometer, 160 weigh or measure (Doctor Blade
type), 154, 159 wet hiding, 167 of paint, 141 of pigment, -141 particle size influence, 148, 151 pigment color influence, 148 pigment concentration, 148, 164-166 reflectivity versus film thickness and
pigment concentration, 162-166 refractive index, effect on, 142, 143; see also Refractive indices of pigments and Refractive indices of vehicles
refractive index influence, 148 scattering power, 146 spreading rate, 152 tinting strength as a measure of, 168-
169
High-vacuum technology, 259-274 distillation, molecular, 267 analytical, 272 apparatus for, 268, 269 methyl esters of dehydrated castor
oil, 272
of drying oils, 271, 272 fish oils, bodied, 272 linseed, polymerized, 271 distillation in, 267-273 measurement of low pressures, 259-
262
type of gages, 260-262 ionization, 261-262 Knudsen, 261, 262 McLeod, 260, 261, 262 Mercury manometer, 262 oil manometer, 260, 262 Pirani, 261, 262 Thermocouple, 261, 262 Viscosity, 262
methods of expressing pressure, 260 atmospheres, 260 dynes /cm., 260 lb./in.2, 260 mean free path, 260 mm. Hg., 260 molecules per cm.3, 260
High-vacuum technology, production of
high vacuum, 262-267 diffusion pumps in, 265-267 mechanical pumps in, 262-264 compound type pumps, 263 eccentric cylinder type, 263 high-vacuum pumps, 263 piston type, 263, 264 vane-type rotary pumps, 262, 264 steam ejectors in, 262, 263 Homogeneity, 278 Homogenization, 323 Hydrolysis of emulsifying agents, 319-
320, 324
Hydrophilic films, 334, 336 Hydrophilic substances, 6, 28, 36, 47,
48, 49, 50, 276, 294, 313, 336 emulsifying agents, 294 examples of, 276
solid, 6, 28, 36, 47, 48, 49, 50, 313 Hydrophobie films, 333-336 Hydrophobie substances, 28, 47, 48, 276,
294, 313
emulsifying agents, 294 examples of, 276 solid, 28, 47, 48 Hysteresis, 12, 13
Imbibition, 199; see also Physical structure of film adsorbate, 199 gelation, 199 pressure, 199, 202 relative polarity, 199 swelling, 199 Immersion, 38
energy of, 24, 29, 34 free, 24, 25, 26, 29, 32, 34, 35, 38 total, 24 work of, 38 Impact resistance, 205 In situ formation of emulsifying agents,
300, 342, 344 Interface, 1, 2, 3, 7, 22, 38, 61, 279 between liquid and liquid, 7, 22 between liquid and vapor, 7, 22 between pigment and air, 1 between pigment and vehicle, 1, 2,
61 between solid and liquid, 3, 7, 38
Interfaoial area in emulsions, 279 Interfacial energy, 2, 5, 29, 46, 47
free, 5, 6, 14, 15 Interfacial film, 294, 295
and emulsifying agents, 293
curvature of the, 295 Interfacial relations, 2, 53-62, 285, 286, 292, 293
in emulsions, 285, 286, 292, 293
in paint, 53-62
Interfacial tension, 5, 6, 7, 8, 10, 11, 12, 15, 21, 22, 36, 285-286, 292, 295
and temperature, 286
at solid-liquid interfaces, 10
explanation of, 285
reduction of, 286, 288, 292, 295, 316
values of, 286
Interior emulsion paint, 337 Internal phase of emulsions, 276 Irreversible films, 296, 336; see also Hydrophobie films
Kinetic energy and surface tension, 283
Langmuir-Harkins theory, 41
Latent heat, 24, 30, 31
Lecithin, 313
Lens formation, 9, 17, 20
Leveling, 1, 53
Liquid, Newtonian, sec Consistency
Liquid-liquid interface, 7, 22
Liquid-solid interface, 7, 22
Liquid-vapor interface, 7, 22
Livering, 223-232
acidity, effect on, 225-227
definition of, 223
elimination of, 231-232
history of, 223-224
in lithographic varnishes, 224-227 acidity influence, 225-227 livering area chart, 227 non-livering area chart, 227 temperatures, influence, 225 viscosity, influence, 226
moisture, effects, 230-231
pigment influence, 225
plasticizers, influence?, 229-230
salts effects, 230
solvent influences, 229-230
tests, accelerated, 228, 229
Livering, tests, control, 229
practical, 228-229 viscosity of varnishes, effects, 231
Manufacture of emulsion paste paint, 347 Metallic soap as emulsifying agents, 299 Methylcellulose, 311 Microscope, 233-258 construction of, 234-238 illumination, 236, 237 dark field, 237 vertical, 237 resolving power, 235 electron, 251-255
