MNL17-EB/Jun. 1995

Author Index


Ashton, Harry E., 696 Gale, Frances, 725 Pellowe, Don, 53
Athey, Robert D. Jr., 415 Gavett, Benjamin, 706 Perera, Dan Y., 585
Austin, M. Jay, 238 Gu6vin, Paul R. Jr., 555, 600 Petraitis, D. J., 95
Aviles, Julio I., 507 Price, Martin B., 717
Pulley, David F., 683

B Hacker, Larry R., 741 R
Hammond, Harry K. III, 447, 470
Bauer, Ronald S., 74 Hansen, Charles M., 383 Ralston, Henry P., 217
Bierwagen, Gordon P., 369 Hartshorn, Jack H., 826 Reiger, Carl J., 229
Billmeyer, Fred W. Jr., 447 Heitkamp, A1 53 Ryntz, Rose A., 711
Brandau, Alan H., 662 Hegedus, Charles R., 683
Braun, Juergen H., 159 Hicks, Lon S., 619
Brezinski, Darlene, 753 Hill, Loren W., 534
Hirst, Donald J., 683 S
Brezinski, J. John, 3
Broekhaus, Raymond D., 289 Santer, J. Owen, 60
Burns, Richard J., 99 Scarborough, Victoria, 748
Schaeffer, Leonard, 481
Kight, Robert W., 85 Schmitt, Thomas M., 835
C Kigle-Boeckler, Gabriele, 470 Schnall, Marvin J., 30
King, Vanja M., 261 Shay, Gregory D., 268
Campbell, David L., 654 Koleske, Joseph V., xi, xiii, 26, 89, 108, Sheehan, John G., 815
Carlozzo, Ben J., 15 252 Sherbondy, Valerie D., 643
Crewdson, Michael J., 619 Krauskopf, Leonard G., 115 Siegmund, A1, 731
Curtis, L. G., 23 Sliva, Thomas J., 439, 725, 748
Smyrl, William H., 609
L Snider, A. Monroe, Jr., 871
Spadafora, Stephen J., 683
Lewis, Peter A., 190, 209 Spindel, Saul, 735
Spinelli, Frank R., 179
Domingo, Rolando, 789
E Marx, Edward J., 74
Mills, George D., 305, 767, 865 Tan, Peter, 115
Eley, Richard R., 333 Miranda, Thomas J., 407
Ellis, Wayne, 667, 677, 891 Morse, Mark P., 525, 547
Eng, Anthony T., 683 W
Eppler, Richard A., 68, 214
Watkins, Michael J., 74
Neag, C. Michael, 841 Weldon, Dwight G., 783
F Nelson, Gordon L., 5~13 Wenzler, C. M., 424

Ferguson, Russell L., 223
Fletcher, J. F., 424 O Y
Friel, John M., 39
Fry, John S., 79 Odell, Loren B., 731 Yuhas, Stephen A. Jr., 125

‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬

Paint and Coating
Testing Manual
Fourteenth Edition of the
Gardner-Sward Handbook

Joseph V. Koleske, Editor

ASTM Manual Series: MNL 17
ASTM Publication Code Number (PCN)

1916 Race Street, Philadelphia, PA 19103
‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬

Library of Congress Cataloging-in-Publication Data
Paint and coating testing manual: fourteenth edition of the Gardner-Sward handbook/Joseph V.
Koleske, editor.
p. cm.--(ASTM manual series; MNL 17)
Rev. ed. of: Paint testing manual. 13th ed. 1972.
"ASTM publication code number (PCN) 28-017095-14."
includes bibliographical references and index.
ISBN 0-8031-2060-5
1. Paint materials--Testing. 2. Paint materials--Analysis.
I. Koleske, J. V., 1930- . II. Paint testing manual. III. Series.
TP936.5.P34 1995
667'.6--dc20 95-10632

All rights reserved. This material may not be reproduced or copied, in whole or in part, in any
printed, mechanical, electronic, film, or other distribution and storage media, without the written
consent of the publisher.

Photocopy Rights

Authorization to photocopy items for internal or personal use, or the internal or personal
use of specific clients, is granted by the AMERICAN SOCIETY FOR TESTING AND MATE-
RIALS for users registered with the Copyright Clearance Center (CCC)Transactional
Reporting Service, provided that the base fee of $2,50 per copy, plus $0.50 per page is paid
directly to CCC, 222 Rosewood Dr., Danvers, MA 01923; Phone: (508) 750-8400; Fax:
(508) 750-4744. For those organizations that have been granted a photocopy license by
CCC, a separate system of payment has been arranged. The fee code for users of the
Transactional Reporting Service is 0-8031-2060-5-95 $2.50 + .50.

NOTE: This manual does not purport to address (all of) the safety problems associated with its
use. It is the responsibility of the user of this manual to establish appropriate safety and health
practices and determine the applicability of regulatory limitations prior to use.

Printed in Ann Arbor, MI
June 1995
‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬


THIS PUBLICATION, Paint and Coating Testing Manual: Fourteenth Edition of the
Gardner-Sward Handbook, was sponsored by Committee D- 1 on Paint and Related
Coatings, Materials, and Applications. The editor was Joseph V. Koleske. This is
Manual 17 in ASTM's manual series.

‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬


ASTM WOULDLIKE TO EXPRESS its gratitude to the authors of the previous 13
editions of this publication. These publications made significant .contributions to
the technology; therefore, ASTM, in its goal to publish books of technical signifi-
cance, called upon current experts in the field to revise and update this important
publication to reflect the changes and advancements that have taken place since
the last edition, which was published in 1972.

‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬


(American Society for Testing and Materials) accepted ownership of the Gardner-Sward
Handbook from the Gardner Laboratory. It was through this laboratory that Dr. Henry
A. Gardner published the previous twelve editions of the manual. Acceptance of this
ownership gave ASTM an assumed responsibility for revising, editing, and publishing
future editions of this well-known, respected manual. The undertaking was assigned to
Committee D-1 on Paint and Related Coatings, Materials, and Applications. This com-
mittee established a permanent subcommittee, D01.19 on Gardner-Sward Handbook,
chaired by John C. Weaver, to provide technical, editorial, and general policy guidance
for preparation of the 13th and subsequent editions of the Gardner-Sward Handbook.
The 13th edition was published in 1972 as the Paint Testing Manual (STP 500) with Mr.
G. G. Sward as editor. The manual has served the industry well for the past two decades;
it contains useful information that cannot be found elsewhere. However, the passage of
more than 20 years since its publication is readily apparent in many and perhaps most
chapters of the manual.
Although updating the manual was discussed through the years, a variety of reasons
prevented this task from being accomplished. Feasibility of updating the manual was
not realized until mid-1989 when Dr. John J. Brezinski, Union Carbide (retired), and
Mrs. Kathleen A. Dernoga, Manager of Acquisitions and Review of ASTM Technical
Books and Journals, discussed the matter and the 14th edition was conceived. Between
then and the spring of 1990 an outline for the 14th edition was developed and was
approved by members of Subcommittee DO1.19. Almost five years later the manual was
completed--no wonder such a long period elapsed between editions!
The scope of the new edition is in keeping with the stated scope of Subcommittee
"To provide technical, editorial, and general policy guidance for preparation of the
Fourteenth and subsequent editions of the Gardner-Sward Handbook. The hand-
book is intended for review of both new and experienced paint technologists and
the past, present, and foreseeable trends in all kinds of testing within the scope of
Committee D-1. It supplements, but does not replace, the pertinent parts of the
Society's Book of Standards. It describes briefly and critically all Test Methods
believed to have significance in the world of paint technology, whether or not these
tests have been adopted officially by the society."
In this new edition, ASTM standard methods are described by minimal detail with the
various volumes of the ASTM Book of Standards remaining the primary source of such
information. An effort was made to include references in the absence of ASTM informa-
tion concerning industrial, other society, national, and international test methods. For
the most part, the manual contains either new chapters or the old topics/chapters in
rewritten form. In a few cases, the old manual was merely updated, attesting to either
the quality of the earlier writing, the lack of development in the area, or the apparent
waning of interest in the topic. A variety of modern topics has been included. Individual
authors, experts in their various fields, were given a great deal of freedom in expressing
information about their topics.
Many things have changed through the years. The chemical emphasis has shifted
from natural products to synthetic products, so this edition of the manual contains
chapters that deal with a large number of synthetic polymers used in the coating
industry. Instrumentation has undergone a marked change with innovative electronics
providing the key to many changes. An effort was made to include chapters dealing with
a broad variety of instruments.
‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬


To the authors, a warm, heart-felt "thank you." You put your talents to work and
sacrificed much personal time to make the manual a success. A "thank you" is also due
the reviewers, who are a special lot. They must be critical, yet carry out their task in a
constructive manner. Because of the customary anonymity accorded reviewers, they
should know that some authors made a special effort to express their appreciation for
the review comments that they felt strengthened their manuscripts. Those organiza-
tions who permitted authors' time, use of support staff, and supplies are truly appreci-
ated. Works such as this manual could not be completed without their generosity--may
they prosper. The staff at ASTM is distinctive--they were interested and smilingly
helpful to the authors, reviewers, Subcommittee DO1.19, and the editor as they guided
us through the maze of the publication assembly process (though they may have gritted
their teeth at times). A very special thanks to Monica Siperko of ASTM, who worked
closely with the editor in dealing with authors, reviewers, ASTM staff, and manuscripts.
Her invaluable, cheerful assistance is appreciated. And last, but certainly not least, the
contributions of Maureen Quinn and David Jones of the ASTM editing staff are ac-
knowledged. Their able assistance ensured that the manual was uniform in style and
Joseph K Koleske
‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬

MNLI7-EB/Jun. 1995

Subject Index

A Wolf abrasion method, 529 automotive products, 714
Abrasion testing, can coatings, 722-723 can coatings, 722
A-A-1555, 726, 727-729, 729 Absorption testing to chalky surfaces, architectural
AAMA 801.1,739 architectural coatings, 699-700 coatings, 705
AAMA 802.3,739 masonry, 725 chemical, 514-515
AAMA 803.3, 739 Acetylacetone, antimicrobial agents that combination of phenomena, 515
AAMA 804.1,739 react with, 263, 265 concepts, 513
AAMA 805.2, 739 Acid-base adhesion, 515 diffusion theory, 514
AAMA 806.1,739 Acidity direct tensile testing, 519-523
AAMA 807.1,739 plasticizers, 115 electrostatic, 515
AAMA 808.3, 739 solvents, 152 fracture theory, 513-514
AAMA 809.2, 739 Acid resistance, 664-665 ISO 4624, 521-522
AASHTO M-247, 745 Acids, used in alkyd manufacture, 56 mechanical, 515
AASHTO T 250, 744, 745 Acid spot test, metallic pigments, 226 peel adhesion testing on plastic
AASHTO T 259, 750 Acid value, alkyds, 57 substrates, 517-518
Ablative coatings, testing, 675 Acid wash color, solvents, 152 peel angle and rate, 519
Abrasion, mechanism, 526 Acrylic emulsion polymers, 46-51 sealants, 737
Abrasion resistance architectural coatings, 46-49 versus stress, 594, 596
air blast abrasive, 527-528 exterior coatings applications, 48-49 substrate effects, 515-516
architectural coatings, 703 industrial coatings, 49-51 surface modification techniques, 5 ! 6
balanced beam tester, 531-532 interior coatings applications, 47-48 tape test, 517-519, 688
maintenance coatings, 49 controversy, 518
Bell Laboratory Rotating Disk
nonreactive emulsions, 49-50 test methods, 517
Abrasion Test, 528
properties, 50 visual assessment, 519
camp abrasion tester, 529
resistance characteristics, 51 weak boundary layer theory, 514
coin mar test, 532
thermosetting emulsions, 50-51 wet, architectural coatings, 704
comparison of wear abrasion testers, Acrylic latex sealants, 736 wetting-contact theory, 514
531 Acrylic/MF clearcoat, dynamic work of, 513
correlation with end-use performance, properties, 539-540 Adhesive shear strength, pavement
525-526 Acrylic polymers, as coatings binders, marking tape, 745
definitions, 525 39-51 Adhesive strength, 515
falling abrasive test, 526-527 acrylic emulsion polymers, 39-40 ADL Ball Rebound Apparatus, 578-579
FDC wear test, 529-530 (see also Acrylic emulsion polymers; Adsorption chromatography, 790
fingernail test, 532" Acrylic solution polymers) Aerosol beam generator and detection
gloss reduction test, 527 Acrylic solution polymers, 39-46 mechanism, 316
gravel projecting machine, 528-529 acid-functional acrylics cross-linked Aerosol spray paints, VOC standards, 8
impinging abrasive method, 532 with epoxy resins, 43-44 Aerospace and aircraft coatings, 683-694
less well-known tests, 532-533 cross-linked with amino resins, 43-45 accelerated conditions, 685
pebble abrasion wear test, 527 isocyanate-reactive acrylics, 45-46 accelerated weathering, 691-692
PEI abrasion tester, 533 thermoplastic resins, 40-42 adhesion, 688-689
Peters abrasion block, 533 thermosetting acrylic resins, 42-46 chemical analysis, 684-685
Princeton scratch tester, 532 Acrylic solvent release sealants, 735 cleanability, 693-694
rain or water erosion, 532 Additives corrosion inhibition, 690-691
RCA tape tester, 531 failure modes associated with, 772- density, 684
relation to hardness, elasticity, and 773 drying time, 686
tensile strength, 525 identification, paint analysis, 763 film thickness, 686-687
Roberts jet abrader, 527-528 Adhesion, 513-523 fineness of grind and coarse particles,
Schiefer abrasion testing machine, acid-base, 515 684
529-530 aerospace and aircraft coatings, 688- flash point, 685-686
straight-line reciprocating machines, 689 flexibility, 689
531 architectural coatings, 703-704 fluid resistance, 692-693
Taber Abraser, 530 artists' paints, 708 hardness, 690
mar test, 532 ASTM D 2197, 522-523 heat resistance, 692-693
traffic marking materials, 744 ASTM D 4541, 519-522 humidity, 692
traffic paint tests, 532 ASTM D 5179, 519-520 mar resistance, 690
‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬


optical properties, 687-688 in water-reducible coatings, 393, 397 exterior coatings, 697
outdoor exposure, 691 Amine value, traffic marking materials, gloss, 702-703
pigment concentration, 684 743 hiding power, 703
pot life, 686 Aminoethylpiperazine, 85 high performance, 697
storage stability, 685 Aminoplast cross-linking resins, 77 interior coatings, 697
strippability, 693 Amino resins, 60-67 properties
total solids content, 684 combining ratios, 63-64 exterior coatings, 705
viscosity, 683-684 cross-linked with acrylic polymers, 43- interior and exterior, 703-704
volatile concentration, 684 45 interior finishes, 704-705
wear resistance, 689-690 cure reactions, 64-65 reflectance, 702
Aging, effects on flexibility and definition and description, 60 roller application, 702
toughness, 554 degradation, 65-66 scope, 696-697
Air blast end uses, 66 service location, 698
abrasive, 527-528 environmental/toxicity, 66-67 spray application, 702
aerospace and aircraft coatings, 690 free formaldehyde, 64 substrate
Aircraft (see Aerospace and aircraft high-performance liquid conditions, 697
coatings) chromatography, 62-63 types, 697
Air pollutants high-solids, 61-62 test selection, 698
hazardous, in paints and coatings, 10 history, 60 touch-up uniformity, 702
volatile organic compounds, physical properties, 64 value judgments, 698
regulations, 3-12 size exclusion chromatography, 62-63 Arco microknife, aerospace and aircraft
Air toxics program, Clean Air Act, 10 solids content, 62 coatings, 690
Alcohols solvent tolerance, 62 Array method, using optical microscope,
soluble phenolic resins, 82 structure/property variations, 61-62 particle-size measurements, 319
as solvents, 129-130 surface tension, 64 Arrhenius expression, 845
Algae synthesis, 61 Articulated-strut meters, 605
associated with paint films, 656 uses, 60-61 Artists' paints, 706-710
determining presence on paint films, viscosity, 62, 64 film properties, 708-709
656 weathering, 65-66 safety and compliance, 709-710
Algicides, 261-267, 657 Analogue electromagnetic thickness storage stability, 706-707
analysis and decontamination, 265- gages, 432-433 working properties, 707-708
266 Angstrom particle sizing, 329 Asbeck-Van Loo method, critical pigment
definition of terms, 261 Anhydrides, used in alkyd manufacture, volume determination, 254-255
methods for determination of efficacy, 56 Ash (see Pigment content)
267 Aniline point, solvents, 132-133 Asphalt emulsions, 17
mode of action, 262-265 Anionic emulsions, bituminous coatings, Asphalts, 15-16
strategies for minimizing resistant 21 Associative thickeners, 348-349
strains, 265 Anodic dissolution, 610-611 ASTM, specifications, 891-893
Alkalinity, solvents, 152 Anodic passivation, inorganic anti- ASTM A 754, 886
Alkali resistance, 664-665 corrosive pigments, 239-240 ASTM B 117, 639
masonry, 727-728 ANSI/AWWA C203, 733 accelerated weathering, 650
Alkali-swellable/soluble emulsions, 277- ANSI/AWWA C210, 733 aerospace and aircraft coatings, 690
278 ANSI/AWWA C214, 733 automotive products, 715
Alkyds, 53-58 ANSI/AWWA C215, 733 bituminous coatings, 20
acid value, 57 ANSI/AWWA C217, 733 chemical resistance, 666
classification, 57-58 Anthraquinone red, 194 inorganic binders, 771-772
color, 56 Anti-corrosive pigments (see Inorganic water-resistance testing, 678
density, 56 anti-corrosive pigments ASTM B 533, 523
drying properties, 56 Antifouling paint films, structure, ASTM B 537, 613
fusion process, 54 electron microscopy, 824 ASTM B 568, 886
higher solids, 57-58 Antimicrobial agents, 656-657 ASTM B 571,523
history, 53 cationic agents, 265 ASTM C 31,729
hydroxyl value, 57 factors impacting efficacy, 266 ASTM C 43, 725, 729
nonvolatile content, 55-56 future development, 267 ASTM C 67, 725-726, 729, 750
processing, 53-54 metal chelating, 265 ASTM C 97, 725, 729
raw materials, 55-56 reacting with ASTM C 119, 725, 729
resins, gas chromatography, 806-807 acetylacetone, 263, 265 ASTM C 125, 725, 729
solvent reflux process, 54-55 nucleophilic groups, 265 ASTM C 140, 725, 727, 729
viscosity, 55 Antithixotropy, 341 ASTM C 192 729
water-borne, 57-58 API gravity, definitions, 146 ASTM C 267 750
Allen-Bradley sonic sifter, 317-318 API RP 5L2, 733 ASTM C 270 725, 729
z~ltek Mobility/Lubricity Tester, 722 API RP 5L7, 733 ASTM C 282 70-71
Alumina trihydrate, 220 Appearance ASTM C 283 70-71
A]umlnum artists' paints, 706-707 ASTM C 285 71
corroeion, 613 automotive products, 714 ASTM C 313 523
flake, 244-245 Application life, sealants, 736 ASTM C 346 71
pigment~ Aqueous solutions, corrosion in, 609-611 ASTM C 372 69
grade classification,224 Architectural coatings, 696-705 ASTM C 374 71
properties, 223-224 acrylic emulsion polymers, 46-49 ASTM C 385 71
Aluminumtriphosphate, 243 ASTM guides, 697 ASTM C 424 69
AmericanArchitecturalManufacturers brush application, 701-702 ASTM C 448 533
Association, 892-893 color, 702 ASTM C 510 738
Amines differences, 702 ASTM C 536 70-71
polyfunctional,in polyurethane definitions, 696 ASTM C 537 71
coatings, 91 dry film appearance, 702-703 ASTM C 538 70-71
‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬


A S T M C 5 3 9 69,71 A S T M C 1034, 69 ASTM D 332, 170, 508
A S T M C 554 69 A S T M C 1070,216 ASTM D 335, 96
A S T M C 556 69 A S T M C 1083,738 ASTM D 344, 502, 703
A S T M C 5 7 0 737,738 A S T M C 1085, 737-738 ASTM D 365, 462
A S T M C 584 69 A S T M C 1087, 738 ASTM D 387
A S T M C 603 738 A S T M C 1109, 788 black pigments, 189
A S T M C 609 69 A S T M C 1111, 788 ceramic pigments, 216
A S T M C 6 1 4 70-71 A S T M C 1193, 738 colored organic pigments, 207
A S T M C 633 72 A S T M D 12,28 pigment dispersion, 508-509
A S T M C 63~ 738 A S T M D 21,604 ASTM D 402, 20
A S T M C 642, 725, 729 A S T M D 4, 15, 19, 733 A S T M D 412, 97, 536, 543
A S T M C 650, 69 A S T M D 5, 19, 733 A S T M D 445, 118, 133, 363
A S T M C 661, 738 A S T M D 26, 692 A S T M D 449, 19
A S T M C 666, 750 A S T M D 36, 19, 733, 745 A S T M D 450, 19
A S T M C 669, 737, 738 ASTM D 41, 20 A S T M D 466, 21
A S T M C 672, 750 ASTM D 43, 20-21, 20 A S T M D 476, 174, 176
A S T M C 675 71 ASTM D 56, 755 A S T M D 480,226
A S T M C 676 71 aerospace a n d aircraft coatings, 686 A S T M D 520,226
A S T M C 679 738 can coatings, 720 A S T M D 521,226
A S T M C 681 738 plasficizers, 117 A S T M D 522, 548-550, 771
A S T M C 690 216 so~ents, 142 aerospace and aircraft coatings, 689
A S T M C 703 71 wate~repellent coatings, 748 a r c h i t e c t u r ~ coatings, 704
A S T M C 711 738 ASTM D 61, 19 artist's paints, 709
A S T M C 712 738 ASTM D 70, 19 bituminous coatings, 20
A S T M C 713 738 ASTMD71,19,733 natural weathering, 642
A S T M C 717 738 A S T M D 86, 116, 140-141 stress-strain analysis, 544
A S T M C 718 738 A S T M D 88, 19 A S T M D 523, 471,473-474, 771
A S T M C 719 738 A S T M D 92, 19, 117 aerospace and aircra~ coatings, 688
A S T M C 724 71 A S T M D 93,755 a r c h i t e c t u r ~ coatings, 702-703
A S T M C 731 738 aerospace and aircra~ coatings, 686 can coatings, 723
A S T M C 732 738 architectural coatings, 699 natural weathering, 641
A S T M C 733, 738 plasticizers, 117 white pigments, 173
A S T M C 734, 738 so~ents, 143 A S T M D 529, 19, 20, 21
A S T M C 735,71 ASTMD 95,19,226 A S T M D 546, 317
A S T M C 736, 738 A S T M D 115, 362 A S T M D 555, 20, 29
A S T M C 738, 69 A S T M D 130, 116, 153 A S T M D 562 20, 273, 683,743
A S T M C 741,738 A S T M D 140, 19 A S T M D 570 771
A S T M C 742, 738 A S T M D 153 A S T M D 600 33
ASTMC 743,70-71 colored organic pigments, 208 A S T M D 601 28
A S T M C 756, 70-71 extender pigrnents, 221 A S T M D 602 221
A S T M C 765, 738 solids, 301-302 A S T M D 603 221
A S T M C 766, 738 traffic marking materials, 745 A S T M D 604 221
A S T M C 771,738 A S T M D 154, 743 A S T M D 6 0 5 221
A S T M C 772, 738 A S T M D 156, 149, 462 A S T M D 607 221
A S T M C 777, 71 A S T M D 185 A S T M D 609 20, 677, 774
A S T M C 780, 727, 729 aerospace and aircraft pigments, 684 A S T M D 610, 20, 641,771
A S T M C 782, 738 architectural coatings, 698 A S T M D 624, 97
A S T M C 792, 738 artist's paints, 707 A S T M D 638, 536-537, 543,745
A S T M C 793, 738 ceramic pigments, 216 A S T M D 658
A S T M C 794, 738 metallic pigments, 226 abrasion testing, 526-528
A S T M C 797, 738 A S T M D 212, 720 aerospace a n d ~ r c r a f t coatings, 690
A S T M C 824, 71 A S T M D 233 127 architectural coatings, 703
A S T M C 834, 738 A S T M D 234 2 8 , 2 5 2 - 2 5 3 wear abrasion, 531
A S T M C 836, 738 A S T M D 235 126,153, 226 A S T M D 6 6 0 641,771
A S T M C 839 71 A S T M D 255 20 ASTM D 661 6 4 1 , 6 8 0 , 7 4 9 , 7 7 1
A S T M C 8 7 2 70-71 A S T M D 256 745 ASTM D 662 20, 6 4 1 , 6 8 0 , 7 7 1
A S T M C 879 738 A S T M D 257 733 ASTM D 673 532,581
A S T M C 895 69 A S T M D 262 5O8 ASTM D 695 733
A S T M C 898 738 A S T M D 267 226 ASTM D 711 444,743, 747
A S T M C 907 738 A S T M D 269 428 ASTM D 713 746-747
A S T M C 908 738 A S T M D 270 294 ASTM D 714 2 0 , 6 4 1 , 7 7 1
A S T M C 910 738 A S T M D 281 ASTM D 715 221
A S T M C 919 738 ceramic pigments, 216 ASTM D 716 221
A S T M C 9 2 0 737-738 colored organic pigments, 207 ASTM D 717 221
A S T M C 927, 71 extender pigments, 221 ASTM D 718 221
A S T M C 957, 737-738 oil absorption, 253 ASTM D 719 221
A S T M C 961,738 white pigments, 169 ASTM D 740 128
A S T M C 972, 738 ASTM D 287, 146 ASTM D 746 120
A S T M C 978, 71 ASTM D 304, 130 ASTM D 770 130
A S T M C 981,738 ASTM D 312, 19 ASTM D 772 641,771
A S T M C 988, 523 ASTM D 319, 130 ASTM D 792 9 8 , 2 9 7 , 3 0 2
A S T M C 1016,738 ASTM D 323, 135 ASTM D 801 127
A S T M C 1021, 738 ASTM D 329, 128 ASTM D 802 127-128
A S T M C 1027, 69 ASTM D 330, 129 ASTM D 803 361
A S T M C 1028, 603 ASTM D 331, 129 ASTM D 804 127
‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬


ASTM D 816, 362 ASTM D 1217, 147 ASTMD 1614, 152
ASTM D 817, 24-25 ASTM D I218, 117, 149 ASTMD 1617, 117, 129, 151
ASTM D 821,747 ASTM D 1227, 20-21 ASTMD 1620, 188
ASTM D 822, 207, 728-729, 865 ASTM D 1250, 147 ASTMD 1630, 602
ASTM D 823 ASTM D 1259, 55, 87, 756 ASTMD 1638, 362
film preparation, 415, 419, 421 ASTM D 126, 743 ASTMD 1639,57
free film samples, 538-539 ASTM D 1260, 720 ASTMD 1640
water-resistance testing, 677 ASTM D 1266, 153 aerospace and aircraft coatings, 686
ASTM D 832 419 ASTM D 1270, 172 alkyds, 56
ASTMD 847 152 ASTM D 1286, 362 artist's paint, 708
ASTMD 848 152 ASTM D 1296, 117, 149, 699 bituminous coatings, 20
ASTMD 849 116,153 ASTM D 1298, 146 driers, 32
ASTMD 850 140-141 ASTM D 1308 drying oils, 28
ASTMD 868 743 architectural coatings, 704 drying time, 439--440
ASTMD 869 701,707,743,771 artist's paint, 709 hardness, 573
ASTMD 870 677, 774 automotive products, 715 water-repellent coatings, 748
ASTMD 871 24 chemical resistance, 662, 664-665 ASTMD 1644, 20, 34
ASTMD 882 536,543 ASTM D 1309 743 ASTMD 1647, 665
ASTMD 883 536 ASTMD 1310 142, 755 ASTMD 1652, 109, 743
ASTMD 891 118, 146-147 ASTMD 1319 150,791 ASTMD 1653, 771
ASTMD 907 513 ASTMD 1328 19 aerospace and aircraft coatings, 692
ASTM D 913 747 ASTMD 1337 362 masonry, 728-729
ASTM D 936 150-151 ASTMD 1338 362 water-repellent coatings, 750
ASTM D 941 147 ASTMD 1347 302 ASTMD 1654, 20, 641,771
ASTMD 960 28 ASTMD 1353 152 ASTMD 1669, 19
ASTMD 961 28 ASTMD 1360 670 ASTMD 1670, 19
ASTMD 962 226 ASTMD 1363 128 ASTMD 1686, 462
ASTMD 968 771 ASTMD 1364 118, 154 ASTMD 1718, 129
abrasion resistance, 526-527, 531 ASTMD 1366 216, 221 ASTMD 1719, 130
architectural coatings, 703 ASTMD 1370 19 ASTMD 1720, 132-133
traffic marking materials, 744 ASTMD 1392 28 ASTMD 1722, 154
ASTMD 969, 743 ASTMD 1394 168,743,763 ASTMD 1725, 133, 361
ASTMD 996, 677 ASTMD 1398 805-806 ASTMD 1729, 465, 744
ASTMD 1002, 733 ASTMD 1400 426, 434, 771 architectural coatings, 702
ASTMD 1005 415, 426, 538 ASTMD 1417 362 artist's paint, 709
ASTMD 1006 774 ASTMD 1439 277, 302,362 natural weathering, 641
ASTMD 1007 130 ASTMD 1462 28 ASTMD 1730, 677, 774
ASTMD 1014 771 ASTMD 1474 ASTM D 1734,418, 677,729
ASTMD 1044 581,733 bituminous coatings, 20 ASTM D 1735678
ASTMD 1045 117 acrylic polymers, 42 ASTM D 1737 722
ASTMD 1076 362 can coatings, 720 ASTM D 1795 839
ASTMD 1078 116, 140-141 cure testing, 412 ASTM D 1824 362
ASTMD 1079 16, 19 hardness, 564, 567, 569-571 ASTM D 1849 20, 685, 701, 748
ASTMD 1084 97, 362 ASTM D 1474A, 714 ASTM D 1856 19
ASTMD 1125 714 ASTM D 1475, 7, 299, 771 ASTM D 1894 603-604
ASTMD 1131 361 architectural coatings, 698 ASTM D 1955 28
ASTMD 1133 132 automotive products, 714 ASTM D 1963 755
ASTMD 1150 774 bituminous coatings, 20 ASTM D 1983 743, 804, 806
ASTMD 1152 130 density, 755 ASTM D 2042 19
ASTMD 1153 128 traffic marking materials, 743 ASTM D 2047 600,603-604
ASTMD 1155 745 water-repellent coatings, 748 ASTM D 2073 86
ASTMD 1159 153 ASTMD 1476 154 ASTM D 2074 743
ASTMD 1186 429,771, ASTMD 1483 169,221,252-253 ASTM D 2076 86
automotive )roducts, 714 ASTMD 1492 153 ASTM D 2090 34
can coatings, 721 ASTMD 1500 462 ASTM D 2091 3 2 , 4 2 , 4 1 1 , 5 7 3
natural weathering, 642 ASTMD 1505 302 ASTM D 2124 100
thickness gages, 432 ASTMD 1513 188 ASTM D 2134, 412, 575-576
ASTM D 1187, 21 ASTMD 1526 556 ASTM D 2192, 150
ASTM D 1199, 221 ASTMD 1535 457 ASTM D 2196, 273, 341,362, 771
ASTM D 1200, 359, 771 ASTMD 1540 20,662 aerospace and aircraft coatings, 683
aerospace and aircraft coatings, 683 ASTMD 1542 20 architectural coatings, 701
can coatings, 720 ASTMD 1544 artist's paint, 708
water-repellent coatings, 748 alkyds, 56 automotive products, 714
ASTM D 1208, 755 driers, 34-35 can coatings, 720
ASTM D 1209, 115, 148-149, 462 polyamides, 87 polyamides, 87
ASTM D 1210, 771 plasticizers, 116 water-repellent coatings, 748
aerospace and aircraft coatings, 684 scales for liquids, 462 ASTM D 2197
architectural coatings, 699 ASTM D 1545, 361 aerospace and aircraft coatings, 688,
artist's paint, 708 alkyds, 55 690
extender pigments, 221 amino resins, 62 adhesion, 522-523
particle-size measurement, 327 driers, 34-35 architectural coatings, 703
traffic marking materials, 743 polyamides, 87 mar resistance, 532, 579-580
ASTM D 1211, 554, 667 solvents, 133 ASTM D 2200, 435
ASTM D 1212, 20, 424, 504, 687 ASTM D 1555, 147, 297 ASTM D 2202, 738
ASTM D 1214, 745 ASTM D 1613, 115, 152 ASTM D 2203, 738
‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬


ASTM D 2240, 97 nonvolatile content, 756 b i t u m i n o u s coatings, 20
ASTM D 2243, 20, 685,748 VOC, 8 can coatings, 722
ASTM D 2244, 465, 771 A S T M D 2698, 684, 879 natural weathering, 642
aerospace and aircraft coatings, 687 A S T M D 2704, 642 peel adhesion, 517-518
archictectural coatings, 702 A S T M D 2710, 153 ASTM D 3360, 221, 321
artist's paint, 708-709 A S T M D 2743, 804, 809 ASTM D 3361, 728-729
traffic marking materials, 744 A S T M D 2745, 171,508 ASTM D 3362, 804
natural weathering, 641 A S T M D 2764, 19 ASTM D 3363, 771
ASTM D 2245 743, 804, 806 A S T M D 279, 207, 708 aerospace and aircraft coatings, 690
A S T M D 2247 20, 692,714 A S T M D 2792, 663 can coatings, 721
A S T M D 2248 43,532 A S T M D 2794, 42, 412, 553, 689 cure, 412
A S T M D 2249 738 A S T M D 2799, 723 driers, 32
A S T M D 2268 151 A S T M D 2800, 743, 804 hardness, 559-560, 564
A S T M D 2288 97 A S T M D 2801, 358 natural weathering, 642
A S T M D 2306 151,804 A S T M D 2804, 128, 151,685, 804 ASTM D 3423, 20
A S T M D 2318 19 A S T M D 2805 ASTM D 3432, 685, 804
A S T M D 2319 19 aerospace and aircraft coatings, 687 ASTM D 3447, 151
A S T M D 2320 19, 301 a r c h i t e c t u r ~ coatings, 703 ASTM D 3450, 704, 705
A S T M D 2348, 763 automotive products, 713 ASTM D 3456, 267, 659
A S T M D 2360, 152,804 hiding power, 491,502, 504 ASTM D 3457, 804
A S T M D 2363, 277, 302 ~affic marking ma~rials, 743 ASTM D 3459, 680
A S T M D 2364, 276, 362 white pigments, 171 ASTM D 3461, 19
ASTM D 2369, 5 - 7 A S T M D 2823, 20 ASTM D 3465, 117
aerospace and aircraft coatings, 684 A S T M D 2824 20 ASTM D 3468, 21
amino resins, 62 A S T M D 2832 20, 756 ASTM D 3505, 148, 299
architectural coatings, 713 A S T M D 2849 116 A S T M D 3506, 130
bituminous coatings, 20 A S T M D 2857 839 A S T M D 3536, 838
can coatings, 720 A S T M D 2863 668-670 A S T M D 3539 135
nonvolatile content, 756 A S T M D 2879 116, 135 A S T M D 3540 129
traffic marking materials, 743 A S T M D 2916 128 A S T M D 3545 129, 151,804
water-repellent coatings, 748 A S T M D 2917 128 A S T M D 3593 838
ASTM D 2370, 733 A S T M D 2921 680 A S T M D 3619 221
bituminous coatings, 20 A S T M D 2935 148,297 A S T M D 3622 130
dynamic mechanical properties, 536 A S T M D 2939 21 A S T M D 3624 787
tensile properties, 543 A S T M D 2962 19 A S T M D 3626 804
aerospace and aircraft coatings, 664 A S T M D 2963 21 A S T M D 3698 130
architectural coatings, 704 A S T M D 2965 296 A S T M D 3717 787
ASTM D 2371, 743, 879 A S T M D 3002 774 A S T M D 3718 685,787
A S T M D 2372 684, 756 A S T M D 3008 804 A S T M D 3719 705
A S T M D 2373 35 A S T M D 3009 151,804 A S T M D 3720 1 6 4 , 7 6 3 , 8 8 0
A S T M D 2374 35 A S T M D 3037 188 A S T M D 3723 7 4 3 , 7 5 6 , 8 7 9
A S T M D 2375 35 A S T M D 3054 151,804 A S T M D 3728 129
A S T M D 2376 738 A S T M D 3055 127 A S T M D 3730 420, 523,697
A S T M D 2377 738 A S T M D 3104 19 A S T M D 3735 126
A S T M D 2393 362 A S T M D 3105 20 A S T M D 3742 151
A S T M D 2414 188 A S T M D 3128 129 A S T M D 3760 151,804
A S T M D 2 4 1 5 19, 733 A S T M D 3130 129 A S T M D 3792 6 - 7 , 7 5 5 , 8 0 4
A S T M D 2416 19 A S T M D 3131 129 A S T M D 3797 151, 8O4
A S T M D 2444 723 A S T M D 3132 134 A S T M D 3798 151,804
A S T M D 2448 221 A S T M D 3134 465-466 A S T M D 3804 35
A S T M D 2450 738 A S T M D 3143 733 A S T M D 3805 2O
A S T M D 2451, 738 A S T M D 3170 20,528, 642, 714 A S T M D 3806 670-672
A S T M D 2452, 738 A S T M D 3257 151,804 A S T M D 3893 128, 151, 804
A S T M D 2453, 738 A S T M D 3258 704 A S T M D 3894 674-675
A S T M D 2455, 804 A S T M D 3260 664 A S T M D 3925 753-754, 774
A S T M D 2456, 804 A S T M D 3265 188-189 A S T M D 3928 702
A S T M D 2485, 667 A S T M D 3271 7 6 4 , 7 9 7 , 8 0 4 A S T M D 3934 144
A S T M D 2486, 705 A S T M D 3272 756-757 A S T M D 3941 143
A S T M D 2503, 836 A S T M D 3273 267, 658-659 ASTM D 3960 6, 8, 774
A S T M D 2521, 19 A S T M D 3274 641,656 aerospace and aircraft coatings, 684
A S T M D 2556, 362 ASTM D 3278 755 architectural coatings, 699
A S T M D 2569, 19 aerospace a n d aircraft coatings, 686 automotive products, 714
A S T M D 2571, 662 architectural coatings, 699 bituminous coatings, 20
ASTMD 2574,267,657 bituminous coatings, 56 can coatings, 720
A S T M D 2613,35 can coatings, 720 chromatography, 809
A S T M D 2616,465 plasticizers, 117 gas chromatography, 804
A S T M D 2621, 100, 743,771 solvents, 143 water-repellent coatings, 748
A S T M D 2627, 128 ASTM D 3281, 523, 552-553 ASTM D 3961, 154
A S T M D 2634, 129 ASTM D 3320, 20-21 ASTM D 3964, 464, 702
A S T M D 2635,130 ASTM D 3329, 128, 151,804 ASTM D 3969, 35
A S T M D 2669, 362 ASTM D 3335, 6 8 5 , 7 8 7 , 8 8 6 ASTM D 3970, 34
A S T M D 2697, 771 ASTM D 3359, 778 ASTM D 3988, 35
aerospace and aircraft coatings, 684 aerospace and aircraft coatings, 688 ASTM D 3989, 35
automotive products, 713 architectural coatings, 703-704 ASTM D 4001, 836-837
displacement, 302 artist's paint, 708 ASTM D 4017, 6-7, 226, 685, 755
‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬


ASTM D 4052, 118, 147, 755 ASTM D 4715, 19 ASTM E 176, 667
ASTM D 4060 526, 771 ASTM D 4735, 8O4 ASTM E t97, 463
aerospace and aircraft coatings, 690 ASTM D 4746, 19 ASTM E 201, 148
architectural coatings, 703 ASTM D 4752, 411,664 ASTM E 202, 151
automotive products, 714 ASTM D 4758, 756 ASTM E 260, 150, 764, 796, 809
can coatings, 722 ASTM D 4764, 762 ASTM E 275, 867-869
natural weathering, 642 ASTM D 4773, 129, 151 ASTM E 276, 317
wear abrasion, 530-531 ASTM D 4796, 745 ASTM E 284, 447, 449, 452, 507
ASTM D 4061 449, 744 ASTM D 4797, 744 directionality, 470-471
ASTMD 4062 274, 358,701 ASTM D 4798, 19 pearlescent pigment, 232
ASTMD 4072 19 ASTM D 4799, 19 ASTM E 300, 117, 754
ASTMD 4079 130 ASTM D 4828, 705 ASTM E 303, 603, 604, 745
ASTMD 4080 130 ASTM D 4834, 762 ASTM E 308, 453-454, 456, 462
ASTMD 4081 130 ASTM D 4835, 129 traffic marking materials, 744
ASTMD 4086 452 ASTM D 4836, 129 tristimulus values, 463
ASTMD 4126 130 ASTM D 4837, 129 ASTM E 313 461-462
ASTMD 4138 429 ASTM D 4838, 508, 708 ASTM E 346 130, 151
ASTMD 4139 221 ASTM D 4866, 20 ASTM E 355 150, 796, 809
ASTMD 4141 ASTM D 4875, 109 ASTM E 413 641
accelerated weathering, 651 ASTM D 4883, 302 ASTM E 430 477
masonry, 728-729 ASTM D 4890, 109 ASTM E 450 462
natural weathering, 638, 640 ASTM D 4892, 19, 302 ASTM E 514 728-729
water-repellent coatings, 749 ASTM D 4893, 19 ASTM E 516 798, 809
ASTM D 4145 523, 722 ASTM D 4941, 707 ASTM E 594 798, 809
ASTMD 4146 523, 552 ASTM D 4946, 42, 704 ASTM E 595 97
ASTMD 4210 757 ASTM D 4951, 788 ASTM E 603 674-675
ASTMD 4212 683, 714, 771 ASTM D 4958, 274, 702 ASTM E 663 788
ASTMD 4213 531, 705 ASTM D 4960, 744 ASTM E 682 809
ASTMD 4214 641,771 ASTM D 4989, 19 ASTM E 685 793, 809
ASTMD 4236 710 ASTM D 5008, 130 ASTM E 697 798, 809
ASTMD 4259 727, 729 ASTM D 5009, 8 ASTM E 774 737
ASTMD 4260 727 ASTM D 5018, 20 ASTM E 782 639
ASTMD 4261 727 ASTM D 5031, 680, 865 ASTM E 805 464
ASTMD 4262 726-727, 729 ASTM D 5066, 8 ASTM E 808 449
ASTMD 4263 727, 729 ASTM D 5076, 20 ASTM E 809 449
ASTMD 4273 109, 836 ASTM D 5087, 8 ASTM E 810 449
ASTMD 4274 109 ASTM D 5095, 8, 748 ASTM E 811 449
ASTMD 4287 274, 701-702 ASTM D 5098, 707, 708 ASTM E 840 809
ASTMD 4302 708 ASTM D 5107, 727, 729 ASTM E 991 449, 462
ASTMD 4303 709 ASTM D 5135, 804 ASTM E 1064, I54
ASTMD 4304 709 ASTM D 5137, 129 ASTM E 1100, 151
ASTMD 4312 19 ASTM D 5146, 696, 697 ASTM E 1131, 675
ASTMD 4360 128 ASTM D 5150, 503, 703 ASTM E 1140, 798, 809
ASTMD 4366 32, 412, 574 ASTM D 5162, 774 ASTM E 1151, 809
ASTMD 4367 152, 804 ASTM D 5178, 580 ASTM E 1164, 448, 463-464, 508
ASTMD 4368 100 ASTM D 5179, 519-520, 771 ASTM E 1247, 449
ASTMD 4400 274, 354,418, 771 ASTM D 5200, 8 ASTM E 1303, 793, 809
ASTMD 4402 19 ASTM D 5201, 8, 710 ASTM E 1331, 449, 463-464
ASTMD 4414 425, 774 ASTM D 5286, 8 ASTM E 1341, 463
ASTMD 4417 771 ASTM D 5324, 696, 697 ASTM E 1345, 464
ASTMD 4446 749 ASTM D 5325 8 ASTM E 1347, 449, 463, 688, 702
ASTMD 4449 472 ASTM D 5326 700 ASTM E 1348, 449, 463-464
ASTMD 4451 743 ASTM D 5327 8 ASTM E 1349, 449, 463-464
ASTMD 4457 6-7, 764, 797, 804 ASTM D 5328 9 ASTM E 1360, 460-461
ASTMD 4479 20 ASTM D 5383 709 ASTM E 1455, 463
ASTMD 4492 151, 804 ASTM D 5398 709 ASTM E 1499, 465, 468
ASTMD 4518 601,603 ASTM D 5401 749 ASTM E 1501, 449
ASTMD 4534 152, 804 ASTM D 5403 9 ASTM E 1541, 460
ASTMD4541 519-522, 704, 77l ASTM D 5478 363 ASTM E 1544, 748
ASTMD 4563 762 ASTM D 5531 464 ASTM F 462, 604
ASTMD 4584 714 ASTM E 11,317 ASTM F 489, 604
ASTMD 4585 679-680, 715 ASTM E 12, 145 ASTM F 518, 523
ASTMD 4587 680, 728-729, 865 ASTM E 20, 318-319 ASTM F 609, 602-604
ASTMD 4603 839 ASTM E 70, 221, 714, 748 ASTM F 692, 523
ASTM D 4610 656 ASTM E 84, 670, 672-674 ASTM F 923, 449
ASTM D 4613 82 ASTM E 96, 19, 728-729, 750 ASTM G 6, 20, 733
ASTM D 4614 129 ASTM E 97, 463, 744 ASTM G 7, 728-729
ASTM D 4615 129 ASTM E 100, 297 ASTM G 8, 733, 771
ASTMD 4616 19 ASTM E 102, 19 ASTM G 9, 733
ASTMD 4639 80 ASTM E 108, 19 ASTM G 10, 733
ASTMD 4640 80 ASTM E 119, 675 ASTM G 11,733
ASTMD 4662 109 ASTM E 136, 668 ASTM G 12, 733
ASTMD 4701 130 ASTM E 161,317 ASTM G 13, 733
ASTMD 4707 702 ASTM E 162, 670, 672, 674 ASTM G 14, 553, 733, 771
ASTMD 4708 416, 538-539, 774 ASTM E 167, 474, 688 ASTM G 17, 733
‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬


ASTM G 19, 733 Barrier coatings, 238-239 Blue pigments, 197-198
ASTM G 20, 733 Basecoat, automotive products, 713 inorganic, 210-211
ASTM G 26, 648, 680 Basic calcium zinc molybdate, 242 BN 8-4, 579
ASTM G 42, 771 Basic calcium zinc molybdate/zinc Boiling point, solvents, 137, 139-140
ASTM G 50, 613 phosphate, 242 Bond strength, thermoplastic marking
ASTM G 53, 774 Basic lead silicochromate, 242 materials, 745
aerospace and aircraft coatings, 692 Basic zinc molybdate, 242 Bone blacks, 179
automotive products, 715 Basic zinc molybdate/phosphate, 242 BON maroon, 192
accelerated weathering, 649-650 Battelle chemical resistance cell, 663 BON reds, 192
water-repellent coatings, 749 Beading, water-repellent coatings, 749 Borates, inorganic anti-corrosive
ASTM G 85, 690 Beer's law, 785 pigments, 240-241
ASTM G 90, 639-640, 652 Bell Laboratory Rotating Disk Abrasion Bourger-Beer law, 869
ASTM G 95, 771 Test, 528 Bragg equation, 872
ASTM G 104, 613 Bell Telephone Laboratories Indenting Bratt conductivity cell, 663-664
ASTM gage, particle-size measurements, Rheometer, 565 Breakthrough time, effects of molecular
327-329 Belt Buckle Test, 582 size and affinity, 401-402
Atmospheric corrosion, metals, 611-612 Bentonite clays, 282 Bridges, sealants, 737
Atmospheric exposure testing, inorganic Benzene, solvent content, 152 Brightness, 507
anti-corrosive pigments, 248-249 Benzimidazolone-based reds, 195-196 Brightwell method, 428
Atomic absorption spectroscopy, 784- Benzimidazolone orange, 203 Brinell Indentation Hardness Tester, 566
786 Benzimidazolone yellows, 199, 201 Brominated pyranthrone red, 194-195
applications, 787-788 Benzoguanamine, 66 Brooldield and Stormer viscometers, 683
background correction, 786-787 Bierbaum Microcharacter, 556 Brooklield CAP 2000 viscometer, 363
coating failure analysis, 779 Binders Brookfield Digital Viscometer Model
cold vapor technique, 786 effect on stress in organic coatings, KU-1,360
flame characteristics, 785 594 Brooldield Synchro-Lectric viscometer,
graphite furnace, 786 role in hiding power, 483 362-363
pigment identification, 762 Biocidal efficacy, microorganisms, 262 Brooklield viscometers, 362-363
sources of interference, 786-787 Biological deterioration, 654-661 Brown magnetite iron oxide, 212
Atomic emission spectroscopy, 786 antimicrobial agents, 656-657 Brown pigment, inorganic, 212
applications, 787-788 bacterial resistance, liquid paints, 657 Brunauer-Emmett-Teller method, 313
background correction, 786-787 description of problem, 654-655 Brush application, architectural coatings,
sources of interference, 786-787 determining presence of fungal or 701-702
Attapulgite clays, 281-282 algal growth, 656 Brush drag, architectural coatings, 701-
Attenuated total reflectance, 829 effect on natural weathering, 627-629 702
Automobile industry, VOC standards, 8 fungal resistance, paint films, 657-659 Brushing characteristics, artists' paints,
Automotive products, 711-716 insect-resistant paints, 659-661 707-708
coatings, 554 Biopolymers, thickeners and rheology Brushouts, 485
hiding power, 713 modifiers, 277 BS 1006, 207
identification, 711-713 Bismuth vanadate/molybdate yellow, BS 2662, 207
material requirements, 713-714 211-212 BS 3900, 441-442, 504, 561
paints, waterborne amino resins, 66 Bisphenol-A based epoxides (see Epoxy El, 550
pearlescent pigments, 230-231 resins) E4, 551
performance requirements, 714-715 Bitumens, history and background, 15- BTL Balanced Beam Mar Tester, 579-
pretreatments, 711 16 580
primer, 711-712 Bituminous coatings, 15-21 Buchholz Indentation Hardness Tester,
process requirements, 715-716 ASTM definitions, 15 566
surface cleaners, 711 general tests for, 20 Bulk modulus, 573
topcoats, 712-713 for paving, 18 Buoyancy-hydrometers, 297-298
viscosity, 714-715 resin modified, 21 Burgers model, 348-349
Azam method, oil absorption roof coatings, 16-18 Butyl alcohols, 129
determination, 253 solvent-thinned or cut-back, 20-21 Butyl sealants, 735
Azo-based oranges, 200-201,203-204 specialty paints and coatings, 16 BYK-Gardner cupping tester, 551-552
tests on, 18-20
types, 16-18
B waterproofing membranes, 18
Black box, 634-636
Bacteria accelerated natural weathering, 638 Cadmium mercury orange, 212
associated with paint, 654-655 Black panel thermometer, 633 Cadmium orange, 212
resistance of liquid paints, 657 Black pigments Cadmium red, 210
Bactericides, 261-267, 657 carbonaceous pigments, 179 Cadmium sulfide yellow, 211
analysis and decontamination, 265- classification, 180 Cadmium zinc yellow, 211
266 iron oxide blacks, 179 Caframo REAX 2 rotating mixer, 416-
definition of terms, 261 (see also Ceramic coatings) 417
methods for determination of efficacy, Bleeding Calcium borosilicate, 243-244
267 artists' paints, 708 Calcium carbonate, 176-177, 217
mode of action, 262-265 traffic marking materials, 743 California, smog, 3-4
reactive with acetylacetone, 263,265 Bleed test, colored organic pigments, 207 Camp abrasion tester, 529
strategies for minimizing resistant Blister formation, osmotic, 768 Can, production processes, 717-720
strains, 265 Block copolymer sealant, 735 can end preparation, 719
Bake latitude, automotive products, 715 Block resistance three-piece can, 718-719
Balanced beam tester, abrasion architectural coatings, 704 two-piece can, 717-718
resistance, 531-532 artists' paints, 708-709 Can coatings, 717-723
Barium metaborate, 240 can coatings, 723 industry, 717
Barium sulfate, 219-220 Blue-green pigments, 214 tests
‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬


on cured surfaces, 721-723 Chemically reactive cross-linking Cleanability, aerospace and aircraft
on liquid paint, 720-721 binders, coating failure analysis, coatings, 693-694
ultraviolet cured, 719-720 770-771 Clean Air Act, 3-5
Cantilever (beam) method, stress in Chemical resistance, 662-666 Amendments of 1977, 5
organic coatings, 589-590 acid resistance, 664-665 Amendments of 1990, 9-12
Capillary forces, 355 alkali and detergent resistance, 664- Title I, 9
Capillary rise, 374 665 Title III, 10
Capillary rise method, contact angle artists' paints, 709 Title V, 10
measurements, 378 household, architectural coatings, 704 Title VI, 11
Capillary viscometers, 363-364 salt fog test, 664, 666 Title VII, 11
Capillary waves, 377 solvent/fuel resistance, 663-664 Cleaning, surface pH after, masonry, 727
Carbazole violet, 198 staining, 662-663 Cleansability, architectural coatings,
Carbonaceous pigments, 179 treated masonry, 750 704-705
Carbon arc lamps, 644-645, 648-649 water and moisture resistance, 666 Clearcoat
Carbon blacks, 179-189 Chemical testing, pearlescent pigments, automotive products, 713
channel process, 181 - 182 235 crack formation, 598
dispersion quality, 186-187 Chloride, effect on atmospheric Clemen Scratch Hardness Tester, 556
formation, 179-180 corrosion, 6l 1-612 Climatology, 628-635
furnace process blacks, 181, 183 Chlorinated hydrocarbons, solvents, 130 desert, 629-630
gloss, 186, 189 Chlorine exposure effects, 630-631
jetness, 183, 185, 188 detection in plasticizers, 119 extreme cold, 629, 631
lampblack process, 180-182 effect on atmospheric corrosion, 611- instrumentation, 632-635
measuring appearance properties, 188- 612 marine, 629-630
189 Chroma, 507 subtropical climate, 629-630
mechanisms of interaction with light, Chromates, inorganic anti-corrosive temperate with pollution, 629, 631-632
181-182, 184 pigments, 241 Coal tar enamels, 731
opacity, 183 Chromaticity coordinates and diagram, Coal tar epoxides, 732
optical function, 179-182 454-456 Coal tar mastic, 732
parameters affecting optical function, Chromatic paints, tinting strength, 508 Coat tar urethane, 732
182-183, 185-186 Chromatography, 789-8 l0 Coated paper techniques, for obtaining
preferred form, 186 adsorption, 790 free films, 416
selecting a grade, 187-188 "classical column," 791 Coating consistency, thickeners and
tinting strength, 183, 185, 189 displacement analysis, 790 rheology modifiers, 273-274
undertone, 185-186, 188-189 elution analysis, 790 Coating failure
Carbon dioxide, supercritical, as frontal analysis, 790 analysis, 767-779
solvents, 131 high pressure liquid, 779, 792-793 application of coating, 775-777
application techniques and
Casson viscosity, 337 liquid (see Liquid chromatography)
equipment, 776-777
Castor oil, 27 paper, 793-794
background information, 777
Catalyzed cross-linking partition, 790-791 determination if specified coating is
phenolics, 410-411 principles, 789 used, 773
silicones, 411 size exclusion, 837-839 electron microscopy, 822-823
Cathodic passivation, inorganic anti- thin-layer, 794-796 evidence collection, 777-779
corrosive pigments, 239-240 (see also Gas chromatography; High field investigation, 778
Cationic agents, as sanitizing agents, 265 performance liquid generic type of coating, 769-772
Caulks, oil-based, in sealants, 735 chromatography) hypothesis testing, 779
CDIC Hardness Penetrometer, 566-567 Chrome-doped futile, 214 identification of system, 768-774
Cellulose acetate butyrate, 25 Chrome green, 212 inorganic binders, 771-772
Cellulose acetate propionate, 25 Chrome orange, 212 laboratory investigation, 778-779
Cellulose esters, 23-25 Chrome yellow, 211 metallic coatings, 772
coating applications, 23-24 Chromium oxide green, 212 modes associated with pigment
production, 23 Chrysler MS-PPI-1,713 system, carrier system, or additive
testing, 24 C.I.E. L * a * b *, artists' paints, 708 package, 772-773
types, 23 CIELAB space, 456-457, 465 organic resin binders, 769-771
Cellulosics, 275-277 C1ELUV space, 457 proper formulation and
hydrophobe modified, 280 CIE system, 452-457, 507 manufacture, 773-774
Centrifugal sedimentation, 321-324 blackbody locus, 455-456 purpose of coating, 774-775
Ceramic black, 215 chromaticity coordinates and diagram, reporting findings, 779
Ceramic coatings, 68-72 454-456 specification preparation and follow
application processes, 72 color temperature, 456 through, 775-776
composition, 69 complementary wavelength, 455 surface/substrate preparation, 776
glass enamels, 71 dominant wavelength, 455 third party inspection, 777
glazes, 68-69 purity, 455 definition, 768
porcelain enamels, 69-71 standard observers, 453, 455 Coating films, 110
refractory coatings, 71-72 standard sources and illuminants, 452- Coatings
Ceramic pigments, 214-216 454 anti-corrosion, 238-239
properties, 215 tristimulus values, calculation, 453- cleaning and pretreatment, 380
testing, 216 454 dry, on substrates, 417-418
CGSB I-GP-71,504 uniform color spaces, 456-457 flexibility, 542
Chalky surfaces, adhesion to, Circular drying-time recorder, 443-444 high solids, xv
architectural coatings, 705 Circulation stability, automotive new technologies, xv-xvi
Channel process, carbon blacks, 181-182 products, 716 performance, properties affecting,
Chemical adhesion, 514-515 Clarion red, 203 547-548
Chemical analysis, traffic marking Clay stabilized emulsions, bituminous processes, extensional viscosity, 350
materials, 743 coatings, 21 strength, 507
‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬


Cobalt blue pigments, 214-215 violets, 210 Contrast ratio, 481-482
Cobalt phosphate violet, 215 yellows, 211-212 aerospace and aircraft coatings, 687
Code of Federal Regulations, subchapter Colored organic pigments, 190-208 specified spreading rate, 493
topics, 11 bleed test, 207 Control technique guidelines, 5-6, 11
Coefficient of friction, 600 blues, 197-198 VOC content determination, 6-7
Canadian government standards, 603, classification, by chemistry, 191 Copper corrosion, plasticizers, 116
605 color and tint strength, 207 Copper phthalocyanine blue, 197-198
concept of, 601 Colour Index, 190 Copper phthalocyanine green, 203-204,
determination, 601-602 exposure testing, 207-208 206
determination methods, 603-605 fastness tests, 207 Copper strip corrosion, solvents, 153
measurement, 604-605 greens, 203-204, 206-207 CoRI stressmeter, 590-591
Coefficient-of-Friction Mar Test, 582 health and environmental concerns, Corrosion
Coefficient of thermal expansion, 853- 204-206 accelerated testing, 248-249
854 oil absorption, 207 in aqueous solutions, 609-611
Cohesion, versus stress, 594, 596 oranges, 200-201,203-205 atmospheric, 611-612
Cohesion energy, 385 reds, 191-197 copper, plasticizers, 116
Cohesive energy density, hydrocarbons, high performance, 194-196 copper strip, solvents, 153
389 metallized azo, 191-192 definition, 238
Coin mar test, 532, 582 non-metallized azo, 192-194 inhibition, aerospace and aircraft
Cold checking resistance, automotive novel high-performance, 196-197 coatings, 690-691
products, 715 specific gravity, 208 metals, prevention (see Protective
Cold crack resistance tests, 554 testing, 206-208 overlayers)
Cold vapor technique, atomic absorption yellows, 198-203 resistance, automotive products, 715
spectroscopy, 786 benzimidazolone, 199, 201 thin films, 612-615
Cold weather, extreme, 629 diarylide, 199-201 Cost factor, weighted, traffic marking
Cole method, critical pigment volume heterocyclic, 199-200, 202-203 materials, 747
determination, 255 monoarylide, 198-199 Cottonseed oil, 27
Colligative properties analyses, 836 Colored pigments, 484 Coulometry, trace sulfur by, 154
Color hiding power, 487 Coulter principle, 316-317
aerospace and aircraft coatings, 687 Colorimeters, 687 Crater resistance, automotive products,
architectural coatings, 702 pearlescent pigments, 231 716
automotive products, 714 tristimulus, 463 Crevice corrosion, 610
change Colorimetry, definition, 452 Critical pigment volume, 303
artists' paints, 707 Color-matching booths, 448 Asbeck-Van Loo method, 254-255
sealants, 737 Color order systems, 457-462 Cole method, 255
colored organic pigments, 207 colorcurve system, 460 Pierce-Holsworth method, 255-256
compatibility, architectural coatings, cylindrical systems, 451 Critical pigment volume concentration
700 DIN system, 459-460 effect on stress in organic coatings,
constancy, 451 ISCC-NBS system, 458 591-595
feasibility, automotive products, 715 Munsell system, 457-458 oil absorption and, 256-257
industrial measurement, 462-465 natural color system, 459, 461 Crock resistance, automotive products,
commercial instruments, 464-465 opponent systems, 451-452 715
instrument selection and calibration, OSA-UCS system, 459-461 Cross-link density, 587
463-464 Ostwald system, 459 determination, 541-542
instruments using eye as detector, printed systems, 460 Cryogenic scanning electron microscopy,
462 scales for liquids, 462 820-821
spectrophotometers, 462-463 universal color language, 458 Cryptometers, Pfund, 486-488
tristimulus colorimeters, 463 whiteness indices, 461-462 Crystal, size, white hiding pigment, 500
liquid, mixing time, 510 yellowness indices, 462 CS 19.1-M87, 739
matching, 467-468 Colour Index, 190, 507 CS 19.2-M87, 739
measurement, can coatings, 723 Combustibility, tests for, 668-670 CS 19.6-M87, 739
metamerism, 451-452 Commercial Standard 98, Section 6.6, CS 19.13-M87, 739
mixing, 466-467 707-708 CS 19.18-M87, 739
perceived, variables, 451-452 Compartment fire tests, full-scale, 674- CS 19.20-M87, 739
temperature, 456 675 CS 19.24-M80, 739
terminology, 447 Compatibility, titanium dioxide CS 19-GP-5M, 739
tolerances, 465-466 pigments, 174 CS 19-GP-14M, 739
traffic marking materials, 743-747 Condensation CS 19-GP-17M, 739
uniform spaces, 456-457 controlled testing, 679 CS 19-GP-22M, 739
variation, artists' paints, 708 effect on natural weathering, 627-628 Cup viscometers, 683
(see also CIE system) Conductivity, automotive products, 714 Cure, 407-414
Colorcurve system, 460 Conical Mandrel tests, 548-549 adequacy of, automotive products, 714
Color differences Consistency concept and illustrations, 407-408
calculations, 465 architectural coatings, 700-701 measurement, 411-414
instrumental measurements, artists' paints, 707 dynamic mechanical analysis, 413
architectural coatings, 702 Constant depth gage, particle-size evaporative rate analysis, 413
visual comparison, architectural measurements, 328 hardness measurements, 411-413
coatings, 702 Construction Criteria Base, 892-893 impedance measurements, 413
Colored inorganic pigments, 209-212 Contact angle, 372-373, 514 solvent rubs, 411
blues, 210-211 measurement, 378 thermal analysis, 412-413
browns, 212 Contaminants, titanium dioxide torsion pendulum, 413
classification, by chemistry, 209-210 pigments, 169 mechanisms, 408-411
greens, 212 Continuous flow method, particle-size radiation (see Radiation curing)
oranges, 212 measurements, 313 reactions, amino resins, 64-65
reds, 209-210 Contrast, visual observations, 482 speed, can coatings, 720-721
‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬


Curing agents, epoxy resins, 74-75 Diethylenetriamine, 85-86 Driers, 30-35
Current, thermally stimulated, 855 Difference spectroscopy, 830-832 function, 30-31
Curtain coating, surface energetics, 379 Differential scanning calorimetry, 759, levels in coatings, 32
Curvature, effects on film thickness 761, 842-845 liquid paint
measurement, 435 coatings characterization, 846-847 specifications, 33-34
Cycle testing, water resistance, 679-680 epoxy-amine reaction kinetics, 845- testing, 34-35
Cycloaliphatic epoxides, 109-110 846 metals, description, 31
films, tensile properties, 545 glass transition temperatures, 843-844 miscellaneous, 31-32
Cyclohexane, 127 purge gas, 846 recommendations, 33
Cylindrical Mandrel bend tests, 549-550 sample preparation, 846 testing of drying efficiency, 32-33
Differential thermal analysis, 759, 761 Drop weight, 374
Diffusion theory, 514 Dry film
D Digital electromagnetic thickness gages, appearance, m-chitectural coatings,
432-433 702-703
Damping, hardness, (see Pendulum- Dilatancy, 339-34l printing, vinyl resins, 105
rocker hardness) Dilatometry, 853 Drying oils. 26-29
Dantuma Scratch Tester, 556-557 Diluent dilution ratio, solvents, 133 classification by iodine value, 26
Database sources, specifications, 892- Diluents, 131-132 physical characteristics, 26, 28
893 Dilution limit, solvents, 133 Drying time, 439-444
Data processing, infrared spectroscopy, Dilution stability, architectural coatings, aerospace and aircraft coatings, 686
829 699 artists' paints, 708
Daylight, natural and artificial, 447, 453 Dimensional stability, water-repellent ASTM D 1640, 439-440
Deadhesion, organic coatings, 616 coatings, 749 B.S. 3900, 441-442
Deborah number, 348 Dime scrape, automotive products, 715 circular drying-time recorder, 443-444
Debye-Scherrer small angle X-ray DIN 33 157, 574 DIN 53 150, 442
scattering technique, particle-size DIN 35 152, 550 environment, 439
measurements, 325 DIN 50 101,551 Federal Test Method Standard 141C,
Debye-Sherrer camera, 872-873 DIN 50 102, 551 Method 4061.2, 440-441
Deformation, definition, 334-335 DIN 53 150, 442 I.C.I. drying time recorder, 444
Degradation, 631 DIN 53 153, 563 ISO 9117, 441
amino resins, 65-66 DIN 53 162, 505 no pick-up lime traffic paint roller, 444
test, metallic pigments, 227 Dinitroaniline orange, 200 specimen preparation, 439
Deleveling, 357 DIN system, 459-460 straight line drying time recorder, 444
Density, 289-303 Dip coating, 421-422 Dry-powder pulse jet disperser, 315-316
aerospace and aircraft coatings, 684 surface energetics, 379
Dry to-recoat, aerospace and aircraft
alkyds, 56 Dipentene, 127
coatings, 686
apparent, 290 DIPPR database, 390
Du Nuoy ring, 374-375
solids, 302 Directionality, gloss, 471-472
Du Pont Scratch Testing Machine, 557
architectural coatings, 698 Direct tensile testing, adhesion, 519-523
automotive products, 714 Dirt pickup, architectural coatings, 705 Durability
bulk, 296 Disazo condensation reds, 196 sealants, 737
can coatings, 720 Disbonding method, 560 testing, titanium dioxide pigments in
concern for, 289 Disk centrifuge, 321-323 coatings, 173
definitions, 145-146, 289-291 Dispersibility, titanium dioxide pigments, traffic marking materials, 747
dynamic model, 290 171-172 Dynamic coefficient of friction, 600
liquids, 297-301 Dispersion Dynamic mechanical analysis, 842, 847-
determination methods, 297-298 carbon blacks, 186-187 850
fluid exWrnal media, 297-298 fineness of applications, 847
fluid internal media, 298-299 aerospace and aircraft coatings, 684 automated instruments, 538
sonic frequency shifts, 299-301 architectural coatings, 698-699 coatings characterization, 848, 850
measurement systems, 296 artists' paints, 708 cure, 413
plasticizers, 117-118 can coatings, 720 studies, 858-860
relative; 290 traffic marking materials, 743 description, 538-539
skeletal, 296 interactions, 385 glass transitions, 847
solids, 301-302 pigments, 508-509 heating rate, 848
solvents, 144-148 rheology, 351-352 plot interpretation, 539-541
static model, 289-290 solubility parameter, 387, 389-391 sample preparation, 848
Density gradient column systems, 301- white hiding pigment, 500 synthetic variables and morphological
302 Displacement analysis, chromatography, character, 847-849
Desert, 629-630 790 Dynamic mechanical and tensile
Detergent resistance, 665 Displacement technique, 294-295 properties, 534-545
Deterioration, biological, (see Biological Dissolution cross-link density, determination, 541-
deterioration) anodic, 610-61 l 542
Dial gages, 426, 428 microwave, 757 definitions, 534-536
Dianisidine orange, 201 Distillation dynamic property relation to other
Diarylide yellows, 199-201 plasticizers, 116-117 mechanical properties, 542
Diatomaceous solid support materials, range, solvents, 137, 139-140 free film sample preparation, 537-538
799-800 Distinctness of image, automotive stress-strain curves, interpretation,
Dielectric analysis, 842, 855-857 products, 714 543-544
film formation, 855-856, 858 Doctor Test, 153 tensile properties, 543-545
frequency selection, 856-857 Drainage equation, 353-354 relation to other mechanical
heating rate, 857 Drawdown, thin-film, oversize particles, properties, 544-545
powder coatings, 855-856 326-327 tensile versus shear tests, 534-535
resin, 855, 857 Drawdown bars, 418-420 Dynamic mechanical thermal analyzer,
sample preparation, 856 Drier acids, description, 31 548
‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬

723 Electrical resistivity/conductivity.iran-mavad. 75 Method 2112. Method 2141. 577. 644 mechanical properties. 434. 759 cross-linked with acid-functional unsaturated. 359-360 Energy dispersive X-ray. 204-206 test standards. 408 solvents. 74-75 FDC wear test. 750 Energy dispersive spectrometer. 432. 551 Method 4021 684 Electron probe microanalysis. 728-729 Enamels Exposure frames. 245 wollastonite. 450-452 Electrochemical analysis.1. 70 colored organic pigments. 731 Exposure testing Method 4061. 736 metallic pigments. transmission Equivalent spherical diameter. 651 Electrochemical impedance Epoxides spectroscopy. sealants. 685 microscopy. particle-size measurements. 710 failures and defects. 866 Epoxy/acrylic copolymers. analysis. 217-218 525 Energy of vaporization. 685 microscopy) Equivalent circle diameter. 815-816 two-package. 822-823 heat-cured solvent-borne coatings.1. 822-823 77 Federal Test Method 4287. can coatings. 128 Method 4541 701 Electrostatic spray. 818-819 curing agents. 818 726. 221-222 Elcometer magnetic coating thickness inorganic anti-corrosive pigments. 78 Method 2051. 830-831 Eddy current thickness gages. 313. coating failure inorganic anti-corrosive pigments. 70 scum on panels.729 identification. 529-530 Electron microscopy. 882-883 coatings. particle-size Environmental Protection Agency Exterior coatings. 280-281 Method 4271. 310-311 Method 3021. for straight mica. ambient-cure coatings. 557-558 Method 4121 489 Electron spectroscopy for chemical Erichsen Lacquer Testing Instrument. 87-88 X-ray diffraction. 220 gage 211. 363 Electromagnetic radiation. 227 Environmental scanning electron Eye. 43 FDC Fine Scratch Test. 849 Fastness tests. 66-67 talc. architectural coatings. ambient cure coatings.431 amino resins. 741 Falling-needle viscometer. regional offices. monitoring fusion bond. solvents. 77 Federal Test Method Standard 141 pigment powder coatings.2. in drying oils. 822-823 Erichsen cupping tester. aerospace and coal tar. 220 masonry. purity. 220 viscoelastic models. aerospace and microscopy.685 ElectronToptical column. 515 Esters. 74-75 Method 3019. 377 77 traffic marking materials. 770 Falling abrasive test. Ethyl hydroxyethyl cellulose. aerospace and aircraft physical properties. 219 Elastic liquids. 220 Elcometer I01. 865 859-861 coatings. chromatography. 689 Emulsions. 220-222 viscoelastic parameters. surface energetics. Method 6261 700 Elutriation. 217-222. 615 barium sulfate. Extender pigments. 218 Elcometer dial gage. Electromagnetic thickness gages. 247 Elasticity. 542 Electromagnetic spectrum. 361 Emulsion particles. 581. 362 latex coalescence and adhesion. 218-219 Elastic modulus. 310 Method 3022.2. Method 4203 699 analysis. 778 kaolin. cure. 11 Extrusion rate. 76. antifouling paint film structure.1. 129 Method 6301 704-705 Emulsion coatings. 74-78 Fatty acids spectroscopy.685 ele'ctron microscopy. measurements.729 coal tar. 652 582 Method 4421 700 Electrostatic adhesion. 689 Electron beam excited X-ray Epoxy resins. cure mechanisms. 691 Envirotest. 377 Electrodeposition coatings. scanning electron acrylics. modified. dynamic Falling weight impact tests. 3 Extraction testing. Method 4401 699 ultrafast weathering. 77 Federal Hazardous Substances Act. 823-824 properties. 761. Epoxy-amine reaction kinetics. 149-150 administered by. 732 aircraft coatings. 702 signal types. relation to abrasion resistance. Fatigue tests. 875-877 Electrical resistance. Erichsen Scar-Resistance Tester. 85 Electron beam X-ray analysis. 691 coating failure analysis. 824 heat-cured waterborne coatings. 701 (see also Scanning electron 75-76 Method 3011. 790 Ethoxylate urethanes. 817-818 calcium carbonate. 76 artists' paints. 314 analysis. 389 nepheline syenite. aerospace and aircraft Electromotive radiation. 87 Method 2131. 219-220 treated masonry. 526-527 Electrochemical methods. hydrophobe. soap titration. 483 Elcometer pull off gage ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . 278 Method 6271 658 314-315 Ethyl alcohol. 117 Method 6211 573 Elution analysis. 816. 702 particle sizing.430 pearlescent pigments. 436 End group analysis. 726 Energetic deposition techniques. colored organic pigments. plasticizers. cure. 440-441 www. 21 hydrophobe-modified. EN-71-3:1988. SUBJECT INDEX 911 E cover coat. reactive crosslinking. 217 Efflux devices. 346~348 Engine oils. 26-27 Electron guns. 710 Everhart-Thornley detector. Evaporation rate Federal Test Method Standard 141B. 151 Method 6192 530 379-380 Ester value. 760 723 Method 4208 685 Electron spin resonance spectroscopy. 344-350 chain hydrocarbons. 207-208 ground coat. 277 Federal Test Method Standard 141A. 591 Environmental impact sodium aluminosilicates. Federal Reference Method 24. 692-693 silica. 768. 430 polyamides. 823-824 reactions with polyamides. 761 Erichsen Hardness Tester. 316-317 federal environmental laws 697 Electrical resistivity. bituminous coatings. 428 colored organic pigments. 410 Falling meniscus method. 720 film thickness measurements. 135-139 Federal Test Method Standard 141C. 845-846 207 434 Epoxy polyester powder coating. Transmission electron types. 484 Efflorescence 835 alumina trihydrate. epoxy resins. 235-236 Extenders. 361 atmospheric corrosion. 582 microscopy. 634-636 Method 2051. 413 Method 6226. 612 Epoxy Falling curtain. 75 tall oil. 426. 5-8. 847. 824 ester. '345-346 coatings resistance. 732 Falling ball viscometer. 821 aircraft coatings. 815-824 electrodeposition coatings. 783-784. molecular weight.

419 strain rate effects. 670-672 Fracture energy. 415-417 architectural coatings. 449 columns. formation Flash point 705 dielectric analysis. materials. ASTM D 2863. 802 Fisher subsieve sizer. 651-652 Filiform corrosion. 435 386 485 electron microscopy. 428-429 Fluid resistance Gardner impact. thermoplastic marking Gardner gage stand. curvature effects. 707 Filed testing. Fluorescent light sources. 714 artists' paints. 675 Fresnel reflector. 672-674 Fracture theory. 488-489 ASTM E 84.iran-mavad. 554 disfigurement of paint films. can coatings stability. 797-798 surface finish effects. accelerated natural aircraft coatings. 552-553 Fusion bond epoxides. 548 Film thickness t-bend tests. 691 terminology. amino resins. 808-810 Fire-retardant coatings. 655-656 wire-wound rods. 803-804 wet film. 797-798 size measurements. 657 free. transparent. 424-427 shear-thickening. 424-438 modifiers. 858 aerospace and aircraft coatings. 548-550 G Film casting knife. 800-801 film. 27-28 free. 843-845 Method 6226. 707 426 can coatings. 675 Food processing. 117 267 porosity solvents. casting techniques. 667-676 temperatures. thickeners and rheology Gardner-Coleman method. programmed temperature. 361 destructive methods. 732 467 humidity effects. 548 Fusion process. chromatography. 265- hardness. 426. 415-423 aging and weathering effects. paint (see Biological deterioration) plasticizers. 466. HETP. 553-554 wet. 668-670 coating failure analysis. 649-650 gas-solid chromatography. 692. 670. 341-343 column efficiency. 437 Newtonian and non-Newtonian. 263. 339 chromatogram interpretation. 547 thickness. 822-823 Flowability. 654-655 drawdown bars. 704 Flexibility. development. 183 effect on coating performance. 785 552-553 pyrolysis. 513-514 Felvation. 420-421 Furnace process blacks. 252-254 hiding power. 790 Film Flame-spread index. 604 ASTM D 3894. cupping tests. 797-798 568 Formaldehyde internal standardization. 670. 722 high-performance detectors. 612-615 662-663 transparent. 415-418 automotive products. 271-272 determination. 798 spectroscopy. temperature effects. 72 l Flammability. 528 Flame retardance. 646 glossary. ASTM E 119. 600 inhibition. oil absorption measurement. 715 656 spin coating. 709 determining presence on paint films. 265 preparation. staining resistance. 513 Fell equation. 261-267. Fungal resistance. 668 750 Feret's diameter. 500-501 aerospace and aircraft coatings. 547- pavement marking tape. 806-807 www. 422 can coatings. cathodic reaction test selection rationales. 484 778 ASTM E 1131. 581 ASTM D 3806. 686. 437-438 693 Gardner needle thickness gage. for coating tests. 429-434 aerospace and aircraft coatings. 755 methods for determination of efficacy. 612 687 Flocculation Gardner Carboloy drill thickness gage. 674-675 Fresnell equation of reflectivity. 435. 713 Fume resistance. 261 448-449 paint. Gardner contrast hiding power board. 438 shear-thinning. 808-809 Fingernail Mar Test. testing. ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . 805-806 Fish oils. 418 Fluorescence. can coatings. 672 Fuel resistance. 722-723 discoloration of paint films. corrosion. time-dependent. 294 aerospace and aircraft coatings. treated masonry. 699 analysis and decontamination. 336 applications. 415 181. 715 Gas chromatography. 418-420 artists' paints. 585-586 686 Fungicides. 547-554 strategies for minimizing resistant white hiding pigment. 672. tests for. 670. and translucent. 421-422 architectural coatings. 674-675 Fracture stress. 657-659 stress in organic coatings. 675 Freeze/thaw resistance. 807 Flame characteristics. 327-329 UV/condensation lamp. 654 spray outs. 311-312 as biocide. 513 Federal Test Method Standard 501a. 670 Fourier transform infrared analysis. 745 Furniture finishes. 667-668 weathering. 801-803 relationship between wet-film and dry. architectural coatings. 798-799 Fineness-of-dispersion gages. 720 definition of terms. 526. 428 dry film materials. alkyds. 802 X-ray fluorescence. 639-640 Filler particles. carbon blacks. particle-size measurements. ASTM E 603. Gardner micro-depth gage. 550-551 Gallon weight cups. 418 interpretation. 674 Freeze-thaw stability. forming tests. 566. 426 substrate composition effects. aerospace and historical methods. 670-675 Frontal analysis.912 PAINT AND COATING TESTING MANUAL Method 6141. 119. 428 statistics. 721 mechanisms. 315 ASTM E 136. 797-798 Four acrylic copolymers. glass transition Method 6193. 310-311 ASTM E 162. 855-856. 709 266 opaque. 408 impact resistance tests. atomic absorption Forming tests. 32-33 artists' paints. 745 Gardner-Holdt bubble tubes. can coatings. 582 UV lamps. 339-341 area normalization. 689 strains. artists' paints. 548 Galvanic cells. automotive products. subtractive mixing. 532. film casting techniques. 482 Flory-Huggins limiting chi parameter. 412 nondestructive methods. 773 Method 1093. 663-664 continuity. 421 cold crack resistance tests. paint films. 548 thin. 447-448. 551-552 test requirements. 758. 704 associated with paint. 64 plasticizers. 262-265 architectural coatings. 675-676 concentration. 616 Flame spread. 265 oils. automotive products. 796-810 437 Fluids apparatus and technique. 424-427 Mandrel bend tests. 453 detector. 668 Friction. 140-144 mode of action. 800-801 Fischerscope Microhardness Tester. 554 Fungus dip coating. automotive products. flexibility and toughness. 54 types. coating failure analysis. 553 ASTM D 1360. particle. 531 Flame ionization detectors. 685. Federal Test Method Standard 406.