pigment examination, 252-255 resolving power, 252 history of, 233-234 use of, 238-251
dried paint films, 247-251 qualitative analysis, 250 fluid paints, 245-247 in particle size measurements, 238-
245
pigment examination, 238-245 fluorescence in, 240 infrared illumination, 240 ultramicroscope, 240 ultraviolet light, 239-240 Microscopy in the paint and varnish industry, 233-258; see also Microscope
Mildew, 320
Mixed non-polar polar molecules, 290 Mobility, see Consistency Mobility, coefficient, see Consistency Monolayer, 49, 50, 51 Monomolecular film, 50, 52, 55 Morpholine, 302, 303, 307 dissociation of, 307
Newtonian liquid, see Consistency Non-polar groups, 199-200, 290 Non-polar liquids, 49, 50 Non-polar molecules, 289 Non-polar solids, 28, 48
Octyl alcohol, 341 Oil phase of emulsions, 276 Opacity of paint films, 145-148; see also Hiding and Hiding power
Opacity of paint films, film thickness, 145
light diffusely transmitted, 145
light distribution, 147
light transmitted, 145
optical properties, 146
pigment concentration, 146
reflection measurements, 146 Organic amines as emulsifying agents,
299
Orientation, 4, 29, 39, 40-42, 59, 60, 291-293, 330
and wetting, 40-42 Oriented adsorption, 41, 291 Osmosis, 203 Ostwald's equation, 10 Oxygenated structure, 202
Paint, 53-62, 331-358
emulsifiable, 331, 349, 357-358
emulsion, see Emulsion paint
false body in, 347
thixotropic structure of, 58
wetting phenomena of, 53-62 Palmitic acid, 296
shape of the molecule, 296 Particle size, 281-283, 322, 323, 327
determination of, 283
dominant, 281
influence on creaming, 327 on stability, 323 on viscosity, 322
optimum range, 323
range of, 281 Pasteurization, 318 Pectin, 313
Pénétrants, 62-65; see also Surface-active agents Permeability, 194-222
change of, with different coatings, see Physical structure of films
coefficient, 206
definition of, 215
elongation, variation in, 220
free film, 214, 215
Henry's law, 207
humidity differential, 214
initial, 218
rate of permeation, 203
research review on, 205-211
semi-permeable membrane, 214
Permeability, specific, definition of, 215 swelling in, 220 tensile strength, 220 vapor pressure differential, 206, 216 Phase inversion, 329 Phase reversal, 329, 330 description of, 329 factors of influence on, 330 influence of emulsifying agents on, 329,
330
reasons of, 329 Phase-volume ratio, 314, 315, 320-322,
325, 328, 329 definition, 314 influence on stability, 320
on type of emulsion formed, 314 on viscosity, 322 Phases of emulsions, 276 Photochemical resistance, 205 Physical structure of film, 194-222 adsorption, 195-199; see also Adsorption
absorption, 195 sorption, 195 "brush heap," 194 fibrils, 194 film structure, 194 gel formation, 194 imbibition, i99; see also Imbibition intermicellar capillaries, 203 linear, 202 orientation, 200-201 osmosis, 203
polarity, 199-204; see also Polarity porosity, 195
rate of evaporation, effect on, 208 three-dimensional, 202 types, 208-211 air-dried, 208 alkyd, 208 baked, 208 linseed oil, 206, 208 nitrocellulose, 208 paraffin wax, 206 pigment films, 209-211 varnish, 208 xerogel, 198 Pigment-air interface, 1 Pigment flooding, 135 Pigment-vehicle interface, 1, 2, 61
Pigment-vehicle ratio, 60, 61 Pigmented systems, 132-133 Pigments, 1, 6
coated, 65
hydrophilic, 6
in emulsion paint, 335, 339, 345-346
refractive indices of, 143 Pine oil, 341
Plastic flow, see Consistency Plasticity, see Consistency Poiseuille's formula, 16 Polar compounds, 49, 50, 55, 56 Polar groups, 17, 21, 28, 41, 290, 292,
293, 297, 309, 310 Polar liquids, 49, 50 Polar molecules, 199-200, 289 Polar solids, 28 Polarity, 28, 48, 199-204, 289-291
and molecular symmetry, 289
octupoles, 199
polar moment, 199
quadrupoles, 199
solubility, 290 Polymerization, 202 Polyoxyalkylene condensates, 310 Porosity, 195 Preservatives in emulsion paint, 340, 341
in emulsions, 318, 320 Protective colloids, 311, 320 Protective film, 321, 323, 325, 328, 335 Pseudoplastic, see Consistency Putrefaction bacteria, 320
Quaternary ammonium salts, 307, 308
Refractive indices of pigments, 143
of vehicles, 144 Reversed soaps, 308 Rhe, see Consistency Rheology, see Consistency Roller coater, 337
Sealer, 338
Sedimentation, 39-40, 325-326
Stokes' law of, 325-326 Sedimentation volume, 4, 39,40,49,50,60 Settling, 2, 39, 54, 58, 325, 337 Size frequency analysis, 281 Soaps, 289, 293, 299-301, 339-340, 344
alkali, 300
Soaps, amino, 301-303
ammonium, 300-302, 336
formation in situ, 300, 342, 344
in emulsion paint, 339-340, 344
lowering of surface tension by, 289
metallic, 301
neutrality point of, 301, 302
reversed, 308 Sodium oleate, 289-293 Solid-air interface, 11, 14 Solid-liquid interface, 3, 11, 14, 38 Solids, 36
as emulsifying agents, 295, 298, 313
hydrophilic, 36, 47, 48, 49, 50, 313
hydrophobic, 47, 48
neutral, 36
non-polar, 48, 49
organophilic, 36, 48, 49, 50
polar, 48, 49
surface characteristics of, 47 Solubility, 10, 290, 291, 314
and polarity, 290, 291
of emulsifying agents, 314
of particles, 10 Specific gravity, 322, 325, 326, 329
of emulsion constituents, 326 Specific surface, 46
Speotrophotometry, ultraviolet absorption, 363-375; see also Ultraviolet absorption of drying oils
analysis, quantitative, 381-385
chemical constitution and absorption spectra, 363, 372-375
methods for, 369-372
principles of, 363-375
absorption intensity, quantitative,
366-369
absorption spectra, 363, 372-375 chemical constitution by, 372-375 spectral region, definition, 303-386 Spontaneous emulsification, 317 Spray gun, 337 Spreading, 3, 5, 7, 16-21
and contact angle, 17
theories of, 17
work of, 39 Spreading coefficient, 2, 4, 7, 16-21, 58
final, 19
initial, 19
semi-initial, 19
Spreading pressure, 29-33, 37 final, 30 initial, 30 semi-final, 30
Spreading rate, see Hiding power, spreading rate
Spreading wetting, 39 Stability of emulsions, 318-324 dangerous zone, 321, 328 factors of influence, 318 influence of emulsifying agents on, 319 of particle size, 323 of phase-volume ratio on, 320 of temperature, 323 of viscosity, 322 major changes of, 318 minor changes of, 318 zone of maximum stability, 321 Stokes' law of sedimentation, 325, 326 Structure of organic coatings, 194—222 of organic film, physical, 194-204; see
also Physical structure of film gel formation, 194 Sulfated alcohols, 304, 305 Sulfated castor oil, 304 Sulfated compounds as emulsifying
agents, 299, 303-305, 306-307 Surface, 43, 45, 46, 274; see also Surface
tension
definition, 279
importance in emulsions, 283 Surface-active agents, 42, 60, 61, 62-65;
see also Emulsifying agents action on pigments, 63, 64 classification, 63, 64 polar groups in, 63 references to, 65 Surface area, 43, 45, 46 Surface energy, 4-6, 284; see also Surface tension explanation of, 4 free, 4, 5 references to, 8 Surface films, 284
Surface tension, 5, 8, 9, 21, 134, 283-286 and temperature, 286 definition, 283
determination of, 6, 284-285 capillary rise method, 6, 285 drop number method, 285
Surface tension, determination of, drop
weight method, 6, 285 important methods, 6 references to, 6 tensiometer method, 285 influence of adsorption on, 288 origin of, 283 reduction of, 288, 289 values of, 285
Suspensions, 55, 58, 61, 280 Symbology of wetting, 2 Symmetry of molecules, 289, 290
Temperature, 286, 317, 323
and emulsification, 317
and stability, 323
and surface tension, 286 Tensile strength, see Adhesion, lest methods
Thermal motion of molecules, 291 Thixotropy, 56, 57, 60, 61; see also Consistency
Traube's rule, 8, 43 Triethanol amine, 302, 303 Turkey red oil, 304 Type of surface coatings, 204
inorganic, 204
metallic, 204
organic, 204
Ultraviolet absorption of drying oils,
362-405; see also Spectrophotome-
try, ultraviolet absorption absorption spectra, 373, 385-389, 391 conjugated compounds, dienoic, 373 drying and related oils, 385-389
castor, 386
corn, 386
dehydrated castor, 386
linseed, 386
alkali-conjugated, 386