203-204. 198-199 insulating. 470-479 sealants. 487 spreading rate. 401 relative dry. 280 solid support. 62-63 image clarity. Graharn-Linton Hardness Tester.iran-mavad. 489 General Electric Indention Tester. 805 waviness. applications. 411-413 titanium dioxide pigments.503 General Electric Impact Flexibility Tool.504 measurements. 786 Fell equation. 71 photometric end-point. 484. 723 Heat-activated binders. 63-64. 481-505 robing materials. 384 additive identification. 295-296 Goniophotometry. 721 test substrates. 709 hardness) (see also Kubelka-Munk two-constant automotive products. 504 adsorption. 370 measurements. Gavarti Gv Cat Test Unit. 484 artists' paints. 800 measurement. 313 determination. 470 Heat aging. 471 Hexamethylene diisocyanate. 802-803 476-477 Heterocyclic yellows. 485 lead-containing. liquids. 483 Gloss. 799 Gloss meter. 472-473 Hexa(methoxymethyl)melamine.803. 801-802 specular. 579-582 early. supercritical. 199 photometric measurements. 578-579 Van Eyken-Anderson method. 141. 202-203 resins. automotive products. 471 Heterogeneous surfaces. 69 rebound. metallic pigments. 477-478 693 size exclusion chromatography. 504 liquids. carbon blacks. thermoplastic acrylic resins. ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . 474-475 Heat of mixing. 483 Hansa yellow G. 486-487 enamels. 68-69 mar resistance testing. 790. particle-size film thickness. 573-578 traffic marking materials. 392 Gooden-Smith method. 314 definition. 397 relative. 714 terminology. 370 Green pigments. 715 Hallet hidimeter. effects on sealants. 690 standard test substrates. fineness of. 477 Hegman gage. 489-490 Gibbs free energy. measurement. 503-504 H Krebs method. 68-69 pendulum-rocker. spectroscopy. 199-200. corrosion. 736 High performance liquid directionality. 763 haze. Herschel-Bulkley equation. 293-294 Gold bronze pigments BSI 3900. 579 automotive products. 482 Gibbs equation. 714 film application. 206-207 German standards. 364 pigment effects on. SUBJECT INDEX 913 qualitative analysis. 502-503 solvent identification. 477. 400-401 pigments.479 Hiding power. 471-472 Heated Black Box Test. 489-490 843-844 aerospace and aircraft coatings. pavement marking tape. 609 Gravity sedimentation. 384-385 pigment role. 573 Hildebrand parameters. 703 Gas chromatography-mass spectrometry. 350 High-shear capillary rheometry. 489 bonding. Hansen solubility parameters. 384 www. 280 High pressure liquid chromatography. 343 Graphite furnace. solvent identification. 482-483 Gas-solid chromatography. visual observations. 490 ceramic. Glycoluril. 483-484 490 liquids. 481 thermoplastic acrylic resins. use. hiding power. 737 Hansa yellow 10G. 471 theory) can coatings. 170-171 leadless. 743) Hanstock method. 555-582 determination. 488-489 553 Gravelometer. Hardness. measurement. 557. 482 displacement. 764-765 GM9150P. 490 panels. 801-802 reflection haze. 737 reduction test. 688 Tukon. 1-GP-71. 487-489 809 1-GP-192. 487 adhesion. 566 Gravimetric method. 722-723 1-GP-200. 847 characterizations. 667 amino resins. 758 goniophotometry. 473-474 aerospace and aircraft coatings. 779 percentage. 471 Heat resistance. 154 Highways. 337-338 quantitative analysis. 525 visual end-point. 481 745 ISO methods. 321 French Standards Association. 40-42 automotive products. 793 measurement. 227-228 measurements. 714 Haze. 302 Goniospectrophotometers. 701 838 orange peel HEEASE polymers. 69 relation to abrasion resistance. 394. 489 satin. 610 retention parameters. particle-size grade classification. 581 Hencky strain rate. 771 697 definition. sealants. 736 white aerospace and aircraft coatings. 224 CGSB 1-GP-71. automotive products. 713 Gases. 692. 149-151. 173-174 Heptane Miscibility Test.891 early photometric methods. 485-486 temperature Hanstock method. 472-473 Heat stability. 474-475 contrast. thixotropy. 702-703 (see also Indentation hardness. architectural coatings. 687 weaknesses. incomplete. 605 early visual hiding power methods. 481-482 Gassing test. 605 485-487 Gearhart-Ball solvent resistance. 801 Glycol ethers. 487 beads Grind (see Dispersion. 189 analysis. 484 664 558 Federal Test for Dry Opacity. 224 colored pigments. atomic absorption Federal Test Method Std. 42 factors affecting. 212 Hallet hidimeter. 527 Herbert Pendulum Tester. 742 New York Paint Club method. 743 matte. solvents. coating failure High performance architectural coating. as hiding power test substrate. 473 Helium gas pycnometer. 499-501 architectural coatings. 764 visual evaluation. determination from tinting Glass transitions surface energy/contact angle data. 638 chromatography. 808. 837- Landolt ring use. 186. particle-size contrast ratio. extender pigments. 45 stationary liquid phase. 313 properties. 232-236 485-486 Gas phase dipole moment. 66 ASTM methods. 327-328 792-793 visual evaluation. 481 Glazes can coatings. sealants. 489 Gel coat. 470-471 HEURASE polymers. pearlescent contrast design and visual sensitivity. 472-473 409 solvents. 485-486 traff• marking materials. as solvents. 505 Glass inorganic. 302 coating failure analysis. 499 dynamic mechanical analysis. 799-800 measurement. 487 as concrete materials. 487 Pfund cwptometers. 471 aerospace and aircraft coatings. 482 differential scanning calorimetry. 806 sheen. 128-129 architectural coatings. 69 measurements. 663. Scratch hiding pigments. 474.

247 absolute. 242 627 Brinell Indentation Hardness Tester. 245 Humidity Imprint resistance. 867. 130 Rockwell Hardness Tester. 691. Inorganic pigments. 759 697 Hydrogen bonding. plasticizers. 329 787 Interface. 239 coatings. active sources. polyurethane coatings. 458 Hydroxyethyl cellulose. 557-558. 45-46 www. 328 ISO 8340 739 Image clarity. 547 performance. 826 ISO 1522 574 Hydroxyl value. 230 ISO 8394 739 measurement. 245 spectroscopy. 146-147 Infrared spectroscopy. 44-45 dispersive instrumentation. 230 Interferometry. in aromatic solvents. 246-247 effect on flexibility and toughness. 392 Infrared spectrophotometry. 615 processes that produce. thickeners Industrial coatings. 245-247 aerospace and aircraft coatings. 563-573 leads. 276-277 sample preparation. 615 naphthenic. accelerated corrosion testing. 210-211 soluble emulsions. 9 ISO 9000 329 aerospace and aircraft coatings. 532. 560 inorganic pigments) aromatic. extender pigments. 424-425 ISO 9046 739 693 Inorganic anti-corrosive pigments. 759-760 Hydrophobe modified alkali-swellable/ additive identification. 363 Inhibitor loading levels. 241-242 atmospheric corrosion. particle-size CDIC Hardness Penetrometer. oxidative passivation. (see Inorganic anti- solvents.914 P A I N T A N D COATING T E S T I N G M A N U A L Hoffman Scratch Tester. 561 hydrophobe-modified. pearlescent Interfacial thickness. particle. in Information Handling Services. spectrum. Inductively coupled plasma spectroscopy. 869 Impact resistance. analysis. 761-762 Inspector's Dur-O-Test Pocket Size Hydrodynamic chromatography. 209 synthetics. 771-772 nonaromatic. 829 Iron oxide reds. 244 chlorinated. 47-48. indentation hardness. 611 Bell Telephone Laboratories Indenting micaceous iron oxide. 507 Impinging abrasive method. 277 quality assurance. 247 Hydraulic fluids. 125-128 572 corrosive pigments. 563 phosphites. 239- resistance. 715 250 ISO 9048 739 cyclic. ISO 6927 739 ICI drying time recorder. 126-127 Inductively coupled argon plasma Inorganic sol-gel films. inorganic anti. 385 Infrared radiation. vinyl resins. 471 pearlescent pigments. 677-678 application and protective coating Holmium glass. 105 ISO 8503 435 Immersion testing VOC standards. 566-568 statistical analysis. Rheometer. 760-761 ISO 6860 550 ICI cone and plate viscometer. 704 flexibility and toughness. 242-243 Hutchinson method. 650. 128 pigment identification. 745 atmospheric exposure testing. 278-279 difference spectroscopy. ISO 9047 739 automotive products. 826-827 ISCC-NBS system. 587 566 phosphates. 249 variation and stress in organic Buchholz Indentation Hardness Tester. 763 Iron blue. 127 spectroscopy. 246-247 ISO 7389 739 ICI Pneumatic Microindenter. 241 Hue. 566-567 pigment volume concentration. 152 571-572 Inorganic coating. 832-833 ISO 3904 504 Hydroxypropyl methyl cellulose. 248 Hydrocarbons Pfund Hardness Tester. 553-554 240 staining from. 179 Hydrophobe modified nonionic data processing. low-energy. 413 chromates. 658 categories. 571 zinc oxide. 828-829 ISO 3905 503-504 sampling accessories. 244 relative Indentation hardness. 659-661 terpenes. cure. 243 Hutto-Davis method. architectural coatings. 244 cohesive energy density. 580 water resistance. testing. coating failure nitrated. 831-833 ISO 4624 521-522 time lapse spectroscopy. 692 Incandescent light sources. 566 silicates. architectural coatings. atomic absorption imprint resistance. 444 corrosive pigments. 826-833 Ion scattering spectrometry. 761 ISO 2813 474 Hydroxypropyl guar. 91 Infrared analysis. 238. 566-568 Inks ISO 8339 739 ICI Rotothinner. 360 particle-size measurements. 827-828 Hydrogen. 565 molybdates. 271 ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . alkyds. 548 Indanthrone blue. 245 effect on natural weathering. 625. 689 cathodic and anodic passivation. 314 Fischerscope Microhardness Tester. diffuse and sharp. 211 Hydroxyethyl acrylate. 239 100% testing. neutralization. aerospace and aircraft General Electric Indention Tester. 758. 477-478 vinyl resins. 568 reactivity and solubility.iran-mavad. 558-559 size measurements. 892-893 Interior coatings. 569 zinc. 786 Knoop Indenter. 567-569 substrate selection. 514 and rheology modifiers. 244 Hydrometer methods. 198 ion exchange pigment. 829-831 Iron oxide blacks. 245- measurements. 557. 571. 516 Hydrodynamic mechanism. 280 spectroscopy. 572-573 steel flake. 244-245 Isocyanate-reactive acrylics. 249 Hydride generation. 829 ISO 3906 504 spectral searching. Inmont wet film gage. in primers. 662 Impedance measurements. 247-248 Hopeite. 830-832 Iron oxide yellows. 275-276 Fourier transform infrared ISO 1518. 248-249 ISO 9117 441 651 aluminum flake. 44-45 infrared absorption. 105 tests borates. 246 Hydrated chromium oxide green. 4 Wilson/Tukon Hardness Tester. 625 572-573 formulation and performance. 449 Intumescent coatings. Ion chromatography. 279-280 applications. 243-244 coatings resistance. 759 Insect-resistant paints. 125-126 Indentation method. X-ray diffraction. 692-693 ICI Pneumatic Microindenter. 581 environmental considerations. 832 ISO 6504 504 vehicle identification. 57 pigment identification. 880-881 thermoplastic marking materials. 453 inhibitor loading levels. 827-828 ISO 1519 550 Hydroxyethyl methacrylate. accelerated weathering. 675 solubility parameter. 212 566. Colored aliphatic. Hardness Tester. 678-679 566 new product development. 248-249 Hot stamp transfer. solvents. 389 Twisting Cork Tester. 447. 240-241 Household chemicals aerospace and aircraft coatings. 759 temperature effects. 573 Inorganic binders. 397 118-119 Ion exchange pigment. 130 Wallace Microhardness Tester H-7.

797 enclosed carbon arc. 191-192 CIE standard sources and illuminants. 727 Judd graph. Fresnel-reflector testing Marangoni effect. 725 traffic marking materials. 779 efflorescence. hiding power. 449 aerospace and aircraft coatings. 564. vinyl resins. carbon blacks. 610 reflection and transmission. electron Liquid phase. 8 Lambert's law. 715 fluorescence. 492 plasticizers. 192 Kaolin. 652 Marine atmosphere. 481 499 single scratch methods. 33-34 Masstone. 495-496. 325-326 specifications. 466-467 Lithol reds. thermodynamics. 507 scuffing methods. 790 Library. 373 measures. 729 Lacquers fineness of dispersion. 493-495 Leveling rate. 491. 170-171 devices. 644-647 372-373 K additive mixing. 542. 373-378 thickeners and rheology modifiers. 530 glass transition. 498 d-Limonene. 581 Lightness. 698-701 pH after cleaning. 448 tensile. SUBJECT INDEX 915 Isocyanates coalescence and adhesion. 769 flash point. 507 Laser light. 47 as concrete materials. 485-486 ultraviolet and infrared spectral can coatings. 451 shear. 34-35 Mastic. automotive products. stationary. solvents. 836. particle-size absorption testing. 728 theoretical problems and practical solvents. 551 ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . 493-495 Linseed oil. 698-699 solvent-borne coatings. 729 cure mechanisms. 449 Magneto resistor. 294. carbon M Ketimine. 603 Katharometers. 297-301 ISO TC 35. 492 applications. 180. 725 scattering coefficient and scattering coating failure analysis. 727 theology. 408 Liquid pycnometers. 701 dynamic properties. for potential. 843-844 Liquids. solvents. 646 Kelvin-Voigt model. 727-729 Laboratory testing coarse particles in. 749 gloss and semigloss. 355-356 surface tension measurement. 323-325 alkali resistance. 824 chromatography. 629-630 Kubelka-Munk relation. 185. 27 artificial weathering tests. 727 traffic marking materials. 119 field testing. 657 Mass. 472-473 bacterial resistance. 491-492 Lightfastness. 778-779 color compatibility. 726 properties. 416 dilution stability. 297-299. color-matching booths. 800 reactive cross-linking. 743 water-reducible coatings. xenon arc. 614 can coatings tests. 448-449 106 Knife scrape. 699 specimens. and translucent Maintenance coatings. 893 Liquid/solid interfaces. 181-184. 128 lamp stability. 700 porosity. 184 Ketones. 728 Lab roller mill. 727 considerations. 536 Karl Fischer reagent method. 41. 507 Latex testing. 726-727 Lampblack process. 295-296 ISO/DIN 4584. 499 measurements. Light scattering. 749-750 182 Liquid paint water vapor permeability. 127 application. Lithol rubine red. 530 Laurie-Baily Hardness Tester. 725-730 techniques. 309. 298 ISO/DIN 3494. 683-684 sources. sources of specifications. 699 selection. 394.839 499 Mar resistance testing. 447-448 Manganese-doped ruffle. 709 hiding power impinging abrasive method. particle-size driers Mass spectrometry. coal tar. 447 Marine finishes. 429-430 purity. 689 Krebs-Stormer viscometer. 214 Krieger-Dougherty model. 188 274-275 (see also Elastic liquids) Judd graph. 567 opaque. Light. 728 Landolt rings. 791-792 definition. 567-569 film. 467 terminology. 690 equation symbols. 412. 150-151 open-flame carbon arc. 727-728 results. 495-497 Liquid chromatography. 448-449 polymers. 351-352 spectrum. untinted white paints from Masonry. gas in polyurethane coatings. drying. 579-580 molecular weight determination. 741 treatments. 579-582 Light absorption. 358 Hansen solubility parameters. 370-372 Jetness. 408 odor. curing agents. 548-550 chart. 354-358 displacement. VOC standards. transparent. I05-I06 Kubelka-Munk two-constant theory. 725 tinting data. 49 Krebs diamond-stripe hiding power retroreflection. artists' paints. 700-701 preparation. 397 J mechanics. 728 Mitton graph and table. 727 coating failure analysis. 448 Lubricants. 732 www. 485-486 regions. 699-600 finish. slip resistance. acrylic emulsion Knoop Indenter. 698 pH. 347-348 interaction mechanisms. 132 fluorescent UV lamps. 644-645 Kauri-Butanol value. 791-792 coatings. 431-432 Knoop hardness number. diffraction. 492-493 837 relative. vinyl resins. 535 154 electromagnetic spectrum. 301-302 architectural coatings. 90-91 microscopy. carbon blacks. 496-498 Liquid coatings performance tests. 217-218 452-454 Loss tangent electron microscopy. 743-746 density. 357-358 Kubelka-Munk equations. 726 power. 785 laboratory testing. 183. 726-727 original equations. 410 film. 726 coating failure analysis. 720-721 Mass color. 150 moisture in. Martin's diameter. 581-582 calculation from tinting data. 481 aerospace and aircraft coatings. 358 Liquid-solid chromatography. 558-559 density. 645 Magnetic recording media. 698 resistance to wind driven rain. 311 general method. 699 water-repellent coatings. 645-646 Mark-Houwink equation. 291 Laplace equation.iran-mavad. 722 Krebs method. volatile organic compound. surface thermodynamics. 293-294 ISO/DIN 4496. 823-824 colored. 699 surface penetration. 646-647 Magne-gage. 76 blacks. 758 measurements. definitions. Kinetic stability. 498. 449 Mandrel bend tests.

278-279 degradation test. 243 Non-metallized azo reds. 227 rainfall. 207 Microbicides Doctor Test. 489 Mechanical properties. hydrophobe- ASTM test methods. 110 225 Mercury arc emission spectrum. National Association of Corrosion diffraction. 227 Modified zinc phosphates. 632 properties. leveling rate thickness gages. 349 Microscopy. 432. 650 Microvoids. high-energy-cured binders. 30-35 analysis. 257-258 in paints and coatings. 210 MIL-P-23377. 30 Moisture vapor transmission. 501 New York Paint Club method. solvents. 313- 820 Mineral spirits. 428 National Cooperative Highway Research 375-377 Microorganisms. 612-615 automatic. 227 Mixing time. 265 Naphthenic hydrocarbon solvents. liquid colors. Program Report 244. 21 aesthetic properties. 750 Maxwell model. 226 condensation. 509-510 Odor Metamerism. sources. 693 Nitrated hydrocarbons. 61 MIL-D-24483A. 627-628 No pick-up time traffic paint roller. bituminous acid spot test.916 PAINT AND COATING TESTING MANUAL "Matrix flushing" ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . 490 Monochromator. determining. 693 Nongaseous molecules. 127 pigments. X-ray diffraction. 551 properties) MIL-C-83286. 563 NFT 30-016. 110-111 MIL-R-81294. 604 doped ruffle.203 characterization of dispersions at oil nitrogen and/or sulfur-containing. 223 effect on natural weathering. 426. Micrometers. reactive crosslinking. 515 Microwave dissolution. 451-452 spatula or hand. 4 Metallic soaps. Muller Obstructed-flow devices. 97. 878 657-661 Engineers. 893 elastic liquids. 692-693 NFT 30-076. 561 Measurement systems. 220 Mebon Prohesion Cabinet. antimicrobial antimicrobial agents that chelate. 265 658-659 agents that react with. 850 properties. 377-378 formulation. 427 water coverage. 264 Naphthol reds. 245 N Ohmic drop. detection in plasticizers. 611 Micelles. definition. 694 Nitrogen. 459. 664 MIL-D-23003A. 226-227 Moisture-cured binders. 819. 30 Moisture resistance. 193 absorption point. 605 pigments. 691 NFT 30-075. 708 Methanol. 225 Modulus. can coatings. 346-348 Microprocessor electromagnetic Natural color system. 428 NBS Technical Note 883. 504 Media mills. 675 critical pigment volume. 425-427 140 particle-size measurements. automotive products. standard. 666 measurements. adsorption. corrosion. rheological gassing test. 126 314 Metallic pigments. grade classification. NACE RP T-10D. 444 pH measurement. 693 NFT 30-019. 219 solvents. 226 Mitton graph and table. properties. MIL-C-85285. 434 Natural iron oxides. 400-401 Non-ionic emulsions. 626-627 Normal Incidence Pyranometer. 132 colored organic pigments. painted. 722 modified. 224 end uses. 318-320 NEN 5336. density. X-ray Microbiological resistance. 263 NASA SP 5014. 360-361 corrosion. 677 Nonthermal. 223-224 relative humidity. scanning electron microscopy. 129 Murphy equation. 750 McArdle-Robertson evaporation index. 336 Non-Newtonian behavior. inorganic anti-corrosive drier. 726. 701 history. Mineral blacks. interior coatings. cylindrical systems. 625-628. 117 Mica. 451-452 thin films and microstructures. coating failure NOx. resistance to. 758 Metallized azo reds. dynamic (see also MIL-C-27227. 463 Object colors pretreatment. film thickness. 713 Methyl ethyl ketone. manufacture. 242 oxide film on surface. 209 NWMA-M-2-81. solvents. 126. 265 atmospheric corrosion. 880. as hiding power test Monoarylide yellows. 226 Mobility/lubricity. 119 Metallic coatings. 574 Dynamic mechanical and tensile MIL-C-81945B. 611-612 Molecular weight. 509 architectural coatings. 428-429 Needle micrometer. 328 coatings applications. 152 particle-size analysis. 835 Nuodex method. 223 effect on coatings. 227 Mohs scale. 693 Nitrogen dioxide. 299 0 panels. in-can preservation. 425. 892 Maximum bubble pressure methods. 356 automotive products. 192-194 economics of use. 253-256 www. 372 Oil Microbial problems. 411 plasticizers. 296 Microstructures. particle-size as bodying and flatting agents. 198-199 substrate. 771 market applications. Monocoat. hiding Mechanical adhesion. 214 Melamine resins. laboratory miniature. 612-615 Nepheline syenite. 537 654-656 National Standards Association. polymers. 555 static. 66 MIL-H-83282. 201. treated Nuclear magnetic resonance. 461 Maxwell relaxation time. 466 Munsell system. 31 pigments. definitions. 510 Nonionic nonurethanes. solvent rubs. 130 Mercury cadmium red. associated with paint. 712. white hiding power. 225 Moisture Non-Newtonian materials. 252-258 mode of action. 509. 772 MIL-STD-810. modified electrical resistivity/conductivity. 694 Nickel MEK resistance. 179 particle-size measurements. Nucleophilic groups. 169 in coatings industry. 495-497 coatings. coating failure analysis. 658 corrosion. 149 Micaceous iron oxide. 749 overlayers) Molybdates. 212 dependence.iran-mavad. prevention (see Protective Molybdate orange. 262-265 Naphthol orange. 693 powder and flake. 757 power. 504 510 MIL-C-85570. 191-192 masonry. thermogravimetry. 227-228 content. 225 647 Nonvolatile residue. 5 coating failure analysis. 733 absorption 261-262 Naphthas. 223-228 Miscibility. 451 881 713 opponent systems. 153 titanium dioxide pigments. 409 MIL-I-46058C. 750 vehicle identification. 770 NPIRI grindometer. 516 Monk cup. 868 MIL-L-23699. 457-458 artists' paints. 699 indices. 761 Metals Mold. 625-627 Notch gages.

575- standard. 473 solvent separation. plastic substrates. architectural coatings. white hiding. Orchard equation. 763-764 metallic pigments. 749 health and environmental Organoclays. 229 modifiers. 459 Parker-Siddle Scratch Tester. in solvents. 793-794 water-based coatings. 229-236 215 material "floating" in can. 756 324 aerospace and aircraft coatings. 305-306 gas chromatography. 183 nonvolatile content by weight. 688 Oxidative binders. 790-791 drying time. weathering effect. 229-230 Orifice cups. 490 powder coatings. 755 permeation through packed powders. 376-377 Paper chromatography. 499-500 Pendulum damping. 27 additive identification. aerospace and aircraft Particles Peel test coatings. 753-765 light-scattering techniques. 574-575 nonattainment areas. 226 Olefins. 315 critical pigment volume fineness-of-dispersion gages. contact 756 by sieving. 323- Optical properties pigment content. 306 bituminous coatings. 499 color measurement. 212 testing. 320-321 688 quality assurance. 321-324 K6nig pendulum. 313 determination methods. 200 Paperboard charts. 756 Partition chromatography.203-205 structural analysis. 172-174 special considerations. 756 sampling techniques. as thickeners and rheology 399 history. artists' paints. Sward Rocker Hardness Tester. water-repellent coatings. comparison methods. 18 Protective overlayers. Stress) X-ray diffraction. 631 Pasteurization. 757 nongaseous molecule adsorption. 769-770 684 PEI abrasion tester. 235-236 Organosilica. 313- Opacity. 510 optical properties. 231-236 Organic solvent resistance. 326-327 measurement. 111 on plastics. 325-326 Rolling Ball Hardness Tester. 805-806 701 hydrodynamic chromatography. 616 vehicle separation. 687. 758-759 spectrophotometric techniques. as hiding power industrial coatings. aerospace volume solids. 252 Package stability. 127-130 pigment. 747 structural analysis. 9 direct microscopic measurement. 559-560 Oxygen. 489 laboratory protocol. 794 weatherability testing. in architectural coatings. 574-575 612 diffraction of laser light. 755. 47 Pearlescent pigments. 542 409 oversize. 326-327 aerospace and aircraft coatings. 690 Oxidative drying. 235 pigments) from tinting data. 829-830 automotive coatings. 742 412 durability. 754 roller particle-size analyzer. 329-330 dry. 756-757 316 Orange pigments. 875-876 sealers. Packaging.iran-mavad. 234-235 OSA-UCS system. can coatings stability. 439-440 water content. 327-329 concentration and. 760-761 X-ray scattering. 765 328-329 Organic coatings vehicle identification. as hiding power test particle size. pigment identification. untinted. 306-307 56 Paint individual particle sensing. 573-578 control in atmosphere. SUBJECT INDEX 917 Asbeck-Van Loo method. 325 deadhesion. 761-763 Stokes' law. 231 Oscillating jet. by sedimentation. 687 flash point. ceramic pigments. stress-strain curves. 183 760 reference test material. 477 solvent identification. 721 Oxidative passivation. 412 Ozone Particle-size measurements. 104-105 test substrate. 378 organic structural analysis. 9 centrifugal sedimentation. vapor pressure. 311 Persoz pendulum. 282-283 Painted metal panels. 754-755 X-ray microradiography techniques. 319-323 Optical measurement methods. 309-311 can coatings. 759. 359-360 Pall glass mill. 315-317 (see also Drying oils) analysis. definitions. sealants. 230 Orthonitroniline orange. 311-314 pearlescent pigments. 375-376 Oxygenated solvents. relative hiding power chemical testing. polymers. 5 320 578 www. 314 carbon blacks. 657-659 Paving (see also Architectural coatings. 533 Oxidative cross-linking. 490 manufacturing. 317-319 angles. 305-330 Pendulum-rocker hardness. 481 density. inorganic anti. bituminous coatings. 325. 754 from surface area. 239 definitions. 327 inorganic. 309-311 Pencil Hardness Tester. 527 Ostwald system. used in alkyd manufacture. 234 Ostwald-deWaele model. 755 Parylene coatings. 329 vegetable. 105 importance. 707 gravity sedimentation. 255-256 felvation. 255 by elutriation. gloss and semigloss. 170-171 nonvolatile content by volume. 321 mechanism. 307-308 Optical density. 691 coarse aerospace and aircraft coatings. thin-film drawdown. 193 Pebble abrasion wear test. considerations. 337 Para reds. theory of. artists' paints. 303 composition. 20 Organic paints. 757 thin-film drawdown for oversize Orange peel sampling. 708 inorganic structural analysis. 323-325 Oiticica oil. 459-461 substrate. films (see also Biological deterioration) Pavement marking tape. 234-235 Pendant drop shape method. 231 Osmometry. 230 sample preparation. vinyl resins. 836 applications. 30-31 shapes. 758-759 fungal resistance. 408. 356 trace analysis. 282 Paintbinders. 256-257 gas adsorption. pull strength. 254-255 stratospheric ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . 574 effect on copper and silver corrosion. 412. 755 314 aerospace and aircraft coatings. history. 698 Pencil hardness. coating failure in aerospace and aircraft coatings. 722 resistance to rapid deformation effects. 692 Paintability. 764-765 time of flight from light blockage. 11 electrical resistance. 200-201. 229-230 and aircraft coatings. 230 Organosols. suppliers and trademarks. 314-315 Pierce-Holsworth method. Federal Test. 315 titanium dioxide pigments. 517-518 analysis. carbon blacks. 315- visual evaluation. 230-231 Organic pigments (see Colored organic white. 753-754 particles. 757-760 total light scattering. 565 corrosive pigments. 318. 214. 559 Peel. 647-648 pearlescent pigments. 252-255 Package integrity. 737 Outdoor exposure. 232. 153 analytical data. 316-317 Cole method. pigment effects. size versus Vickers hardness. 521 deterioration.

108-109 base catalyst. 713 plasticizer absorption. 199 silicone-modified. product design.iran-mavad. 879 vinyl resins. 296 metallic. 424-426 solute adsorption. 836 Pigment usage. 731-732 coatings. 836-837 colored inorganic. used in alkyd 119 Pipeline coatings. 244 application techniques. 835-836 cathodic reaction inhibition. extender. 79-84 X-ray diffraction. 574-575 mixing of colors. effect on natural weathering. 56 Phosphosilicates. 148-149 Phase shift. 253. 104-105 measurement. 238 Plastics Pfund wet film gage. inorganic anti-corrosive Pigment yellow 99. inorganic anti. 193 intermediate pH catalysis. 86-87 82-83 physical properties. 568. Polyalcohols. 483 Platinum-cobalt scale. 486-487 823-824 sampling. 245-246 primers. 117-118 Pfund Hardness Number. 115-116 organic resin binders. 199 saturated. 118-120 145. 117 Penetration rate. 835-839 255-256 quality control. hiding power. solubility relations. 483-484 viscosity. 806 Phosphates. electron microscopy. architectural coatings. 118 Permanent dipole interactions. 517-518 pH void. 732-733 Polymer. 835 carbonaceous. 253. 732 miscibility. 116-117 Penetration. 86-87 polymers. 79-80 Pigment red 188. 875-877 627 acid catalyst. 118 Pfund cryptometers. 104 rainfall. 399-400 ester value. 345 pigments) Pollution. 199 history. 79-81 corrosive pigments. 731 definitions. 733 molecular weight. 118-119 Persoz pendulum. 193 reaction with epoxy resins. hiding coal tar mastic. 401 vinyl resins. 731-733 manufacture. 732 addition. 119-120 Perylene reds. 616 behavior. 193 amines. 508-509 density. non-Newtonian end group analysis. clear. contact angle effect on stress in organic coatings. 408-409 definition. 224-225 Pensky-Martens Closed-Cup Tester. 82 organic pigments. 733 colligative properties analyses. 195 oil absorption. 615 Phthalates. residual water. 732 Phosphorus. 39 alcohol-soluble resins. 76 Pigment red 5. as hiding power test size exclusion chromatography. 407 power. 87 nonheat-reactive resins. Pigment red 122. 117 Permeation. 199 Polyesters varnish resins. 80 Pigment red 170. 199 traffic marking materials. 510 substrate. 193 imidazoline content. 193 synthesis. 400 pigment volume determination. of objects and colors. ideal viscous and elastic white hiding (see White hiding Polar solubility parameter. I 16 packings. 407 120 internal protection systems. 605 stability. 117 Peters abrasion block. 773 condensation. low-temperature properties. 743 color. 57-58 pigments. 487-488 sacrificial. 227 wetting/suspension characteristics. 699. 199 Polyethylene. relations. Phenolics. 82 Pigment yellow 65. automotive products. 80. gas-solid chromatography. 102-104 Pfund Hardness Tester. 242-243 Pigment yellow 97. 839 content absorption by pigments. 86 raw materials. 120-121 Permanent red 2B. 467 qualitative methods. Inorganic anti. 118 Pfund precision cryptometer. 378 591-595 grade classification. 86 Pigment red 22. 119. 521 automotive products. dispersion. 179 Plastic behavior. 118 Permanent magnet thickness gages. 120-121 oxidative cross-linking. failure. 217-222 identification methods. 756 acidity. 313 peel adhesion testing. 303 compatibility. 385 fUl~Ction. 629. 117 hiding power. 407 Photometric measurements. 392 bodies. 120 Permeability. infrared spectrophotometry. pipeline coatings. 79 Pigment orange 38.918 PAINT AND COATING TESTING MANUAL Pendulum-type COF devices. 85 as cross-linking agents for other Pigment orange 60. electron microscopy. coating failure ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . metallic pigments. hiding. White pigments) acids. 570 quantitation by X-ray diffraction. 193 Polyamine adducts. 190 copper corrosion. 533 particle sizing. 85 chemistry. 684 Plasticizers. 450 /773 instrumental methods. 199 resins. 193 heat-reactive aromatic soluble resins. 193 environmental~toxicity. 726 corrosive pigments. 203 chemical properties. 569 role in hiding power. 82-83 curing agents. 80. 223-228 properties. 807 measurements. solubility parameter distillation range. 490 839 aerospace and aircraft coatings. 343-344 by light scattering. 243 Pigment yellow 116. 179 pour point. 209-212 Plastic film. 117 700 techniques. 203 Pigment orange 62. 509-510 flash point. critical market. 632 white. 118-119 Perception. 119. 420. 741 pigments. 715 iron oxide blacks. 772. 115-121 viscometry. gas chromatography. Pine oil. 837- concentration. 83 Pigment red 187. properties. 490 external coatings. 79 Pigment red 7. detection in plasticizers. 85-88 catalyzed cross-linking. Pearlescent Polyamides. 390. 117-118 808 www. 256 noncarbon. 83-84 Pigment yellow 73. inorganic anti-corrosive Pigment yellow 75. 714 volume concentration. 410-411 pigments. 192 823-824 permanence. 177-178 pull strength of organic coatings. 111 Pigment yellow 74. Colored Polyacrylates.685-686 failure modes associated with. detection in plasticizers. 76 testing. gas chromatography. Plastisols masonry. 119 432 identification. 252-258 refractive index. 82 (see also Carbon blacks. 769-771 critical volumes. 127 Polyhydric alcohols. 87 Pigment red 146. 115 771-772 traffic marking materials. 731 mixtures. 53 Phenoxy. 87-88 first coatings. 483 liquid chromatography. 58-59 Phosphites. 160-161 isolation. paint. 429. 143. 193 definition. 400-401 Pierce-Holsworth method.256 specific gravity. 79 history. solvents.

93 non-Newtonian behavior. 261-262 aerospace and aircraft coatings. 733 dispersion rheology. 339-340 radiation-curable. 578 helium gas. 297. properties. 578-579 capillary viscometers. 339-341 powder coatings. 358-359 Polymerization Quinacridone reds. 531 365 686 Reaction kinetics. 448-449 702 nonconductive. cross-linking reaction. automotive products. 483-484 Roof coatings. X-ray analysis. 289 Rotational viscometers. 858 SAE J400. 351-352 viscoelasticity. 747 films. 361- Pot life. 855. 837-838 Rolling friction. 69-71 Rain gage. 90-91 effect on natural weathering. 758 relative viscosity. 323-324 Pull strength. 712 Reflectivity Roller mill. 711 directional. 361-352 Purge gas. 615-616 hiding power. sagging. 359-361 Porcelain enamels. 387. Rotothinner. 871 shear-dependent viscosity. 336-350 catalysts. 315 Princeton scratch tester. 651 modifiers post processing. 350 viscosity. 571 Primer. 449 measures.iran-mavad. 547-548 164. theology and viscometry. vinyl resins. 707 Relaxation behavior. 363 epoxy polyester. 690 350-351 Polyurethane sealants. 855 Pycnometers Resilience. vinyl resins. aerospace and aircraft coatings. architectural coatings. 626-627 yield behavior. 147-148 dielectric analysis. 725 Raman spectroscopy. artists' paints. 429 solid density. 27 O pavement marking tape. water-borne. 846 3-12 Rutile. 167-168 PVC latex. 580 Fresnefl equation. 100 (see also Thickeners and rheology Polymethacrylates. 393. 576 Protective overlayers. 574-575 architectural coatings. 646-647 shear-thickening fluids. wire-wound. 736 wind driven. 117 18. 117 Reactive crosslinking. 354-358 emulsion. 521 concerns about density. plasticizers. 301 gas chromatography. 89-94 curable polyurethane coatings. 560-561. 783-784 plastic behavior. 363-364 dielectric analysis. 420-421 conductive. 745 Sagging traffic marking materials. 354-355 www. 334-336 used in sealants. 409-410 Brooldield viscometers. 744 Roller application. 16- thin metal films and microstructures. xiii-xiv Rebound hardness testing. 364-365 epoxy resins. practical aspects. 736 Power law. 363 Pour point. 269 suspension. 702 Rockwell Hardness Tester. 352-345 vinyl resins. 209-210 vendors. organic coatings on Regulations Rotational casting. 365-366 polyurethane coatings. 93 (see also Colored organic pigments. 336 sealants. 337 Reference intensity. 510 weatherable. 93 aerospace and aircraft coatings. 344-350 chemistry. 351 Position-sensitive detector. 93 duration sensor. 845-847 Brookfield CAP 2000 viscometer. 712 determination. masonry resistance. 714 SAE J861. 832-833 Reynolds number. architectural coatings. 350-351 359-361 definitions. 320 83 paint analysis. 714 Resistivity. 231 inorganic. 39 R modifiers) Polyols. cure. 100 definition. 200-201 gel coat. 728 quality control instruments. 91 curing. vinyl resins. 298 cloud. 857 Saberg drill. polymers. 688 Roberts jet abrader. 334 Porosity. 492-493 Roller particle-size analyzer. 333-365 solubility parameters. 106 Relaxation map analysis. 111 Radiant power. 277 reactive cross-linking. architectural coatings. 409-410 Quality control Rheology and viscometry. 483 Rolling Ball Hardness Tester. 317-318 Pseudoplastic. 191) sealants. 839 Polysulfides. 532. 806 SAE J2020. 91-92 erosion non-Newtonian fluids. 364-365 research rheometers/viscometers. plasticizers. solvents. Putrefaction. 341-343 raw materials. 20 612-615 solvents. 872 Rank pulse shearometer. automotive products. laboratory. 528. 715 Retroreflectance Safflower oil. 704 Refractive index. 90-93 electromagnetic. 78 Red pigments rotational instruments. 634 recurrent failing in testing. 93-94 Radiometers. RCA tape tester. 399-400 rank pulse shearometer. 89-90 safety. 879 time-dependent effects. 532 polymer melt and solution rheology. Snell's law. 609-616 glass beads. 754 Rhamsan gum. 361-362 pearlescent pigments. xiv-xv elastic liquids. 735-736 pipeline coatings. 484 Roller spatter. 712 traffic marking materials. architectural coatings. 572-573 X-ray fluorescence spectroscopy. 108-109 molecular weight ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . 859-861 RED numbers. 736 Radiation nomenclature. 93 Rainfall shear-thinning fluids. 885. 744. 700-701 solutions viscosity. 855-856 Red lead. 831-833 methods. 711-712 Reflection. 416-417 plastics. masonry. differential scanning volatile organic compound emissions. 302 Resin liquid. in titanium dioxide pigments. 361 Preservation. 632 Reflectance Rising-bubble viscometers. 336 thermoplastic. 337-339 markets. 746 Rondeau Scratch Tester. extensional rheology. 106 reds. 360 calorimetry. electrodeposited. 633-634 time-dependent fluids. 398-399 instruments. vinyl resins. 343-344 definitions. 715 Pyrazolone orange. 333 Polyurethane coatings. 92-93 abrasion resistance.580 corrosion control. 547 886 instrumentation. 711-712 pavement marking tape. 702 Print resistance. 339 Refractory coatings. bituminous coatings. light. 420 Quality assurance Retroreflection. 572-573 Refraction. 149 Ro-tap sieve shaker. automotive products. 356-357 Precision Spectral Pyranometer. 82. infrared spectroscopy. 194 leveling. 745 Rods. 344 reactions. 100 QUV/HO. in-can. 527-528 Pretreatments. 362-363 Powder coatings. 71-72 Rotating cell holder centrifuge. 241-242 ICI cone and plate viscometer. 868 Newtonion fluids. SUBJECT INDEX 919 phenolics as cross-linking agents. coefficient.

152 Schopper Hardness Tester. 130 Wolff-Wilborn Scratch-Hardness coefficient of friction. 131 AAMA standards. 561 Solvents. traffic marking materials. 759. 220 automotive products. synthetic. 353 sealants. 688 pigments. 736 polymers used in. 54-55 Laurie-Baily Hardness Tester. 411. 383 Scrape adhesion test. 420 sources of specifications. test procedures. 560-561 rheology modifiers. 603 classification by function. architectural coatings. masonry. emulsion particles. 352 Solid support. 131 Dynamometer. 218-219 calculation. 759. 557. 313- aerospace and aircraft coatings. 339 Solubility. 690. 574 accelerated weathering. 96 solvents. Sikkens Scratch Hardness Tester. 130 Scuffing methods. acid wash color. 816 thickeners and rheology modifiers. paint. thickeners and rheology total. 507 Setaflash-Closed-Cup Apparatus. 313 Erichsen Hardness Tester. 353 cellulose esters. 579 dispersion. 707 693-694 backscatter electrons. 98 procedures. 125- Universal Hardness and Adhesion Test Slip resistance. 384-385 Dynamometer. 310 Sodium aluminosflicates. 62-63 aniline ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . 837-839 alkalinity. 393. 561-562 of solvents in water. 562-563 determination methods. 389-391 Scheppard-Schmitt Scratch Sieving. 755-756 objective lens. 741 Hoffman Scratch Tester. 686 745 Scanning auger microscopy. 756 metal coating. 392 Scratch hardness. 817-818 Shear thickening. 152 Rondeau Scratch Tester. 301-302 paint film weatherability. 602-603 coalescing. 664 Parker-Siddle Scratch Tester. adsorption onto pigments. 152 Steel Wool Scratch Tester.920 PAINT AND COATING TESTING MANUAL resistance. particle-size Soap titration. 739-740 Smoke characteristics. 663-664 Inspector's Dur-O-Test Pocket Size testing conditions. 536 paint volume. 559 Simmons Scratch Tester. 819 modulus. 707 Sodium carboxymethyl cellulose. gas chromatography. 739 sensor materials. calculation. due to gravity. 561 instrumentation. 134 Clemen Scratch Hardness Tester. 547 Saturation. coatings. 666 Sensor materials. 818-819 Shear flow. solvents. 837-838 in. 557-558 oxime cure systems. 98 materials. measurements. determination. 581-582 measurement. 390. 319-323 314 691 Sedimentation E. 600 chlorinated hydrocarbons. 399-401 constant theory. 269-270 coatings. solvents. forms. 600-601 supercritical carbon dioxide. 557-558 elastomeric coatings. 557 catalyzed cross-linking. 603-605 nitrated hydrocarbons. 760 Settling Soil.iran-mavad. 3-4 test film casters. 551 acidity. calculation. 715 Seeding. 127-130 Sealants. 736-737 products. 385 Scattering coefficient fluids. D. inorganic anti-corrosive partial. 387. 561 calibration and calculations. 132-133 Sheen Scratch Tester. relation to tensile by weight. 149 Setaflash test. 411 Solutes. 650 Sedimentation. 602-603 Softening point Sampling. 397 Schopper Hardness Tester. 393. 560-561 SI system. 559-560 SIS 18 41 77. 375-376 coating. xvi. 684 image formation. in aerospace and aircraft environmental. 799- X-ray microanalysis. 95-98 polymers. paint. 838-839 approved. 743 classification by chemical type. particle-size measurements. 753-754 Sessile drop shape method. 690 applications. 392 Scholzite. 664. 95 Solvent reflux process. Snell's law of refraction. 339-341 800 Scattering. 536 by volume. 701 ISO standards. 560-561 amino resins. architectural coatings. artists' paints. 821 artists' paints. 507 Shear thinning. 152 561-562 Skinning. preparation for aerospace and Scanning electron microscopy. 639. Solids. 293-294 condenser lens. 556 addition cure system. 471 inorganic anti-corrosive pigments. 384 Schiefer abrasion testing machine. 745 benzene content. drainage equation. 556-557 applications. 145 thermoplastic marking material. 4 Sikkens Scratch Hardness Tester. 727 Hardness Tester. traffic marking 558 new requirements. 739 lubricants. 601-602 hydrocarbons. paint. S. 96 Solvent/fuel resistance.. 736 Solvent rub resistance. 125-128 Tester. 735-740 definitions. 560 Size exclusion chromatography. 563 ASTM activity. 125-154 Pencil Hardness Tester. 561 hydrogen bonding 530 Silica. 880-881 Silicas. 383-402 Scattering power. 398-399 Bierbaum Microcharacter. 824 Shear storage modulus. 821 modifiers. 529. aerospace and aircraft Solubility parameters. Hansen solubility parameters. 393 www. 819 Shear stress. alkyds. 303 scan coils. 131-132 Canadian standards. Sheen Scratch Tester. 819 274-275 as concrete materials. 815. 243-244 polar. 483 Salt spray/fog testing 760 SNV 37 112. 96 Solvency. nonaromatic hydrocarbons Simmons Scratch Tester. 561-562 application.542. 701 aircraft coatings cleaning tests. 561-562 Skid resistance. 492 Shore scleroscope. 397. 820-821 Shade. 604-605 oxygenated. 97 supplementary calculations and Dantuma Scratch Tester. 277 chemical resistance. 154 492 Shore hardness. 713 274-275 Secondary ion mass spectrometry. 247 Kubelka-Munk two-constant theory. 132-134 Graham-Linton Hardness Tester. pavement marking tape. 534 density. 295-296 cryogenic. 282-283 nomenclature. 555-563 Silicone coatings. 744- Saybolt color. 24 titanium dioxide pigments. 152 Scheppard-Schmitt Scratch 336 active. 735-736 Smog. 815-818 Shear loss modulus. 507 content electron guns. 560 317-319 Hildebrand parameters. 819-820 Shear modulus. 838 aromatics. aerospace and Silicates. Kubelka-Munk two. automotive thickeners and rheology modifiers. 385-388 aircraft coatings. balance. 173-174 Sheen. 558-559 unique properties. 392-393 du Pont Scratch Testing Machine. 600-605 131 Instrument. 558-559 Silicone sealants. X-ray diffraction. as thickeners and temperature effects. 97-98 Solvent-reducible coatings. 556 application methods. 143. 132 Teledyne Taber Shear/Scratch Tester. 739 Slumping. units for rheological variables. 95-97 Solvent-borne coatings.

152 SS-S-200E. definition. 370-371 www. 632-633 139-140 Stokes E. 3t0 Sun yellow. 306 identification. 756-757 438 weathering. 707 temperature variation. 662-663 composition. 146 Strand Gauge. 611 in film thickness measurement. 380 organic. description. 585-598 Surface tension. 334-335 coatings application and defects. 249 Sunchex apparatus. 586 effect on stress in organic coatings. 133 Spoilage. 133-134 St. solvents) Storage stability Surface area. 214 relative humidity variation. accelerated natural Stress relaxation. particle size from. 150-151 by lamp method. 347 emissions. radiant exposure. 134-144 measurements. 372 Spatula and hand muller. 482 Strippability. 726 thermoplastic marking materials. 706-707 Surface cleaners. artists' paints. accelerated natural separation from vehicle. 144-148 definition. 149-151 grade classification. particle-size film formation. 737 Styrene. 296 Spectrocolorimeters. 891 in tension and shear tests. 590-591 147-148 techniques. 302 can coatings. 537 gas chromatography. 639 Stress-strain analysis. 153-154 Steel Wool Scratch Tester. 435 Strontium yellow. 253-255 Strain substrates for coating. stress response. 117-118 Stress 435. 399 Sun. 437 Strontium chromate. 149-151 State implementation plans. Louis gage. 463 in organic coatings. 311-314 Sonic frequency shifts aerospace and aircraft coatings. 600 refractive index. 621-623 volatility. 587 diluent dilution ratio. corrosion-accelerating Statistics selection using solubility parameters. 621-625 supercritical gases. 373 vapor pressure. effect. 737 measurement. Spreading rate Stress-strain curves 773 contrast ratio at. 323-324 interdependence of stresses. 805 determination. 308-309 solvents effect. 659 cleaning and pretreatment. 594 calculations and conversion tables. 153 State operating permit program. 149 SS-W-110c. 622-625 viscosity reduction. 444 Surface energetics. oil absorption Straight-line reciprocating machines. Spray rack. 208 effect on flexibility and toughness. 153 color measurement. 144-145 Spinel brown pigments. 437 oxygenated. 644 boiling point/distillation range. 132-134 Steel flake. 885 (see also Hydrocarbons. particle-size spectral power distribution. Surface active agents. 140-144 320-321 rough. 687 versus adhesion and cohesion. 591-595 significance. 772. solid density. pearlescent pigments. 290 definition. 224 Sulfur gas chromatography. SUBJECT INDEX 921 color. 492-493 interpretation. 147-148 Spin coating. 334-335 Surface excess concentration. 133 Spinning riffler. 62 342-343 seasonal variations. 586-587 593-596 702 weathering and. X-ray fluorescence water solubility. automotive products. 27 Stormer viscometer. 154 Stopped method. S. 397 water content. 592 Surface interactions. effects on film thickness aircraft coatings. 299-301 artists' paints. 745 internal. 378- bituminous coatings. 422 pigmentation effect. 594. 629-630 esters. 585-586 definitions. 317-318 traffic marking materials. 676 coatings. 463 measurement. 543-544 Heptane Miscibility ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . 435. 289-303. 493 ductile film. 10 liquid chromatography. 148-149 Spectrophotometers. 241 latent. architectural coatings. amino resins. 147 Spectroradiometers. contact angles. 589-591 hydrometer methods.iran-mavad.437 solvents. 593-596 dilution limit. 651 solvency. 693 Kauri-Butanol Value. 135-139 Stokes' law. 154 SS-A-118. 231 calculation. 16. 369-380 flash point. 347 714 weathering. 417-418 purity and composition. 154 hiding power. aerospace and Staining. 597-598 electrical resistivity. 225 Subtropical climate. 561-562 effect on natural weathering. 359-360 Surface elasticity.. 421 Stress memory time constant. 150 in solvents. Stokes equation. 131 SSPC-VIS1. 145-146 measurements. D. 509 Straight line drying time recorder. 586 38O Specifications oscillating. 437- 393. 5 detection in plasticizers. paint. 749 Substrates o|efins content. 400-401 Step-shear method. 435. 144-148 double beam. 119 ketones. 428-429 spectroscopy. 345-346 contact angle measurements. 361 radiation intensity. 137. resistance. 370-371 colored organic pigments. plasticizers. 722 711 Sonic sifter. aerospace and aircraft Karl Fischer Reagent Method. 370 liquid density. 489-490 paint films. copper strip corrosion. 149 Sulfur dioxide. following. 585-587 pycnometer methods. 803. 713. 622-623 tolerance. 153 Stain chambers. 151 properties. 211 nonvolatile residue. 764-765 hiding power. 531 cleaning and pretreatment of determination. Tg determination. 639 solubility parameters. 462-463 596 density and specific gravity. 134-135 Stokes-Smoluchowski-Einstein theory. 397. 43 odor. 380 Specialty paints and coatings. 370 Soybean oil. 378 considerations. 534 dynamic properties. 369-380 Spatula rub-out method. 373 sources. 548 Surface finish definition. 470-471 origins. 149-150 Spray outs. 20-21 internal. 543 failure modes associated with. 721 effects on film thickness measurement. 335 masonry. 692 sealants. 685 Surface area to volume ratio. Surface. 370-373 Specific gravity. 327 electromagnetic spectrum. automotive products. 132 SSPC PA2. 245 Sunlight sulfur content. 154 338 Surface analysis. Spray application. 743 Surface effects. 826-827 binder effect. 214 evaporation rate. thixotropic recovery. particle-size measurements. 146-147 Specular glass. 153-154 Static coefficient of friction. 587-589 digital density meter. 134 inorganic anti-corrosive pigments. 393 Stainless steel flakes dry coatings on. 891-893 Strain rate thermodynamics.

629 bentonite clays. settling. 183. 841-842 rhamsan gum. 842 "Thixotropic Index" test. 282-283 static. 277 effects on paint film durability. 214 Technical societies. 712-713 Terpenes. 852 Tint. 169-170 561-562 Thermosetting acrylic resins. 532. 508 aerospace and aircraft coatings. 855 Time lapse spectroscopy. 850-853 Time-temperature superposition. 376-378 solving. 272-275 (see also White pigments) Tensile storage modulus. 872-873 tensile properties) functions. 852 hiding power. 278-280 performance.714 Thermal analysis. 274-275 aerospace and aircraft coatings. organic. 142. 525 cellulosics. 370-373 dielectric analysis. 283 Total light scattering. 412-413 thickening mechanisms. calculation from. 174 weathering effect. 498- Tag tester. 850 particle-size measurements. 370-372 845 Thin-layer chromatography. 853 carbon blacks. 168 definitions. 343 Swelling. 500) pavement marking tape. 708 Tape test instrumentation. 172- aircraft coatings. 144 purge gas. 530 Thermal mechanical analyzer. 857-860 mechanism. 271-272 Surface thermodynamics. automotive products. 854-855 untinted white paints. 342-343 modifiers. 385 thermoset cure studies. 315- can coatings. 207 can coatings. 164-165 effect on alkali-swellable/solubleemulsions. 170 flexibility and toughness. pigment. 842. 170-171 Tensile loss modulus. 173-174 Tensile adhesion test. 548 Time of flight from light blockage. aerospace and biopolymers. 693 Thomas-Stormer Viscometer Model ETS- Synthetic brown oxide. 537 nonionic synthetics. 341-342 hardness values. 374-376 cure. 85 dilatometry. 689 inorganic. 853 316 mar test. cure. 795-796 Sward Rocker Hardness Test. 282 effects on gloss. 842. 196 Sward Rocker Hardness Tester. 275-278 surface. 508 TAPPI Method T649sm. 499 fatty acids. scanning electron micrographs. 372-373 differential scanning calorimetry. 390 283 crystallites. thermogravimetry. 408 Titanium dioxide pigments. 578 855 gel coat. 272-273 compatibility. thickeners and rheology Thermal conductivity test methods. syneresis.168 Temperature Thickeners and rheology modifiers. 412 dynamic mechanical analysis. 170-174 586 mechanisms. stress in organic coatings. 126 relation to abrasion resistance. 164-170 Teledyne Taber Shear/Scratch Tester. 853. 852 Tinting Tag Open Cup Flash Point test. 507 Tag Closed Cup Tester. (see White hiding Tensile strength alkali-swellable/solubleemulsions. aerospace and aircraft hydroxypropyl guar. 275-277 174 Tensile creep experiment. 274 particle size. 745 279-280 Toluene. 850. 142. 277 measurement. contaminants. 373-378 combined techniques in problem shear flow. sag. 127-128 leveling. 321 traffic marking materials. 282 measurements. 535 hydrophobe modified Titanium oxide. 277 Tooke inspection gage. 693 Through-dry time. 857-860 characteristics. 700 uses. 274. 534 269 scattering coefficient. 537 classification. 280 Toluidine red. 165-167 variation. Thermoplastic polymers. 275 liquid/solid interfaces. 535 coating consistency. 171-172 Temperate climate. 841-863 275 Torsion pendulum. 714 Thermally stimulated current. 624-626 application properties. 173-174 Tensile properties conventional. 441 coatings. 341 compared with K6nig and Persoz reaction kinetics. sealants. 64 coatings and. 855-857 water-soluble. 842. 168-169 natural weathering. 548 277-278 packing. 832 Taber Abraser. 610 Time-of-wetness. 722 Thermodilatometry. 169 critical. 507-508 Tape and wrap systems. 576 industrial applications. 413 classification of material properties. 325. 737 heating rate. relation to shear in coating manufacturing operations. 189 adhesion. 40-42 colored organic pigments. 842. 174-177 Tensile modulus. 686 Thermomechanical analysis. 722 Thermoplastic pavement markings. 281-282 dispersibility. 575-578 experimental techniques. 859 Tack-free time. 578 thermogravimetry. 853 Tinting strength. 850-853 Thixotropy comparison of rockers. 42-46 commodity composition. 144 sample preparation. Thermoset polymers. 27 applications. xanthan gum. 185. 341-342 Syneresis. 273-274 product ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . associative. 741-742 Titanate green pigments. 690 Thermal stability. solvent emissions. particle-size 841 organoclays. 201 Tensile tests. 536-537 elongational flow. 166. 577 thermomechanical analysis. 842. 499 Talc. 759 Throwpower. specification sources. 360 Thermal fatigue. 854 chromatic paints. 192-193 Tensile stress relaxation experiment. 162 dynamic (see Dynamic mechanical and definition. Tall off. 797-798 1000. 611-612 Table sampling. 842 Third party inspection. 845-847 Thixotropic loop. 270 transmission electron micrograph. with pollution. white paints. 688-689 cellulosics. 777 calculation of number of rocks. 573 847-850 Thioindigoid reds. architectural coatings. hazards. aerospace and aircraft Through-dry state. 281-283 Topcoat. 517-519 sample preparation. 163 modulus. 277 liquid surfaces. 713 . 278-279 Tolyl orange. aerospace and aircraft coatings. 429 coatings. 268. 853. 408 color. 647 attapulgite clays. automotive products. 581 Thermodynamic stability.iran-mavad. 688 Thermoplastic acrylic resins.922 PAINT AND COATING TESTING MANUAL amino resins. 732 heating rate. 269-270 dynamic. 842. 854 artists' paints. 270-271 hiding and opacity. 162-176 891-893 Thermoset cure studies. 794-796 Sward hardness. applications. 218 855 relative hiding power determination. 308-309 Thermogravimetry. 268-269 X-ray diffraction. 327 www. 212 detectors. particles. 842. 860-863 synthetic silicas. 441 T Thermal gravimetric analysis.