oiticica, 386
olive, 386
perilla, 386
rapeseed, 386
sardine, 386
soybean, 386
alkali-conjugated, 386
tung, 386 fatty acids, 375-381, 391
Ultraviolet absorption of drying oils,
application of, 389-404 absorptive changes in oils, bleaching,
402-403
blowing, 401-402 bodying, 396-401 deodorized, 402-403 refining, 402-403 analysis, 389-392 isomerization studies, 392-396 miscellaneous, 403—404 structure studies, 392-396
Valence, primary, 198
secondary, 198, 202 Vehicles, refractive indices, 144 Viscosity, 40, 322, 323
coefficient, see Consistency
kinematic, see Consistency
of emulsions, 322, 323
plastic, see Consistency
coefficient of, see Consistency Volatile thinners in emulsion paint, mineral spirits, 326
specific gravity of, 326
Washability of emulsion paints, 332-334,
340, 357
Water-air interface, 42 Water-dispersible drying oils, 342 Water-dispersible pigments, 346, 347 Water paint, 332-333 improved, 333 washability, 334 Water phase of emulsions, 276 Water resistance, 194, 201, 203, 205, 211-
220
methods for measuring, 211-220 Burr and Stamm's, 216 chemical reactions, 219-220 Bauer and Gonser's, 219 copper sulfate in, 219, 220 dialysis in, 220 Kirsch's, 219
méthylene blue in, 219, 220 Toeldte's, 220
electrical breakdown, 218-219 dielectric strength test, 218 Dixmier's, 218 Hague's, 219
Water resistance, methods for measuring electrical breakdown, Niesen's, 219
Wulff-Kondatski's, 219 permeability apparatus, 214-218;
see also Permeabilit y Bell Telephone Laboratories, 215 Gardner's, 214 Gettens and Bigelow's, 215 Jenckel and Woltmann's, 216 Kittelberger's, 214 Lishmund and Siddle's, 217 McBain-Baker's, 217 Muckenfuss's, 214 New York Paint and Varnish
Production Club, 215, 216 Newsome, 217 Payne cup, 215, 217 Payne and Gardner's, 214, 217 standard, 216 Taylor, Hermann, and Kemp's,
217 water immersion, 211-213
boiling water method, 211-212 cold water method, 211 Forest Products method, 213 glass plate method, 212-213 microscope slide, 212 Water-soluble salts, 324, 341 Weather resistance of emulsion paint,
338, 357
Wet abrasion test, 334, 357 Wetting, 1-79
and adhesion of particles, 52
and adsorbed layer, 46
and adsorption, 42-46
application to paint, 53-62
chemical aspects of, 51
complete, 12
contact angle, 8-11; see also Contact
angle
complete wetting, 12 no wetting, 12 partial wetting, 11, 12 definition of, 3 degree of, 4 early history of, 7 electric relations, 52 good, 54, 56, 58 heat of, 2, 7, 23-29, 41, 54, 55
Wetting, no, 12
orientation, 40-42
partial, 12
poor, 53, 55, 58
references to, 66-79
relation to other phenomena, 40-52
three types of, 38
Wetting agents, 6, 62-65; see also Surface-active agents Wetting power, 21 Withelmy balance, 6, 13
Work of adhesion, 2, 4, 7, 18, 19, 21-23,
30, 38, 39, 46 of cohesion, 18 of flocculation, 47 of immersion, 38, 47 of spreading, 39, 58
Xerogel, 198
Yield value, 60,61,64; see also Consistency
Zeta (?) potential, 52, 53

PREFACE

This is the fourth volume of a set of books dealing with the protective and decorative coatings industry. It presents to the technologist the most important subjects concerned with pigmented coatings, both during and after manufacture, and in the dried film.
Of first importance is the practical application of wetting and grinding principles in pigment-vehicle systems. Next in importance is a thorough knowledge of the properties of the manufactured product, such as color, consistency, and hiding, and also of adhesion, permeability, and structure of the dried film. This knowledge is of specific value in the design and control of finished products to meet definite requirements.
Microscopy is coming into its own in the field of protective coatings. It is valuable for the examination of both pigments and paint films.
At this time, the paramount interest in emulsions and especially in emulsifiable paints necessitates a more extended discussion of emulsions than was given in previous volumes of this series.