728-729 100-102 relative. 235-236 additive identification. 743-744 products. 867 industrial processes and. 194 architectural coatings. 737 maintenance and marine finishes. 105 cold crack resistance tests. 822-823 power. 822 osmometry. 551-552 TT-S-01543A. 99 temperature effects. 742 instrumentation. 547. 110 104-105 evaluation. 741 Underwriters Laboratories Inc. 273-274 TT-C-555B. 100 Toxicity powder coatings. traffic marking materials. 99 Total ultraviolet radiometer. 548 U post-polymerization process. 728-729 separation from pigment. architectural TT-P-97D. 348-350 laboratory testing. 100 solution. 337-339 TT-P-29. 726. 335 particle-size measurements. 106 amino resins. abrasion resistance tests. manufacture. 892 Viscometers. 729 565 ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . 573 plasticizers. 547 Turpentine. 564 organosols. 489 definition. 100-102 epoxy. carbon blacks. laboratory Universal color language. 741 calibration of instruments. 245 Ultraviolet and visible spectroscopy. 836 high-shear. 100 appearance and physical Ultraviolet transmission. for rheological variables. 453-454 773 medium-shear. 700 analysis. 27 packaging. coal tar. 83-84 low-shear 11 Vat reds. 345-346 polyester. removable tape. 554 TT-S-001657. 274 1. 742 spectral interpretation. automotive trends. 732 amino resins. 765 Ultraviolet light. 707 electron-optical column. 760-761 rheology modifiers. staged phaseout. staining in. 741 Undertone. 726. 867 waterborne dispersions. 729 emulsion polymerization. 106 cupping tests. 737 magnetic recording media.103 Trace analysis. 715 TT-S-00227E. 658 Vinyl chloride copolymer coating resins. 839 TT-C-598B. 210 laboratory testing. 101-102 polyamides. 708 Transfer efficiency. Tristimulus values. Viscoelastic models. 458 viscometry) testing. 839 www. 319-320 Vapor pressure dynamic. versus pencil hardness. 102. hiding artists' paints. 737 Vickers hardness. Viscoelastic properties. 106 glass beads. 867-869 (see also Elastic liquids) laboratory testing. 99 automotive products. measurement.iran-mavad. 772. 104 impact resistance tests. 729 definition. 747 Ultraviolet/visible spectroscopy. 449 suspension polymerization. 745 Unbalanced magnetron sputtering. 737 inks. 110. 62. 101 inorganic anti-corrosive pigments. 536 types of contrast. 55 Traffic paint. 552-553 799 market. 66-67 UL-94. 868 polymers. Urethane. 102-104 strain rate effects. 866-869 Vinyltoluene. 719-720 solution characteristics. 547-554 TT-P-2756. phenolic resins. TT-P-55B. reduction. 737 history. 866 wood finishes. 346-348 permanent tapes. 548 Tukon hardness. 548-550 Twisting cork hardness tester. 868 Violet pigments. artists' paints. colored organic pigments. 106 field evaluation. 100 Toughness. 720 Transmission. 87-88 Ultraviolet cured coatings. TT-W-572b. thickeners and rheology Transportation industry. 547 TT-P-19. 550-551 polymerization. 24 Transmission electron microscopy. 713 vinyl chloride copolymer coating auto-no-track time. 572-573 pavement marking tape. 185-186. 756 melt. gas chromatography. 104 t-bend tests. 632 TT-P-96D. 463 Vehicle thickeners and rheology modifiers. 563 aerospace and aircraft coatings. 839 TT-P-24D. 463 identification. thickeners and from spectral data. 99 743 TT-P-95C. 507 failure modes associated with. 726. 60-61 alkyds. 336 Viscometry (see Rheology and thermoplastic material. 416 changes 824 Van Eyken-Anderson method. 702 TT-P-00620C. 727. 746-747 electromagnetic radiation.1-Trichloroethane. 211 properties. 105- effect on coating performance. 118 TT-F-1098D. automotive products. cans. 103-104 Mandrel bend tests. 745-746 mercury arc emission spectrum. 134-135 modifiers. 741-747 Ultraviolet radiation. 548 plastisols. 749 106 548 Tubing materials. inorganic. 692 formulation. 64 532 artists' paints. Instrument. 710 Ultramarine blue. 644 solution process. 101. 99 forming tests.1. 105-107 humidity effects. automotive products. 105 interpretation. reactive crosslinking. 103 aging and weathering effects. 105 Touch-up uniformity. 99-107 shear-dependent. 554 TT-S-00230C. 100 coatings. 726. 43 laboratory testing. 744-745 Universal Hardness and Adhesion Test Viscosity thermoplastic pavement markings. 727. plasticizers. 729 dry film printing. 448-449 cellulose esters. 95 primers for plastisols and organosols. 741 principle of operation. 188. 729 characteristics. 714-715 715 V can coatings. 204-206 UL QMJU2. 729 Vinyl resins. 553-554 Tung oil. 106-107 characteristics. solvents. 742 Units. 865-870 resins. 869-970 Viscoelasticity liquid coatings. 727 FDA status. 822. paint. 742 189 548 solvent-borne coatings. 743 radiant power.. 409 684 water-borne coatings. 106 pearlescent pigments. 741 Urea resins. 742 111 Viscoelastic parameters. 763-764 solubility. Vacuum plate. light. 700-701 Tristimulus (filter) colorimeters. 133-134 TT-P-19D. PVC latex. paint analysis. 662 solvents. 683- 741-742 Urea. SUBJECT INDEX 923 Total solids. 127 pigmentation. 683-684 temporary tape. Varnish. 100 Traffic marking materials. 274-275 calculation. 743-746 potential problems.

638 pigment Water-repellent coatings. bituminous moisture effect.234 Wilson/Tukon Hardness Tester. 377-378 masonry treatments.iran-mavad. 161. 614 carbon arc lamp. 741 exposure frames. 226. 749 reporting scales. 638-640 874 cure. 859 biodeterioration effect. 634 Volume E. Wood 649-650 finishes. 692 untinted. 876-877 pigments. 710 water fog testing. masonry.427 direct comparison method.162 new source performance standards. 715 viscometer. 714 Water vapor Whiteness indices. 677-680 Wet film comb. 643 Xanthan gum. 880-88l. 220 fluorescent UWcondensation lamp. 877-879 Water ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . 624-626 specimen preparation. scanning electron White hiding pigments) inks. 571. 689-690 substance. 176 7 Wax melt characteristics. 641 manual search procedures. 677-678 White hiding pigments. 652 radiation safety. 749 ultraviolet. metallic pigments. 627-629 goniometer system. 850 Weathering Wire-wound rods. 501 automotive products. solvents. 290 UV light-cyclic immersion. 461-462 can coatings. 721 light. 720 controlled condensation testing. 499-501 Volatile concentration. 647-648 Washability. 885-887 Water resistance. 650 treated.924 PAINT AND COATING TESTING MANUAL stability. 8-9 paint film. 277 705 sealants. 5 Wavelength dispersive spectrometer. 871-872 coatings. 425. 625 metal pretreatment and other thin Water erosion. 678 microvoids. 737 Xenon arc lamp. measurement. Wolff-Wilborn Scratch-Hardness Tester. conversions. 874 traffic marking materials. 514 market. 154 ultrafast. reproducibility. 651-652 WACO Enamel Rater. 699 specimen preparation. 677 concentration. 643-652 WMO instrument house. 679-680 Wetting-contact theory. 749 stress development. 291-293 bulk contaminant detection. 500-501 artists' paints. 749 orientation of specimens. 755 failure modes. 134-144 accelerated. 715 (see also Titanium dioxide pigments. 871-880 Water absorption. coating failure analysis. 177-178 automobile industry. 726-727 exposure angles. 508 content determination. composition. aerospace and methods. 872-874 treated masonry tests. complementary and tinting data. 372-373 Viscosity cup. 106 W fluorescent UV-salt fog. 759. aerospace and tinting strength. pearlescent 554 computer-assisted searches. 748 origins of testing. 160 standards coatings. 885 aerospace and aircraft coatings. Waterborne coating accelerated. 749 application. 363 dedicated spectrometers. 4-5 Wear resistance. relative hiding power from definition. 597-598 X-ray fluorescence spectroscopy. 499-500 Volatile organic compounds 679 dispersion. preparation. 532 mechanical properties. 644-647 Wallace Microhardness Tester H-7. 748 pollution effect. 650-651 (see also X-ray diffraction. 817 calcium carbonate. D. 375. 619-642 d-spacing intensity table. 779 Water-based coatings. 641-642 analysis. 647 X-ray analysis. 748-750 nondestructive testing. abrasion resistance. 720 permeability.. moisture effect. 677 xenon arc lamp. 824 Wilhelmy plate. 852 manufacture. 679 Wetting. 8 automotive products. 529 Volume measurements. 748-749 temperature effect. 873-874 treated wood tests. 728 application. 884 www. coating failure analysis. 420-421 Volatility. 896-897 cycle testing. X-ray effect on coatings. 880-881 Waterproofing membranes. 159-178 from coatings. 499 emissions dominant. 692 Wells-Brookfield cone and plate comparison to other techniques. 65-66 X-ray diffraction. 871 density. 3-5 transmission rate. general application. 645-646. 749 effects on flexibility and toughness. masonry. 874-878 paintability. 779 880-887 weathering. 471 economics of hiding. 621-625 quantitative analysis. problems with. 479 extenders. can coatings. 9 microscopy. 571-572 thermogravimetry. 5-8 aircraft coatings. 643 Wolf abrasion method. 514 Visual system. 500-501 aircraft coatings. 640-642 "matrix flushing" method. 641 qualitative analysis. 749 Fresnel reflector. 850. 159-160 regulation information. 3-12 Waviness. 749 sunlight effect. 878 physical properties tests. 875-876 Water coverage. pearlescent pigments. 18. 159 regulatory definition. 677 film porosity. control. 5. plasticizers. 637-638 identification. 161-162 aerosol spray paints. S. 648-649 fluorescence spectroscopy) residual. 450-451 immersion testing. water repellency. 871 coatings. aerospace and aircraft research and development. 648-649 Water temperature effect. 627 879 dimensional stability. 231 natural. 455 White pigments. inspection and reporting. water absorption. 20 mounting specimens. 291 691-692 562-563 Voroni tesselation. 885 automotive products. 879-880 beading. 635-638 instrument operation conditions. water-repellent artificial. architectural coatings. 8 Weatherability void pigments. 500 architectural coatings. aerospace and aircraft coatings. 8 testing. 762-763 classification. 871-887 content in solvents. 666 Weight. 759. 648-649 Wollastonite. 684 100% relative humidity testing. crystal and particle size. 634-636 limitations. 625-628 physical principles. 4 Wavelength. 728 White paints Clean Air Act. 749-750 (see also Climatology) thin film units. paints. 477. 11-12 Weak boundary layer theory. 704. 678. 118 amino resins. 232. 647 X 572 oxygen effect. 749 water-repellent coatings. 882 Water-resistance testing. 619-620 procedure for calculating composition. vinyl resins. 878 227 instruments and sensors. 311 advantages. 872 masonry. 642 coatings. 176-177 regulations.

211 qualitative analysis. 242-243 scanning. 564. 884-885 coating layers. 882 Yellow pigments Zinc borate. 778-779 pigment identification. 778 Young's modulus. 352 grade classification. 786 film thickness measurement. 238 on-line units. 244 quantitative analysis.iran-mavad. artists' paints. 885 test methods. 817-818 Young equation. 344 Zinc phosphate. 884 Y cathodic protection. 462 in primers. 881-882 Yellowing. 241 X-ray photoelectron spectroscopy coating Young-Laplace equation. 885-886 yellows) Zinc oxide. 241 failure analysis. practical aspects. ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . 882-883 measurements. 243 quality control. 211-212 Zinc chromate. scanning electron 344 properties. 573 www. particle-size Z spectroscopy. 438 Zinc fundamental parameter methods. 224-225 surface analysis. 883 (see also Colored organic pigments. 659 field analysis. 224 microscopy. 884 Xylenes. 373 Zinc tetraoxychromate. 762 Yellowness indices. 883-884 Yield behavior. Zinc hydroxy phosphite. 886-887 Zeeman effect. 882 physical basis. 709 coating failure analysis. 240-241 procedures. 325 empirical methods. 883 inorganic. 372 Zinc potassium chromate. mixed. 244 portable units. X-ray microanalysis. SUBJECT INDEX 925 electron beam excited X-ray X-ray scattering. 882 Yield stress Zinc pigment standard addition method. non-Newtonian behavior. 126 Zabel test.

etc.Contents Preface xi Introduction xiii PART 1: REGULATIONS Chapter 1--Regulation of Volatile Organic Compound Emissions from Paints and Coatings by John J. Koleske Chapter 5~Driers and Metallic Soaps 30 by Marvin J. Urea. Friel Chapter 7--Alkyd and Polyesters 53 by Al Heitkamp and Don Pellowe Chapter 8--Amino Resins (Reaction Products of Melamine. G. Eppler ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ .iran-mavad. with Formaldehyde and Alcohols) 60 by J. Curtis Chapter 4~Drying Oils 26 by Joseph V. Owen Santer Chapter 9mCeramic Coatings 68 by Richard A. Schnall PART 3: SYNTHETIC MATERIALS Chapter 6~Acrylic Polymers as Coatings Binders 39 by John M. Brezinski PART 2: NATURALLY OCCURRING MATERIALS Chapter 2--Bituminous Coatings 15 by Ben J. Carlozzo Chapter 3mCellulose Esters 23 by L.

Eppler www. Petraitis Chapter 15mVinyl Resins for Coatings 99 by Richard J. Bauer. ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . Jr. Koleske Chapter 14~Silicone Coatings 95 by D. Kight Chapter 13~Polyurethane Coatings 89 by Joseph V. SpineUi Chapter 21mColored Organic Pigments 190 by Peter A. Koleske PART 4: PLASTICIZERS Chapter 17~Plasticizers 115 by Peter Tan and Leonard G. PART 6: PIGMENTS Chapter 19--White Pigments 159 by Juergen H. Lewis Chapter 22~Inorganic Colored Pigments 209 by Peter A. J. Edward J. Watkins Chapter 11 ~Phenolics 79 by John S. and Michael J.iran-mavad.CONTENTS Chapter 10mEpoxy Resins in Coatings 74 by Ronald S. Krauskopf PART 5: SOLVENTS Chapter 18--Solvents 125 by Stephen A. Lewis Chapter 23~Ceramic Pigments 214 by Richard A. Fry Chapter 12~Polyamides 85 by Robert W. Yuhas. Burns Chapter 16--Miscellaneous Materials and Coatings 108 by Joseph V. Braun Chapter 20mBlack Pigments 179 by Frank R.

Mills Chapter 33ARheology and Viscometry 333 by Richard R. Eley Chapter 34nSurface Energetics 369 by Gordon P. King Chapter 30~Thickeners and Rheology Modifiers 268 by Gregory ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . Jr. Miranda Chapter 37--Film Preparation for Coating Tests 415 by Robert D. Rieger Chapter 27--Inorganic Anti-Corrosive Pigments 238 by M. Athey. CONTENTS vii Chapter 24mExtender Pigments 2t7 by Henry P. Shay PART 8: PHYSICAL CHARACTERISTICS OF LIQUID PAINTS AND COATINGS Chapter 31ADensity and Specific Gravity 289 by Raymond D. Jay Austin Chapter 28mOil Absorption of Pigments 252 by Joseph V. www. Ralston Chapter 25--Metallic Pigments 223 by Russell L. Ferguson Chapter 26--Pearlescent Pigments 229 by Carl J. Hansen PART 9: FILMS FOR TESTING Chapter 36--Cure: The Process and Its Measurement 407 by Thomas J. Bierwagen Chapter 35~Solubility Parameters 383 by Charles M. Fungicides. and Algicides 261 by Vanja M.iran-mavad. Koleske PART 7: ADDITIVES Chapter 29~Bactericides. Brockhaus Chapter 32nParticle-Size Measurements 305 by George D. ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . P. Nelson Chapter 45--Abrasion Resistance 525 by Mark P. and Harry K. Morse Chapter 4 6 ~ D y n a m i c Mechanical and Tensile Properties 534 by Loren W. Jr. Guevin. Wenzler and J. PART 12: ENVIRONMENTAL RESISTANCE Chapter 51--Prevention of Metal Corrosion with Protective Overlays 609 by William H. F. Guevin. Smyrl www. Perera Chapter 50mSlip Resistance 600 by Paul R. Jr. Sliva PART 10: OPTICAL PROPERTIES Chapter 40--Color and Light 447 by Fred W. Hill Chapter 47inFlexibility and Toughness 547 by M. Hammond III Chapter 41~Gloss 470 by Harry K.viii CONTENTS Chapter 38--Measurement of Film Thickness 424 by C. Jr. M. Morse Chapter 48mHardness 555 by Paul R. Billmeyer. Chapter 49mStress Phenomena in Organic Coatings 585 by Dan Y. Aviles PART 11: PHYSICAL AND MECHANICAL PROPERTIES Chapter 44--Adhesion 513 by Gordon L. Fletcher Chapter 39--Drying Time 439 by Thomas J. Hammond III and Gabriele Kigle- Boeckler Chapter 42~Hiding Power 481 by Leonard Schaeffer Chapter 43--Mass Color and Tinting Strength of Pigments 507 by Julio I.

Crewdson Chapter 53~Accelerated Weathering 643 by Valerie D.iran-mavad. Eng. David F. Hicks and Michael J. OdeU and AI Siegmund Chapter 65--Sealants 735 by Saul Spindel Chapter 66--Traffic Marking Materials 741 by Larry R. Ryntz Chapter 62--Can Coatings 717 by Martin B. Hegedus. Ashton Chapter 60~Artists' Paints 706 by Benjamin Gavett Chapter 61--Automative Product Tests 711 by Rose A. Hirst Chapter 59~Architectural Coatings 696 by Harry E. Brandau Chapter 56~Testing Coatings for Heat Resistance and Flame Retardance 667 by Wayne Ellis Chapter 57--Water-Resistance Testing of Coatings 677 by Wayne Ellis PART 13: SPECIFIC PRODUCT TESTING Chapter 58--Aerospace and Aircraft Coatings 683 by Charles R. Sherbondy Chapter 54~Biological Deterioration of Paint Films 654 by David L. Sliva www. and Donald J. Pulley. CONTENTS Chapter 52--Natural Weathering 619 by Lon ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . Price Chapter 63--Masonry 725 by Frances Gale and Thomas Sliva Chapter 64--Pipeline Coatings 731 by Loren B. Anthony T. Stephen J. Spadafora. Hacker Chapter 67--Water-Repellent Coatings 748 by Victoria Scarborough and Thomas J. Campbell Chapter 55~Chemical Resistance 662 by Alan H.

Mills Chapter 77--X-Ray Analysis 871 by A. Hartshorn Chapter 74--Methods for Polymer Molecular Weight Measurement 835 by Thomas M. and Inductively Coupled Plasma Spectroscopy 783 by Dwight G. Michael Neag Chapter 76~UltravioletNisible Spectroscopy 865 by George D. Sheehan Chapter 73~Infrared Spectroscopy 826 by Jack H.iran-mavad.x CONTENTS PART 14: ANALYSIS OF PAINTS AND PAINT DEFECTS Chapter 68--Analysis of Paint 753 by Darlene Brezinski Chapter 69--The Analysis of Coatings Failures 767 by George D. Monroe Snider. PART 16: SPECIFICATIONS Chapter 78--Paint and Coatings Specifications and Other Standards 891 by Wayne Ellis Appendix 895 Index 899 www. Weldon Chapter 71--Chromatography 789 by Rolando C. Domingo Chapter 72~Electron Microscopy 815 by John G. ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . Jr. Schmitt Chapter 75--Coatings Characterization by Thermal Analysis 841 by C. Mills PART 15: INSTRUMENTAL ANALYSIS Chapter 70--Atomic Absorption.

Part I: Regulations ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ .

1974 SDWA ings. MNL17-EB/Jun. AMENDMENTS ronment has increased appreciably. can be dealt with by dilution and Act and its amendments that. to water. 1975 TSCA It was. sistent eye-irritating smog in the basin. Fortunately. 1980 sions resulting from the evaporation of solvents during high. flowing with a light westerly wind most of the year. plains that originate in the high mountains to the east. have dispersion of the objectionable materials to bring the had (and will continue to have) the greatest impact on coat- concentration below a level that can be detected by the neighboring citizenry. trucks. The frequency of smog conditions in of pollutants to air. 1986 prevailing view of this period was summarized by Francis Title III. in the author's opinion. RCRA released from some paints and coatings. Toxic Substances Control Act. in general. recognized that objectionable odors were Resource Conservation and Recovery Act. Title Scofield in his article in the 13th edition of the Paint Testing Right-to-Know. predictable regulatory and economic environment. California Smog lanche of new laws and associated regulations that affect A precipitating factor influencing the basis for selection of virtually all industry. Safe Drinking Water Act. Emergency Planning and Community SARA. formulator developing a solvent-based coating selected sol. of course. Among the new federal laws adminis- solvents for coatings in the 1960s and early 1970s was the tered by the U. this area had increased steadily during the 1950s and 1960s In addition. St. There was no ap. flammability. www. Albans. T H E CLEAN AIR ACT AND ITS Since the 1960s societal concern about health and the envi. an area uniquely situated in a series of (MSDS) and product labels. The 9 Hazard Communication Standard (HCS). they make and to provide appropriate safety information to The smog problem was (and is) most acute in the Los employees and users through the Material Safety Data Sheet Angeles air basin. 1983 basin enjoys predominantly sunny days with cool moist air 9 Occupational Exposure to Hazardous Chemicals in Labo. WV 25177. of course. and sophisticated analytical procedures are rarely needed to deal with these "nui- sance" problems. among the new federal standards administered as the number of automobiles. cost. Further. Clean Air ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . nor was there any appreciable incentive to Clean Water Act of 1972 CWA Amendments of 1977 reduce the solvent content of commercially acceptable coat. Law Abbreviation vents on the basis of evaporation rate. Comprehensive Environmental Response CERCLA Compensation and Liability Act. They are designed to control the emission Southern California.S. 1995 Regulation of Volatile Organic Compound Emissions from 1 Paints and Coatings by J. buses. 1970 CAA density.S. 1990 factors cause a nearly permanent temperature inversion layer. Amendments of 1977 CAAA-77 parent need to consider the relative photochemical reactivity Amendments of 1990 CAAA-90 of these materials. trapping air emissions that combine to produce a per- 11046 College Circle. most of the materials ings. John Brezinski I PRIORTOTHE 1960S the coatings industry enjoyed a somewhat TABLE 1--Federal environmental laws administered by the U.iran-mavad.astm. and airplanes by the Occupational Safety and Health Administration are increased and as industrial development expanded with the those that require manufacturers--including those making accompanying growth of petroleum and chemical processing paints and coatings--to evaluate the hazards of products and power plant utilization. and. These "nuisance" types of pollution are a continuing The discussion in this section will focus on the Clean Air problem but. and to soil. These ratories. air emis. 1980 (Superfund) temperature processing of oils and resins caused occasional Superfund Amendments and Reauthorization SARA complaints from persons living near the coatings Copyright9 1995 by ASTMInternational www. 1986 III Manual entitled "Atmospheric Pollutants" [1]. solubility parameter. The Act. used by the paint industry are not toxic at concentrations significantly below the range at which they can be de- tected by the human nose. Actions taken by federal and state legislative bodies have resulted in a steady ava. The paint Environmental protection agency. Environmental Protection Agency (EPA) recognition that the emission of solvents from coatings to the that impact significantly on the coatings industry are those atmosphere contributed to the growing "smog" problem in shown in Table 1.

About one half of the organic solvent all sources. passed by the Los Angeles Air Pollution Control District. Only a few materials showed negligible 9 Internal combustion engines photochemical reactivity. 1.2-trifluoro- amounts of the combinations shown in Table 2.1-trichloroethane approved solvents can contain no more than designated (methyl chloroform). *Calculated as the percent by volumeof the total solvent. John Gordon. NC of the Sources of NOx: Flame of almost any kind. On this basis. alcohols. Thus. 1.2- ethylene). In effect. Vol. led to the conclu- A 1962 estimate of the contaminants discharged into the sion that most organic compounds emitted to the atmosphere Los Angeles air during the summer period revealed that mo. even those Processes that Produce Hydrocarbons solvents considered acceptable under Rule 66 reacted to form 9 Petroleum production. metallic carbides or carbonates. hydrocarbons branched ethers with no unsaturations. contribute to the formation of ozone. No. ethers or ketones (W/8 C ketones. forest fires. 1- Quality Management District.1-difluoroethane (HFC-152a). 1. www. ethane (CFC-113). and perfluorocarbon compounds which fall TABLE 2--Rule 66--Limits of solvent categories in approved into these classes: mixtures. e s t e r s . pentafluoro- oped recently in the consideration of solvent photochemical ethane (HFC-125). 1. VOC Definition nents of smog [2]. which together in the presence of UV radiation react to produce oxidants and ozone. Regulatory Definition o f VOC tion. excluding carbon monoxide. Hydrocarbons. 1992. pp.1. emitted was attributed to the coatings industry.1. Approximately 66% of the NOx released was assigned to gasoline (motor vehicle) combus. or linear. oxide were irradiated for periods of up to 36 h. as aliphatic and naphthenic hydrocarbons.4 PAINT AND COATING TESTING MANUAL In a presentation entitled "Solvent Restriction--Problem reactivity in state. chiefly to the use in paint and coatings. adopted as a regulatory objective the limit of essentially all ganic solvents (for all purposes) accounted for about 18% of volatile organic compounds emitted to the atmosphere from the organic gases.2.2. A part of this definition is Based on the results of laboratory studies in "smog cham. inter. Aromatic Ethylbenzene. refining. Renewed interest has devel. and international programs re- or Opportunity.1-trifluoroethane (HFC. having an olefinic or atoms) toluene.2. normal ketones. 1. Rule 66.1-trichloro-2. major compo. 22 Feb. among which were: methane. 22.1. Usage of Solvents. while the combustion of fuels (energy supply) accounted The regulatory definition of volatile organic compounds for about 26% [1]. 3941-3946. Rule 66 promoted the use of specific solvents such dichlorodifluoromethane (CFC-12).1. cig. then of the University of lated to air quality control.124). superseded in 1976 by dichloroethane (HCFC-123).1-difluoroethane (HCFC-142b).100 Definitions 2 exposed for 6 h to light approximately the intensity of noon Volatile organic compounds (VOC) means any compound sunlight. while the use of or. chamber revealed that when organic materials and nitrogen arettes.2-tetrafluoroethane (HCFC. The United States Environmental Protection Agency (EPA) Sunshine was created in 1970 by Congress as part of a plan to consoli- HC + NOx UV Radiation Smog (03) date several federal environmental activities. or linear. boilers. ethane. 1. trichlorofluoromethane (CFC-11). Missouri-Rolla.2-tetrafluoroethane (CFC-114).iran-mavad. which were prompted in part 9 Surface coatings by the passage of the Clean Air Act of 1970. by the California South Coast Air (HF-134a). Studies directed by the EPA laboratories in Research Triangle Park. completely fluorinated 5% 8% 20% alkanes. branched. (ii) Cyclic.1-trifluoro 2.1. trifluoromethane (FC-23). FederalRegister. 2-chloro- various other state jurisdictions. 1. discussed the major sources of hydrocarbons and nitrogen oxides. the solvents could be classified as "low" or "high" in of carbon. carbon dioxide. These studies. chlorodifluoro- methane (CFC-22). Rule (1) This includes any such organic compound other than 66 identifies an "approved" solvent as one that contains less the following. photochemical reactivity related to the amount of peroxides carbonic acid. ylene chloride (dichloromethane). space heaters.1. branched. photochemical reactivity of materials in a laboratory smog nal combustion engines.2-tetrafluoroethane (HFC-134). completely fluorinated aldehydes. or cycIoolefinic trichloroethane 240 Code of Federal Regulations (CFR) Part 51. including paint and coatings applications [3]. meth- limited to certain combinations of these chemicals. volcanoes." in which a mixture of a solvent and nitrogen oxide was Section 51.1.* (i) Cyclic. and am- and ozone produced. an air pollution control regulation photochemical reactions.1. as follows: bers. eth- 9 Natural processes--forests and plants (isoprene and ter.1." Dr. and nitroparaffins.2-tetrafluoroethane Rule 442. which participates in atmospheric well-known Rule 66. 1. which have been determined to have negli- than 20% by volume of specific chemicals and is further gible photochemical reactivity: methane. (VOC) was revised by EPA in 1992. 1. esters. transport peroxides and ozone. ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . chloropentafluoroethane (CFC-115).1. chlorinated hydrocarbons (except trichloro. was subsequently adopted by chloro 1.1. 57. and fluorin- penes) ated compounds.1.143a). methylene chloride. Adoption and Submittal of Implementation Plans. These studies formed the basis for the monium carbonate.2-dichloro. alcohols. 1. Ap- proval and Promulgation of Implementation Plans. Requirements for unsaturation Preparation.1-dichloro 1-fluoroethane (HCFC-141b).1-trichloroethane. ane. 1. EPA tor vehicles accounted for about 60%.

the amount of The CTG documents relating to surface coatings opera- negligibly-reactive compounds in the source's emissions. Where such a method of Reasonably Available Control Technology (RACT): the lim- also measures compounds with negligible photochemi. its are expressed as pounds of VOC per gallon of coating cal reactivity. 24. The control of VOC emissions from new coatings plants pounds if such determination is not reflected in any of and from significant modifications of existing plants was the above provisions. tions issued through 1992 are shown in Table 3 with recom- (4) For purposes of Federal enforcement for a specific mended limits for VOC content. p p m as the annual arithmetic mean con- centration. including those shown in Table struction or significant modification of existing sources. Standards for ozone and nitrogen oxides are: The emission limits in both the CTG and NSPS documents. branched. Criteria pollutants are those for pressed as kilograms of VOC per liter of applied solids. be excluded as VOC if the amount of such compounds is The Clean Air Act Amendments of 1977 directed that states accurately quantified and such exclusion is approved by had to revise their implementation plans for areas out of the enforcement authority. as applicable. rather than placing a ceiling on individual plant emis- Nitrogen Dioxide The nitrogen dioxide concentration in sions. Ozone The ozone concentration in the atmosphere can. were given primary responsibility to develop appropriate reg.12 p p m as a daily m a x i m u m one-hour per unit of coating or of coating solids applied in the opera- average more than once per year. lead. materials [4].iran-mavad. The Federal EPA was as. these neglibflity-reactive compounds may (minus water). source. documents for the states related to various industrial coating rine. VOC will be measured by the test methods in tile Organic Emissions from Stationery Sources. and (iv) Sulfur containing perfluorocarbons with no unsat. These documents. nitrogen dioxide. The revised version of Federal www. The responsibility for establishing emission limits for the atmosphere cannot exceed 0. or linear. including the addition in 1990 of instructions for testing signed oversight responsibility for the state programs that multicomponent coatings and the deletion of sections dealing were described in "State Implementation Plans" (SIP). define the emission sources more narrowly and The Clean Air Act of 1970 targeted six criteria pollutants for impose a tighter level of emission control than that for related control: carbon monoxide. ozone. with testing at shorter times. or under 40 CFR parts 52 or 60. The EPA will not be STANDARDS bound by an State determination as to appropriate meth- ods for testing or monitoring negligibly-reactive com.053 particular plants. to the lished. appendix A. The revised (3) As a precondition to excluding these compounds as SIPs were to include sufficient control of VOC emissions from VOC or at any time thereafter. 5. and sulfur dioxide. tion. operations or end-use categories. Since 1980. focus on restricting the VOC content not exceed 0. the Agency issued the first of a series of guidance urations and with sulfur bonds only to carbon and fluo. based on EPA's assessment part 60. satisfaction of the enforcement authority. if appropriate. existing sources. which apply uniformly to all parts of The Ozone Standard the country. was left to the states [5]. Control of Vola- (2) For purposes of determining compliance with emis- sions limits. D E T E R M I N A T I O N OF VOC C O N T E N T CONTROL OF VOC E M I S S I O N S F R O M Federal Reference Method 24 COATINGS The procedures specified by the federal EPA for testing paint products for compliance with VOC limits are described The Clean Air Act addressed air pollution eminating from in Federal Reference Method 24 [6]. ex- ticulates. CHAPTER 1--REGULATION OF VOC EMISSIONS 5 (iii) Cyclic. States with areas that did not comply with the ozone standard Method D 2369 is a key procedure of Federal Method 24. This standard employs both existing sources and that from future new plant con- several ASTM test standards. the first of which issued in 1980. are which criteria were issued by EPA." include rec- the approved State implementation plan (SIP) or 40 CFR ommended VOC emission limits. compliance with the national ozone standard. several important revisions have been made in ulations for existing sources to meet the time schedule for this standard to make it compatible with revisions in Method compliance specified by Congress. The VOC limits defined in the NSPS. in the majority of cases. called "Control Technique Guidelines (CTG) Series. These mandatory standards. national ambient air quality standards (NAAQS)--levels that The New Source Performance Standards for surface coat- protect against adverse effects to health and to plants and ings operations issued through 1992 are shown in Table 4. the enforcement authority stationery sources. subpart I or appendix S. completely fluorinated Control Technique Guidelines tertiary amines with no unsaturations. the EPA will use the test methods specified in the applicable EPA-approved SIP in a permit issued pursu- ant to a program approved or promulgated under title V NEW SOURCE PERFORMANCE of the Act. as applied. par. These documents include based on the best demonstrated technology (BDT) for the specific coating operation. such controls to incorporate the RACT may require an owner or operator to provide monitoring limits for coatings operations for which a CTG was pub- or testing methods and results demonstrating. In 1977. or under 40 CFR part 5 I. addressed by EPA in a series of New Source Performance Standards (NSPS).com ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ .

Dec. 1978 (Consult CTG or state regulations) flexography Magnetic tape See Paper coating Magnet wire Dec.9 0. a voc .8 0. ganic C o m p o u n d s E m i t t e d by Paint.42 Powder coatings 0.35 Plastic parts for business machines None Polymeric coatings of supporting None. 1993 e x e m p t solvent ] VOC = [7].66 End seal compound 3. 5285 Port Royal Road.3 0.5 0.34 Final repair 4. e m p t solvent. 1978 Printed interior panels: 6..6 0. 1977 3.W~x)(Dr (1) for the investigation in ASTM of the precision of VOC co n t en t 100%.34 Topcoat 2.8 0. 1977 Fabric coating ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ .\ w at er ] \ e x e m p t solvent] ASTM D 3960. 100% .0 lb/1000 sq. Persons subject to emission control for any of the operations are advisedto consult the state/local regulations for details. vex vide a guide for the calculation of VOC and to establish a base (W~ .0 0. 1977 Sheet basecoat 2. bReasonably available control technology (RACT)limits recommended in CTG and. in most cases. electrodeposit 1.7 0.36 Miscellaneous metal parts and June.weight % The general expression for calculating VOC c o n t e n t in nonvolatiles).. 1977 2.45 and/or Graphic Arts Packaging Rotogravure.0 lb/1000 sq.51 Side seam 5.20 Metal coil May.8 0. (Ww)(Dc/D~).0 lb/ 1000 sq. large Dec. flexible Fabric: May 1977 Vinyl 3.. Inks.52 Extreme performance 3.5 0.2 0.VA 22161.. gr a m s p er liter of coating less w a t e r and e x e m p t solvent Ww = weight % of w at er (ASTM D 3792 or ASTM D specified in the EPA Control T e c h n i q u e Guidelines issued 4017). Springfield. Wu = weight % of total volatiles = (100% .8 0. (Wo)(Oc) standard developed in ASTM S u b c o m m i t t e e D01. 1977 Primer.8 0. (Volume% 1 _ ( Volume% 1 Substantial revisions during 1989-1991 were also m a d e in 100% . 2nd ed. 1977 Prime and topcoat or single coat 2. 1978 Wood paneling.(W~)(D~/Dr determination..8 0. Practice for D e t e r m i n i n g Volatile Organic or C o m p o u n d (VOC) Content of Paints and Related Coatings.23 Guidecoat (surfacer) 2.34 Auto and light duty trucks May. that was published in 1984 [8]. (ASTM D 2369). flat June. Vw .14 Prime coat 1. 1977 2. ft of surface coated Class II finishes 10.05 All others 3.34 Interior body spray 4.2 0. Ink a n d Other Coatings" 141o = weight % of organic volatiles = Wv . aCTG documents are available from the National Technical Information Service.58 Cans May.0 0.31 Metal furniture Dec. The definitions a n d symbols used in D 3960 where are those ad o p t ed by the EPA and included in the Agency VOC = VOC co n t en t in g/L of coating less w a t e r and ex- d o c u m e n t "Procedures for Certifying Quantity of Volatile Or.4 0.8 0. 1977 (Based on the use of an incinerator) 1. Allowable Limitsb Lb VOC/Gal Kg VOC/L Coatings Operation CTG Date" Minus H20 Minus H20 Appliances.21 to pro. and Related Coating Products.7 0. ft of surface coated NOTE:The information presented in this table is not complete. may be substrates considered fabric coating Pressure sensitive tapes and labels See Paper coating Vinyl and urethane. adopted in state/local regulations.iran-mavad.45 Graphic arts--rotogravure and Dec.44 Fabric May. film and foil May. Reference M e t h o d 24 is also included in the ASTM Manual on Weight % total volatiles Determination o f Volatile Organic Compound (VOC) Content less w a t e r less | (Density of coating) in Paints. www. 1978 Air dry 3.W~ .34 Vinyl coating 3.36 Paper.6 PAINT AND COATING TESTING MANUAL TABLE 3--VOC content limits in control technique guidelines (CTG) for surface coating operations.8 0.42 products Clear coat 4.5 0. fl of surface coated Natural finish plywood: 12.9 0. t h r o u g h 1991 is: 14~x = weight % of e x e m p t solvent (ASTM D 4457).Wex.Ww .

Method 24. m u l t i p l y t h e r e s u l t (VOC Related Products c o n t e n t ) b y 8. . . T o c o n v e r t g/L t o kg/L.89 Fabric (coating) See Polymeric coating of supporting substrate Graphic a r t s .1983 Exterior base 2.1.40 Top coat 12.47 Cans (beverage cans only) Aug...90 Miscellaneous metal parts and None . Allowable Limitsb Lb VOC/Gal Kg VOC/L Coatings Operation NSPS Date~ Applied Solids Applied Solids Appliances.2 0.1. D 1475-60 Density of Paint.16 Guide coat 11.3 1. and T o c o n v e r t f r o m g/L t o lb/gal. .. Direct Injection into a Gas The general expression for VOC content defined in terms of Chromatograph the mass of VOC per unit volume of coating solids applied as D 4017-81 Water in Paints and Paint Materials by Karl s p e c i f i e d i n t h e E P A N e w S o u r c e P e r f o r m a n c e S t a n d a r d s is Fischer Method ( W .com ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ ..345 • 10 -3 (lb/gal)/g/L).. 1982. the limits are expressed as kilograms of VOC per liter of applied solids..2 2.52 1. .. TABLE 5 . . In the NSPS.2 Consult NSPS Magnet wire None .28 With emission control device 1. a n d D. bBest demonstrated technology (BDT) emission limits established as NSPS standards.r o t o g r a v u r e and Rotogravure only Consult NSPS d o c u m e n t flexography Nov. 1982 w/o emission control device 2.We~)Dc VOCm = (2) D 4457-85 Analysis of Dichloromethane a n d 1.67 0.5 0. 5285 Port Royal Road.0 Wood paneling.Ww . ASTM Method Test Method f o r . . 1985 7. 1988 Prime a n d color coat 12.8 0. . . Apr.x = density of e x e m p t s o l v e n t a t 25~ i n g/L ( A S T M D D 2369-81 Volatile Content of Coatings 1475).iran-mavad. . Trichloroethane in Paints and Coatings by Direct Injection into a Gas where Chromatograph V O C m = V O C c o n t e n t i n g/L o f c o a t i n g solids. . v. Metal coil Nov. 1982 Magnetic tape Oct.46 Inside spray 7.0 . 1988 1. NOTE: The information presented in this table is not complete.5 0. flexible June. Dc = density o f c o a t i n g a t 25~ i n g/L ( A S T M D 1475).. products Plastic parts for business machines Jan. Dw = density o f w a t e r a t 25~ i n g/L -.5 Texture and touch-up 19. Lacquer.. . 1984 8.3 0. a n d www. large Oct. Varnish. 1980 Prime coat 1.. CHAPTER 1--REGULATION OF VOC EMISSIONS 7 TABLE 4 . VA 22161.90 Auto and light duty trucks Dec..2 1. .4 0. . . flat None .3 0.(Ww)(Dc/Dw). 1989 90% control from process: substrates Consult NSPS Pressure sensitive tapes Oct.4 0. Springfield..15 Metal furniture Oct.3 Polymeric coatings of supporting Sept. Persons subject to emission control for any of the operations are adv/sed to consult the specific language of the referenced documents and state and local regulations. ~NSPS documents are available from the National Technical Information Service (NTIS).7 1.7 0. 1983 1. D 3792-79 Water Content of Waterborne Paints by d i v i d e t h e r e s u l t b y 10 a. .V O C limits in New Source Performance (NSPS) for surface coatings operations. 9 9 7 • 103. .29 Clear base coat 3.A S T M standards referenced in Federal Reference Vex = volume % of e x e m p t s o l v e n t = (Wex)(Dc/Dex).20 Vinyl and urethane...1982 7. Vw = volume % o f w a t e r -.

EPA stated: "Though certainly less Cans than ideal. solvent content. to H. 4 The EPA would have preferred to limit volatile organic In this standard. a catalyst is added prior to the bake cycle compound emissions in the Control Technique Guidelines on to simulate the catalytic effect provided by masonry during the basis of the unit volume of coating solids applied. Motor Vehicle Manufacturers Association. EPA. 9 D 5327 Practice for Evaluating and Comparing Transfer Ef- 9 D 5087 Test Method for Determining the Amount of ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . Use of any of these stan. a modification of Practice D 5066 developed developed or in process of development are the following: for use in the automobile industry. Studies and discussions in ASTM Subcommittee D01. adoption in the 1970s of Eq 1. cent Volatile Content of Water-borne Aerosol Paints ing sample obtained during a plant inspection. Environmental Protection Agency [9]. in which VOC content is defined as mass per unit volume of coating less water and less Aerosol Spray Paints exempt solvents. percent nonvolatile content. Smith. Berry of U. Among the new standards This standard.iran-mavad. Federal EPA for use in demonstration of compliance with 9 D 5286Test Method for Determination of Transfer Effi- VOC emission control regulations. Gary McAllister. Blends Used in Masonry Water-Repellent Treat- ing. these units require only one volumetric and one proposed regulations in California to limit the level of volatile gravimetric measurement" [5]. was necessary as no acceptable consensus procedure was available for determining the volume percent 9 D 5200 Test Method for Determination of Weight Percent nonvolatile content. Test Method for Volume Nonvolatile sfer Efficiency Under Laboratory Conditions Matter in Clear or Pigmented Coatings: Use of the Helium These standards were developed with the cooperation of Gas Pycnometer (Under Study) representatives from automotive coating suppliers and the The use of the helium gas pycnometer provides a quick. In the sim. 9 Revision of D 2697. but states that the value be calculated from the Letter. analytical laboratory determinations). The values obtained dards has expanded significantly since 1980. The actual application of the water-repellent treatment. NJ Dept. 9 Direct Measurement of Volatile Organic Material in Water- Reducible Coatings (Under Study) Masonry Treatments Federal EPA funds supported the preliminary investigation 9 D 5095 Test Method for Determination of the Nonvolatile of this novel approach to the "direct" gravimetric determina- Content in Silanes. of Environmental coating manufacturer's formulation. In a presentation in Copenhagen in 1990.S. organic material in aerosol paints. the major attraction is that the expression permits 9 D 5325 Test Method for the Determination of Weight Per- the determination of compliance from the analysis of a coat.and siloxane-based coatings: for determining V~. These standards were developed for potential use related to plest case. The general Removal in a VOC Control Device (Abatement) approach employed is derived from that developed in Method 9 D 5066 Practice for the Determination of the Transfer Effi- D 5009 except that D 5327 employs a fixed rather than moving ciency Under Production Conditions for Spray Ap- plication of Automotive Paints--Weight Basis spray station. ficiency under General Laboratory Conditions tile Organic Compounds (VOC) Released from Sol- Practice D 5327 provides a useful guide for general re- vent-Borne Automotive Coatings and Available for search studies related to transfer efficiency. = Volume % nonvolatile content of the liquid coat. Many of the may not be acceptable for demonstrating regulatory compli- standards listed in this section have not been approved by the ance. www.8 PAINT AND COATING TESTING MANUAL V. a critical parameter in the calculation of volume the U. OTHER VOC-RELATED METHODS AND ASTM D 5201 describes procedures for the calculation of STUDIES formulation weight solids. The calculation of various physical constants directly from the paint formulation is a common practice in industry. ASTM D 2697. volume solids. Siloxanesl and Silane-Siloxane 4This standard has been accepted by the Federal EPA for use in the 3EPAReference Method 24 does not include an analytical method determination of the VOC of silane. Volatile Content of Solvent-borne Paints in Aerosol James C. ciency Under General Production Conditions for dards to demonstrate compliance should be coordinated with Spray Application of Paints appropriate regulatory agencies. 3 ments.S. 9 D 5009 Test Method for Evaluating and Comparing Tran. Method D 5009 reliable approach to the determination of the dry coating was derived from a study of transfer efficiency conducted for density. 25 March 1992. describes conditions for determining transfer efficiency under production conditions S t a n d a r d s Specific to t h e A u t o m o b i l e I n d u s t r y applicable to spray application of miscellaneous parts. Protection.21 that led to the modification and improvements of ASTM standards referenced in Federal Method 24 and in ASTM General Application Standards Practice D 3960 were conducted with the cooperation of EPA 9 D 5201 Practice for Calculating Formulation Physical Con- personnel of the Office of Air Quality Standards Development stants of Liquid Paints and Coatings at Research Triangle Park. NC. and density of liquid paint based on formulation data (not ASTM development activity on other VOC-related stan.

weighed tubes. After radiation cure.280 and above 20 (2010) 5U. and the protection of ozone in The method involves ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . will be imposed on areas.''s A TABLE 6--Clean air act amendments--1990 ozone nonattainment area classifications.180-0. Attachments in the second edition of this man. industry." ~Onlythe Los Angelesarea is in this classification. after Method 30 of 9 wood furniture California's Bay Area Air Pollution Control District in which In addition. EPA Office of Air and Radiation. are currently under study. ozone nonattainment areas are placed in five compliance with VOC emission control regulations is avail. "Implementation Principles for the Clean Air Amendments of 1990. CHAPTER 1 .160 6 (1996) of ozone in the atmosphere. Further information about the development. able in the ASTM Manual on Determination of Volatile Or. the magnitude to 24 and a publication from EPA's Emission Standards Divi. the organic effluent evolved on heating a paint Features of the Act that will impact most on the coatings specimen for 1 h at 110~ while purging the reaction vessel industry include: with dry nitrogen.160-0.180 9 (1999) Severe 0.280 15 (2005) Extreme~ 0. EPA plans to promulgate national rules to the specimen is baked for 1 h at 40~ D 5328 is applicable to control VOC emissions from architectural and industrial paste printing inks and vehicles that dry primarily by absorp. EPA was also directed to prepare new baked at 110 + 5~ for 60 min. the states.iran-mavad. maintenance coatings and from traffic paints. 9 D 5403 Test Method for Volatile Content of Radiation Cur- able Materials Title I m O z o n e Control in the Atmosphere The test methods in D 5403 determine the weight percent Title I specifically directs EPA to develop control technique volatile content of paint. sion from consumer and commercial products. Increasingly strict provisions. be related to the severity of the ozone problem. and regulation of this broad category of products is planned. that from aerosols. reduction of acid rain. as about the use of ASTM standards for the demonstration of In CAAA-90. polymerization. control of hazardous air pollu. including further reduction ual include the 1992 revision of Federal Reference Number of VOC emissions. the requirements of the national ambient air quality stan. including tion of heat. negotiated rulemaking may be employed. major impetus for these amendments was the continued in- ability of a number of heavily populated urban areas to meet Years to Achieve Design Value Compliance.S. and environmentalist groups to negotiate the con- and limitations of these VOC-related ASTM standards as well tent of a proposed rule. In the develop- ment of these rules. control technique guidelines for additional coatings uses that include: Inks 9 autobody refinishing 9 plastic parts (business machines) 9 D 5328Volatile Organic Compound (VOC40) Content of 9 plastic parts (others) Non-Heatset Paste Printing Ink Systems at 40~ 9 offset lithography This standard is patterned. and inks that are designed guidelines and maximum achievable control technology to be cured by exposure to ultraviolet light or to a beam of (MACT) standards for aerospace coatings and for shipbuild- accelerated electrons. Supplementary Information a process bringing together representatives of EPA. classifications based on the mid-1991 ozone level (Table 6).121-0. Serious 0. Marginal 0. Ink and Other Coatings" required: [8].138-0. Depending on sion titled "Procedure for Certifying Quantity of Volatile Or. Products [7]. in part. stationery sources 9 New source review and permits for new or modified sta- tionery sources 9 Reduced emission threshold levels for the definition of CLEAN AIR ACT A M E N D M E N T S OF 1 9 9 0 major stationery sources. Included in the latter publication are "VOC Data Sheets" 9 Increased monitoring and more accurate VOC and N O 2 applicable to coatings "as supplied" by the manufacturer and emission inventory for coatings "as applied" by the user. Solvent emis- tion.. ranging between 10 tons/year for severe classification areas to I00 for marginal or moderate The Clean Air Act Amendments of 1990 defined a compre- areas hensive long-term approach "to achieve and maintain a healthy environment while supporting a strong and sus- tainable economic growth and sound energy policy. www. on activated charcoal in the stratosphere. The form used for "as 9 Revision of state implementation plans to incorporate supplied" coatings is patterned after a recommendation of RACT limits from previous and future CTGs for all major the National Paint and Coatings Association. and compliance with the national ozone standard by specific ganic Compounds in Paints. tants.R E G U L A T I O N OF VOC E M I S S I O N S 9 tion of volatile organic content of waterborne coatings [10].138 3 (1993) Among the specific issues addressed in the Act are: control Moderate 0. coatings. Classification (Ozone Level) year dards for ozone and carbon monoxide. and Related Coating years is mandated in the law. the specimens are ing coatings and repair. several or all of the following will be ganic Compounds Emitted by Paint. the area classification. or related means without the applica. Methanol is not captured on the charcoal. significance. Inks.