The application of high-vacuum technology is vital in the segregation of drying oils into their relatively slower-drying and harder-drying constituents (the latter to serve as substitutes for tung oil, which is no longer available because of the war). Investigations in this field are important and should continue after the war.
Finally, the ultraviolet absorption studies of drying oils give us an insight into the chemical and structural changes that take place during the heat-bodying of drying oils. Knowledge of what these changes are accounts for the improved properties of the bodied oils.
The subjects presented in this volume of the series warrant continued investigation and clarification. It is hoped that their presentation will encourage others to initiate studies which may carry the industry further into the realm of science.
As editor of this book, I wish to express my sincere appreciation to the contributors, whose cooperation and sound advice have been invaluable In the preparation of this volume.
I feel particularly grateful to Carl J. Schumann, Lonnie W. Ryan, Lincoln T. Work, John F. Broeker, Vincent C. Vesce, Robert J. Moore,
Austin 0. Allen, John C. Moore, Raymond E. Kirk, Durant W. Robertson, Ralph H. Everett, William .1. Greco, John J. Bradley, Frank Brescia, William Howlett Gardner, Guido Henry, and Captains Arthur W. Van Heuckeroth and T. F. Cooke, Jr., for their advice and assistance.
For reviewing chapters of this volume of the series, I am indebted to Henry J. Stalzer, Dominick D. Razzano, Thomas J. Craig, William Wright, Clayton R. Cornthwaite, Kenneth J. Howe, William L. Schwalb, Burton Hannewald, Frank Munns, Majors E. L. Hobson and A. I. Totten, Jr., those mentioned in the previous paragraph, and the collaborators.
I wish to thank Miss Dorothy V. Duffy and Miss Rose Reynolds for typing much of the material and for other assistance.
To the American Chemical Society, the American Society for Testing Materials, the National Paint, Varnish and Lacquer Association, and other associations and business corporations, I make grateful acknowledgment for permission to use material previously published by them.

Joseph J. Mattiello
New York
January, 1944

CONTENTS

1. THE THEORETICAL AND PRACTICAL ASPECTS OF WETTING 1
Austin O. Allen, M.S.
Vice-President and Technical Director, Vita-Var Corporation Alexander Knoll, Ph.D.
Chief Chemist, Flake Laboratory, Metals Disintegrating Company Lonnie W. Ryan, M.S.
Technical Director, United Color and Pigment Corporation Charles A. Murray, Ph.D.
Reichhold Chemicals, Inc.
2. THEORY OF GRINDING . 80
Henry L. Beakes, B.Chem.
Director, Customer Service Department, Kentucky Color and Chemical Company
3. COLOR .95
M. Rea Paul
War Production Board
4. CONSISTENCY. 106
Henry Green, B.S.
Head of the Physical Department, Intcrchemical Corporation Laboratories
Louis A. Melsheimer, Ch. E.
United Color and Pigment Corporation
5. HIDING. .141
Earle Watson McMullen, M.S.
Director of Research, Eaglc-Picher Lead Company Everett J. Ritchie, M.S.
Paint Research Chemist, Eagle-Picher Lead Company
6. THE ADHESION OF DRIED COATINGS . . 173
Lincoln T. Work, Ph.D.
Director of Research and Development, Metal and Thermit Corporation
Gilbert M. Leigh, B.S.
Chemical Engineer, Metal and Thermit Corporation
7. ADSORPTION, PERMEABILITY, WATER RESISTANCE, AND
STRUCTURE OF ORGANIC SURFACE COATINGS 194
Henry Fleming Payne, M.S. Development Chemist, American Cyanamid Company

8. LIVERING OP PRINTING INKS .223
Herbert J. Wolfe, B.S.
V'ice-President in Charge of Research, Kienle and Company
9. MICROSCOPY IN THE PAINT AND VARNISH INDUSTRY 233
Roscoe H. Sawyer, M.S. R(search Division Head, E. 1. du Pont de Nemours and Company
10. HIGH-VACUUM TECHNOLOGY .259
Richard S. Morse, Ph.D. President, National Research Corporation
11. EMULSIONS.275
Georgk M. Sutheim, Ch. E. Chemist, Atlantic Calsomine Company, Inc.
12. ULTRAVIOLET ABSORPTION STUDIES OF DRYING OILS 362
J. Peter Kass, Ph.D.
Senior Chemist, Interchemical Corporation; formerly Senior Chemist, Northern Regional Research Laboratory, United States Department of Agriculture
INDEX .407

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