clude those that emit 10 tons or more per year of a single The Agency was required to p u b l i s h emission limits based regulated hazardous air pollutant or 25 tons per year of a o n m a x i m u m achievable control technology (MACT) for 40 of c o m b i n a t i o n of hazardous air pollutants. the regulations. shipbuilding a n d ship repair. by the end EPA is to approve (or disapprove) state permit programs w i t h i n one year of receipt. Under Title V of rects that the health impact a n d economic factors he consid. Sufficient funds will be available to the states tants was published by EPA in 1992 (57FR44147. deadlines. from requiring a permit for five years after the Diethanolamine state p e r m i t p r o g r a m is approved by EPA.1-trichloroethane (methyl chloroform)~ Methylene chloride~ of VOC shown in Table 8 are identified as m a j o r sources.iran-mavad. a n d all permits m u s t be issued a n d be ORGANICMATERIALS legally b i n d i n g by the e n d of 1997.S t a t e Operating Permit Program U n d e r Title III. By the end of 1994 emission standards were due for pollutant emitted.g. Lead compounds~ Area Classification tons/year Mercury compounds~ Marginal or moderate 100 ~Materials included in the EPA/Industry33/50 Project. U n d e r the rule. The Act di. Title III--Air Toxics Program Title V . ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . a threshold limit of 50 tons/year of VOC emission applies. a n d wood Major sources required to have state operating permits in- furniture. with some Dibutyl phthalate exceptions. u n d e r which operating permits are required (57FR31576. 189 products The state operating p e r m i t p r o g r a m is considered by EPA are identified in the Act. 16 July 1992) included u n d e r Surface Coating of sources that discharge pollutants to water. the fee to be assessed against all m a j o r the following surface coating processes: magnetic tapes. printing/publishing. a n d the final rule on operating p e r m i t programs. the m a j o r sources m u s t apply for TABLE 7--Clean air act amendments--1990 selected hazardous the five-year p e r m i t within one year of the EPA's approval of air pollutants used in paints and coatings.10 PAINT AND COATING TESTING MANUAL 9 Higher VOC emission offset r e q u i r e m e n t s for new or modi. Cobalt compounds Ozone Nonattainment VOC Emission Limit. EPA is directed to evaluate a n d control the emission of hazardous air pollutants (HAPS). sources. A draft timetable for wherein the states are given authority to m o n i t o r a n d enforce regulating the categories of sources of hazardous air pollu. states have Bis (2-ethylhexyl phthalate) the option of exempting all n o n m a j o r sources. 24 Sept. 21 July 1992). a n d EPA has the authority to delete as a cornerstone of the CAAA-90 a m e n d m e n t s designed to or add additional products to this list. Also included is the Manufac. of 1995 sufficient categories a n d subcategories m u s t be listed fied sources to ensure that 90% of the area sources that emit the 30 most hazardous air pollutants are subjected to regulation. I n the p r o g r a m Processes those processes for which a CTG or n a t i o n a l rule u n d e r Title V. Dimethyl formamide Dimethyl phthalate The characterization of a m a j o r source in ozone non- Ethylene glycol a t t a i n m e n t areas is also based o n the a m o u n t of volatile Formaldehyde organic c o m p o u n d s emitted annually. a voluntaryindustry Serious 50 initiative to reduce the total release and transfer of 17 targeted chemicals by Severe 25 one third by the end of 1992and by one half by the end of 1995 (using 1988as a Extreme 10 baseline year).. regulations will be consolidated u n d e r a single d o c u m e n t ture of Paints. Styrene Toluenea For ozone transport regions (e. one is established in the Xylenes~ Northeast). This p r o g r a m will impact o n m a n y previously un- Among the materials included o n the initial HAP list that regulated coatings m a n u f a c t u r e r s a n d users. pollution equivalent" of the NPDES permit p r o g r a m of the ucts. The final rule are used in paints a n d coatings are those shown in Table 7. dard (NESHAP) has been established. re the operating p e r m i t p r o g r a m was issued in 1992 The control of emissions of hazardous air pollutants is to (57FR32250.. The threshold a m o u n t Glycol ethers (ethylene oxide-based) is related to the area classification a n d sources in ozone Methanol n o n a t t a i n m e n t areas that emit above the designated a m o u n t 1. Coatings and Adhesives. be achieved t h r o u g h the p r o m u l g a t i o n of emission standards The operating permit p r o g r a m has been called the "air for source categories a n d subcategories that emit these prod. These pollutants these categories by the end of 1992. the state program. Methyl ethyl ketonea These limits vary between 10 tons/year for the "extreme" Methyl isobutyl ketone~ classification to 100 tons/year for the "marginal or moderate" 2-nitropropane classification.1. CAAA-90. from a m i n i m u m a n n u a l fee of $25 per ton for each regulated 1992). with MACT limits to be include those materials for which a n a t i o n a l emission stan- identified for the r e m a i n i n g categories by 2000. I n d u s t r y groups m a y ensure that the ozone n o n a t t a i n m e n t areas meet compliance petition EPA to delist products. The initial list of categories of sources published by EPA Clean Water Act. INORGANICANDOTHER Ammonia Antimony compounds TABLE 8--Clean air act amendments--1990 major source Cadmium compounds~ identification based on VOC emissions: limits for area Chromium compoundsa classifications. ered in defining appropriate MACT limits. Further. all federal a n d state air pollution rules a n d has b e e n issued or is planned.

flat law that will issue d u r i n g the 1990s will have a m a j o r i m p a c t EPA-450/2-78-033 Vol.1. CO 80202 Phone (800) 759-4372 American Somoa. Hawaii. Dearborn ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . Michigan. Rhode Island. District of Philadelphia. Guam. Kansas. U. Fabric m o n i t o r i n g data. Title VI--Stratospheric Ozone Protection Subehapter Subject Parts The m o s t significant feature of the p r o g r a m to protect C Air Programs 50-87 ozone in the s t r a t o s p h e r e is the staged p h a s e o u t of 1. a m a t e r i a l widely used in coatings a n d clas- D Water Programs 104-149 I Solid Waste 240-281 sified as a "VOC-exempt" solvent by the EPA. West Virginia. A m o n g the m a n y u n c e r t a i n t i e s are flexography the n a t u r e a n d level of MACT limits to be defined for essen- Vinyl and urethane. Also i n c l u d e d are provisions Metal Coil Paper. a n d reports. South Atlanta. Puerto Rico. Wyoming Suite 500 Denver. Nebraska 726 Minnesota Ave.1- New Source Performance Standards 60 trichloroethane. Seattle. Suite 1200 Dallas. Montana. PA 19107 Columbia Phone (800) 438-2474 Alabama.. CHAPTER 1 . VII Wood paneling.S. IV Magnet wire Scenario for the 1990s EPA-450/2-77-034 Vol. 345 Courtland St. Georgia. a n d false s t a t e m e n t s in records. South Dakota. V Appliances. IL 60604 Phone (800) 572-2515 in IL (800) 621-8431 in other Region 5 states Arkansas. R Toxic Substances Control Act 700-799 t h e n to the 20% level for the p e r i o d 2000-2001. Oregon. North Carolina. WA 98101 Phone (206) 442-5810 www. Maryland. New York. California San Francisco. North Dakota. violation of s o m e of the Cans o p e r a t i n g p e r m i t provisions. and foil for field citations b y inspectors. 841 Chestnut St. Virginia. Region States Address Connecticut. Pennsylvania. Florida. Oklahoma. Massachusetts. NE Mississippi. Washington 1200 6th Ave. Utah. Arizona. large CAAA-90 a n d the m y r i a d of n e w federal a n d state regula- EPA-450/2-78-015 Vol. Nevada. TABLE 10--Control technique guidelines and surface coating Title VII--Enforcement operations reference documents. VI Miscellaneous metal parts and products tions associated with i m p l e m e n t a t i o n of this c o m p r e h e n s i v e EPA-450/2-78-032 Vol. 230 S. Environmental Protection Agency. NY 10278 Phone (212) 264-2515 Delaware. Tennessee Phone (800) 282-0239 in GA (800) 241-1754 in other Region 4 states Illinois. Kennedy Federal Bldg. Room 2203. 1445 Ross Ave. the level of new o r stricter VOC TABLE I 1--Regional offices. II Auto and light duty trucks of the State I m p l e m e n t a t i o n Plan. Idaho. Missouri. F. Minnesota. Wisconsin Chicago. Kentucky. New Mexico. KS 66101 Phone (913) 236-2803 Colorado. P r o d u c t i o n (and J Superfund/Right-to-Know 300. 26 Federal Plaza Virgin Islands New York. Maine. 215 Fremont St.iran-mavad. Vermont Boston. New Hampshire. MA 02203 Phone (617) 565-3715 New Jersey. Ohio. 999 18th St. CA 94105 Phone (415) 974-8076 10 Alaska. TX 75202 Phone (214) 655-2200 Iowa. Indiana. Kansas City. GA 30365 Carolina.R E G U L A T I O N OF VOC E M I S S I O N S 11 TABLE 9--Code of federal regulations subchapter topics. after w h i c h the use of the m a t e r i a l will be prohibited. III Metal furniture EPA-450/2-77-033 Vol. EPA is g r a n t e d b r o a d n e w a u t h o r i t y to i m p o s e penalties EPA Document Reference Coating Operation a n d substantial fines for various actions including: violations EPA-450/2-77-008 Vol. J. VIII Graphic arts--rotogravure and on the coatings industry.372 use) will be r e d u c e d in i n c r e m e n t s (from the 1989 a m o u n t ) N Effluent Guidelines and Standards 401-471 b e g i n n i n g in 1993 to a 50% level for the p e r i o d 1996-1999. Texas 12th Floor. EPA-450/2-77-032 Vol. Louisiana. flexible tially all coating operations. film.

10 July 1992. Part 60. EPA Contract No. sentation to the Chicago Coatings Society. [1] Scofield. Environmental Protec- tion Agency." presentation at the International Symposium on Paint the National Technical I n f o r m a t i o n Service (NTIS)." EPA-450/3-83-013R. Subchapter C. m a n y new regulations a s s o c i a t e d with the a m e n d m e n t s . Recommended Policy on Control of Vol- lations as well as those of related state a n d local codes are atile Organic Compounds. Information S o u r c e s [10] Method Development for Measuring the VOC Content of Water- Based Coatings. velop a n d provide e n v i r o n m e n t a l l y acceptable m a t e r i a l s as A m o n g the i n d u s t r y o r g a n i z a t i o n s that provide informa- well as to p a i n t f o r m u l a t o r s to develop new o r modified tion to their m e m b e r s h i p a b o u t p e n d i n g regulations a n d coatings with r e d u c e d VOC content. Paints. are p u b l i s h e d in the Code for Testing and Materials. 68D90055. DC.12 PAINT AND COATING TESTING MANUAL e m i s s i o n limits for coating operations. Dry Colour M a n u f a c t u r e r ' s As- a p p l i c a t i o n of coatings is expected. NC. 30654-30656. 1978. a n d the time.. 40. REGULATION INFORMATION REFERENCES Published Sources F e d e r a l e n v i r o n m e n t a l regulations. 133. Agency. December 1983. EPA- 600/2-88-026a and EPA-600/2-88-026b. 5285 and the Environment. VA 22161.. tions (Table 9). J. American Society m u l g a t e d u n d e r the Clean Air Act. Table 10. [7] Manual on Determination of Volatile Organic Compounds in P r o p o s e d regulations are p u b l i s h e d by the EPA in the Fed. Springfield. p... 1993. including those pro. 1989. Amendments in a Rule published in the Federal Register. Re- c o m p l i a n c e to air quality regulations m a y be a d d r e s s e d to the search Triangle Park. EPA-450/3-84- sented. These regu. sociation (DCMA). [4] "Glossary for Air Pollution Control of Industrial Coating Regulations of p a r t i c u l a r interest to the coatings i n d u s t r y Operations. [5] Berry. F. No. Copenhagen. 13 Nov. Inks. of Federal Regulations (CFR). a n d often a public [8] Procedures for Certifying Quantity of Volatile Organic Com- h e a r i n g is s c h e d u l e d at w h i c h oral c o m m e n t s can be pre. The U. C. I and II.S. EPA Publication Nos. Washington. U.iran-mavad. DC. i n c r e a s e d g u i d a n c e on c o m p l i a n c e with finalized regulations are Chem- attention to the i m p r o v e m e n t of coating processes a n d to the ical M a n u f a c t u r e r s Association (CMA). [3] EPA Policy Statement. a p u b l i c (written) c o m m e n t p e r i o d of MNL4. Environmental Protection can be found in s u b c h a p t e r s of the Code of Federal Regula.S. a series of b o o k s that are gener. pounds Emitted by Paint. pp. U. Washington. Ink and Other Coatings. www. Additionally. 57. 11).S. J. and Related Coating Products. N a t i o n a l Paint a n d use of a b a t e m e n t e q u i p m e n t for e m i s s i o n control d u r i n g the Coatings Association (NPCA). Environmental Protection Agency. EPA regional offices o r to the specific state regulating m a n p o w e r . ing TransferEfficiency. Vol. NC. [2] Gordon. each responsible for several states (Table pose a c o n t i n u i n g challenge to r a w m a t e r i a l suppliers to de. Typically. 28 and 40. FederalRegister. Port Royal Road. CTG d o c u m e n t s [6] Code of Federal Regulations. (VOC) Emissions from Painting Operations in the United erations are not included in the CFR. 1990. ASTM Manual Series. 12-14 Nov. the 1990s will ten regional offices. Research Triangle Park. 13th ed. EPA. Environmental Protection Agency. 8 July 1977. the Federal Register together with the r e g u l a t i o n c o m p l i a n c e [9] Development of Proposed Standard Test Method for Spray Paint- date. also o b t a i n a b l e from the associated r e g u l a t o r y offices. 2nd ed.. Vol. "Solvent ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . b u t are available from States. The c o m m e n t s received are c o n s i d e r e d by the Agency 019. t h r o u g h 1991 are i n c l u d e d in the EPA p u b l i c a t i o n s listed in Appendix A. "Control of Volatile Organic Compound The F e d e r a l Control Technique Guidelines for coating op. Problem or Opportunity. 413. 30 to 90 days on the p r o p o s a l s is allowed." pre- ally available in m a j o r libraries a n d law libraries. Vols. a n d cost a s s o c i a t e d with c o m p l y i n g with the b o d y responsible for air quality control. Several coatings j o u r n a l s p u b l i s h ex- cerpts from regulations a n d s u m m a r y reviews. De- in the d e v e l o p m e n t of a final regulation that is p u b l i s h e d in cember 1984. a n d ments No. E n v i r o n m e n t a l Protection Agency has established As did the decades of the 1970s a n d 1980s. 1972. in Paint Testing Manual. a n d Chemical Specialty M a n u f a c t u r e r s Association (CSMA). applicability. Work Assign- Questions relating to the interpretation. Philadelphia. eral Register.

Part 2: Naturally Occurring Materials ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ .

fide. are Gilsonite. semi-solid. in fact. Cuban. of 80 to 90% purity. as well as the extent to which coatings applications i s from petroleum processing [3]. Water.the terms "bituminous" and "asphal. glance pitch. 1995 Bituminous Coatings by Ben J. etc. the adhesive A separate class of natural bitumens are the asphaltites. bitumen re. for example. pitches and asphaltites. i.). This leads to the classification of bitumens into two classes: stances. of ap- proximately 50 to 57% bitumen. composed principally of (1) natural asphalts (bitumens) and (2) artificial or oil as- high molecular weight hydrocarbons. 15 www. refined. natural deposits of soft bituminous material or as hard. was able to u u m or steam distillation of crude oils containing high produce a good-quality material suitable for paving work. Most oil asphalts are generally greater plied the natural deposits (the Trinidad Lake asphalts on the than 99% soluble in CS2. impurities are present. and waterproofing properties of bitumen have been known These are also called the solid bitumens and are asphalts since the earliest days of civilization. The purity of bituminous materials is generally related to (2) a generic term used to denote any material composed the degree that they are soluble in certain organic solvents. OH.e. principally of bitumen. They are obtained from the vac- straight run distillation. impurities. In the early 20th century. asphalts are found throughout the world in several the generic material [1]. natural asphalts. most asphalt used in the United States today for graphical region of their origin. As one of man's oldest engineering materials. "mumiya.astm. and Bituminous Materials (D 1079-87a) [2] defines formations. soluble in carbon disul. tar sands. . tions will be used. Oil or petroleum asphalts are soft to hard asphalts of high The first asphalts produced in the United States were de. free of inorganic tion as a high-grade standard paving bitumen. the ASTM defini.. The natural asphalts can be further classified by the geo- phalts). colored (solid. The Egyptians were known to have used plications is Gilsonite. The area between the without impurities (silts. refined. and various rock asphalts.. Mexican asphalt obtained from Mexican crude oil was used tic" are often used interchangeably. limestone. the part-Per. ASTM Test Method for Bitumen Content ents are bitumens which occur in nature or are obtained in (D 4-86) formalizes this procedure with CS2 solubility as the petroleum processing. Island of Trinidad or the Bermudez Lake. with History and Background of Bitumens varying degrees of bitumen content. Additionally." While the term has historically Copyright9 1995 by ASTM International www. Asphalt is often considered the impure form of Today. Artificial bitumens have been classified into three major sian word for asphalt. siduum" and is often a solid material. or viscous) cementitious sub. asphalts are derived from colloi- bitumen as either ". A classed as pure bitumens. Examples of these materials cradle of civilization. long believed to be "the degree of CS2 solubility varies.. MNL17-EB/Jun. phalts (petroleum asphalts). black bitumen associated with certain rock forma- ASTM Definitions of Terms Relating to Roofing. Venezuela as. the degree of solubility in carbon disulfide (CS2) Asphalt is similarly defined as " .iran-mavad. tars. natural or manufactured. .. tions or impregnating various limestone or sandstone-type proofing. as well as phalt and heavy liquid petroleum. primary screening test." contains the earliest deposits of ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ .(1) a class of amorphous black or dark dally dispersed asphalt hydrocarbons in crude petroleum. Bermudez. Early historical and bibli. 1. Inc. The most important of these for coatings ap- foundation mortars. asphalt content. although their Tigris and Euphrates rivers in Iraq. clays. or manjak. In Europe. such as the cal accounts tell of the use of asphalt in shipbuilding and pyrobitumens. harder materials that show no softening point.. Trinidad. grahamite. a dark brown to black has been a typical method for determining the purity of cementitious material in which the predominating constitu. asphalt in the mummification process." is where our word groups [5]: "mummy" is derived [4]. For our purposes. often without steam. The distillation concentrates the colloi- dally dispersed asphalt into the "still bottoms" or "re- 1Mameco International. IN THE UNITED STATES. solubility in carbon disulfide (more than 99%) and are rived from California crude oils in the late 19th century. sandstone. glassy. Cleveland. refined." For years. salts. or. of 85 to 92% purity. extensively in the eastern United States and gained a reputa- fers to the mixture of heavy hydrocarbons. Carlozzo 1 INTRODUCTION Most of this material was competing with foreign imports from the Lake Trinidad region on the Isle of Trinidad off the General Overview north coast of South America. etc. and found in asphalts.

minimize water penetration (pond liners. There has been a growing concern with the toxicity of ter-gas tars. They are variable in pitches. seepage control for ings have been used to protect metal from the effects of levees and dams. Coatings for this application have included coal tar epoxies and coal tar resinous systems. The roofing industry. The result has been that trade sales and light industrial coatings have moved away from coal tar 3. Recently. asphalts and other bitumens have become increasingly Given the severe penalties associated with contamination of groundwater. petroleum asphalts are gen- were consumed by the road-paving industries with 20% used erally used. rusting. Coal tars and their products are not adhesion to metal parts. as sound deadening on sheet metal and binding other bitumi- 2. where asphalt coatings are used ex. water-gas tars. Today. . wood. or other organic materials. highly condensed bitumens found in coal tars. cost associated with the use of an expensive binder is offset by the large replacement costs involved. where bituminous coat. Resi- used in these coatings have generally been the coal tars and dues are distilled to produce asphalt." The "free carbon" ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . the base bitumen forms an inter-penetrat- high temperatures through soft or liquid petroleum residues. coatings are fast becoming a sizable market. Industries Additional areas where bitumens have shown applicability considered are: as specialty coatings have included the areas of sealing soil to 1. and petroleum asphalts. Many years ago. with a higher softening point. ous barrier to groundwater and the effects of catastrophic rity and produce considerable amounts of bitumen. The solid bitumens and asphaltites of natural ori. wa. rials since the turn of the century. tems stable.16 PAINT AND COATING TESTING MANUAL Precipitation methods are also used to recover asphalt Specialty Paints and Coatings from raw lubricating oils. but are most frequently used have been the epoxides. The materials several specialty areas in the paint and coatings industry. is derived from the cross-linked epoxy network. coal carbonization tars. Coal tar. and ate or butyl benzyl phthalate are required to soften and electrical insulation. plasticizers such as di-octyl phthal- gin found their greatest consumption in lacquer. . bituminous coat- tent. 3. The thermoset resins 2. where the adhesive properties of as. In recent to prevent chipping from road debris.. the predominant included in the category of asphalt. bitumens have been important raw mate- 4. as well as the asphaltic hydrocarbons approximately intermediate in ease of working with a liquid material. chemical and moisture-resistant coatings for important as the cost of other natural and synthetic binders containment dikes are being used more and more in the has continued to escalate. in a large part. Today. where concrete and mortar Roof Coatings are waterproofed. The bitumens obtained from by-products in oil-cracking processes. These materials represent highly aromatic materials with epoxy resins. or other benzene insoluble matter. To use the harder bitumens such as asphaltites in roofing. but the scope and area of used for this purpose. and their pitches are derived from or its pitches. Some form of compatibilizer has also which the predominating constituents are bitumens ob.. On deep buried pipes or those set in concrete. by the industry of use. This de-asphalting operation uses Asphalt. oil-shale. many commercial phalt as binder is put to good use in roads. approximately 70% of all oil asphalts from highly aromatic products. roofing systems use some form of asphalt or chemically mod- www. paint. the paving industry is still the liquify the bitumen. and other bitumens have been used in propane or other low-boiling hydrocarbons. distinguishes coal ings have found extensive use. The final film hardness aromaticity between oil asphalts and the completely aro. coal tar. predominate use has been in the area of pipe coatings and high asphaltene asphalts as the precipitate. and hazardous waste containment) as well water and oxygen degradation. bitumen in use had been coal tar. a brown or black been used in these types of coatings. Their ability to act as adhesives chemical process industry. The latter are with rubbery materials to give flexible coatings with excellent devoid of free carbon. Most state and local regulations with excellent moisture vapor transmission (MVT) properties require the use of a containment wall around every storage continues to result in new and varied uses. from the processing of coal. Today. In roof coatings. "Cracked" asphalts are also petroleum derivatives. This was primarily due to the compatibility of these composition and may contain a certain amount of uncracked paraffinic material. petroleum asphalt ure- The types of asphaltic or bituminous coatings available can thanes and epoxides are available. liquid or semi-solid in consistency. ing network with a thermosetting resin to form an impervi- This procedure can take semi-asphaltic materials of low pu. with the hard. The trend has been to bituminous material. tensively to weatherproof buildings. These materials are modified tar from the asphaltites and oil asphalts.iran-mavad. matic. and their pitches. Natural and synthetic waxes are added specialty coatings has broadened considerably. The re. nous materials such as coal or lignite for pelletization. Aromatic processing oils have also been largest user of these materials. Oxidized or "blown" asphalts are obtained by blowing air at In pipe coatings. be classified. with the move away In the early 1960s. the sulting material is harder. The construction industries. tank that may potentially rupture and contaminate the water table. been necessary to make these lower aromatic-content sys- tained. the asphaltites and oil asphalts have tars. The paints and coatings industry. ASTM D 1079 defines tar as " . Gilsonite-based resinous coat- Coating Types ings have been widely used and. The paving industry. In automotive under-body rustproofing. petroleum. Variations are automotive under-body coatings. highly aromatic systems. years. although containment made by controlling the propane stream. depending on the chemical nature of the contained material. in use softer asphalts. The produced are the so-called asphaltic resins.

The solvent predominantly used today is mineral for reinforcement and modified with latex resins to obtain a spirits. and surface defects that are present on the old roof. Bentonite The water-in-oil emulsions are produced from finely pow- and attapulgite clays are then used to obtain the required dered clays. into a weatherproofing membrane. When physically of petroleum asphalt emulsions that use organophosphate- possible. available which offer greater detail in the area of emulsion lene. purpose. The solids repair damage to the roof and re-establish or maintain the of such coatings vary from 25 to 50% by weight. A final application flow properties and that which will subsequently dry or cure gives a reasonably water-tight monolithic appearance. These materials generally consist philosophy is to maintain the existing roof. This has led to the use of cellulose. or. These cut (solubilize) the asphalt. treated leafing-aluminum pastes. asphaltite. It is reported that some reduction process and composed of silicates and alumino. if weight considera. from 30 to 70% by weight. coating may be applied to act as an ultra-violet (UV) barrier lowed by the application of a reinforcing membrane. synthetic. Splits and thixotropes as well as various additives to result in a formula. A wide variety of bitumens plied may be a flood coat of the adhesive coating. colored roofing granules.2 kg) of the solvent-borne coatings are beginning to find their place in the smaller roofing granules can be used. fillers. They are applied in heavy applications tion viscosity is required. xy. these coatings are applied to hold the ings for this application have been solvent-borne aluminum reinforcing membranes together. and the aromatic naphthas. and blast-furnace slag recovered from the iron ore leafing grade of aluminum paste. The bituminous coating market. depending on the cure times smooth buttery emulsions are very stable and can be fibered required. pigmented bituminous coatings. which can act as dispersants for the water. glass fibers as a partial replacement for asbestos. early formulations used cumerone indene resin to improve silicates of lime [6]. usually not left this way. the cure times. After the repairs are complete. Dis- thixotropy. in the strictest quently coated with reflective topcoats to help control roof sense. bitumen paints in use today are asphalt vehicles made from ation and serves to improve the fire resistance. Asphalt emulsions consist of two types. fol. the current industry trend has been away these purposes. Their viscosity has generally been low with moderate levels of nificantly improved when these roofs are gravel surfaced. The application of an as.29 m 2) of roof is ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . These materials gel asphalt after evaporation of the water. there are still a significant number of man. The first are or naphthas. giving it more stability on storage. In general. weather-tight seal. The most petroleum asphalt cutbacks. For several years. and more detail in that section. alternatives to these tions are important. be considered coatings. Other materials. crushed stone. The bentonite clays form extremely The asphalt portion of these coatings usually consists of colloidal gelatinous mixtures and pastes with water and re- materials referred to as cutbacks. Although the last coat ap.. volatile solvents are varied to control dispersed in the asphalt external phase. The pigment used has generally been a granite. The oil-in-water emulsions are more terials have driven the products toward asbestos-free roofing widely used in the paving industry and will be discussed in materials. Asphalt emulsions can be left untop-coated. the major type of coat- in performance. Most commercial products are unmodi- Faster evaporating versions of these cutbacks have been used fied and yield a final coating possessing all the properties of a as primers for better substrate adhesion.91 kg) of aluminum paste per gallon of paint similar to those used on shingles. CHAPTER 2 . where a roofing kettle that Asphalt cutbacks and emulsions are the primary coating heats the materials up to 450~ (232~ to reach their applica. The later are oil-in-wa- thixotropy and reinforcement. but are fre- The preceding materials. The asphalt content varies technology [7-9]. This allows the coating to cover minor Here. Today. or additional gravel added. Roofing emulsions are predominately and removing old installations with asbestos-containing ma. the water is In these coatings. sufficiently hygroscopic to hold water and bring it into dis- tions. In the other. is typical in these coatings [IO]. and toward cold-applied systems. while they can.12]. volatile solvents present. of 40 to 80 rail thick. This requires the use of coatings whose purpose is to the aluminum. is the and thermal reflector. Additional www. A level of 2 lb (0. the solvents are either mineral spirits asphalt is dispersed in a water external phase. different types of coatings have been available for each of In some markets. Several basic construction of a modern built-up-roof (BUR).B I T U M I N O U S COATINGS 17 ified asphalt in their construction. From 400 to 600 lb (181 to 272 kg) of river-washed gravel With the recent increase in environmental legislation and per 100 ft2 (9.68 to 27. tar. including toluene. In one. current terborne versions [11. from the use of hot melt coatings. that is. Most of the solvent-based aluminum This graveled surface blocks harmful ultraviolet (UV) radi. the asphalt is usually modified with solvents. a reflective phalt or polymer-modified hot melt asphaltic material. used for restoration. been mineral spirits. While asbestos was long a preferred additive for called water-in-oil (W/O) emulsions. include a variety of small. persing agents of this type show some affinity for water or are ufacturers that continue to use asbestos in their formula. Weathering characteristics are sig. water-in-oil emulsions.iran-mavad. the hazards of working with ter (O/W) emulsions. Several books are generally use faster aromatic solvents. also available for this the leafing characteristics and act as an anti-bronzing agent. an increased awareness of health issues. with a flash point (tag closed cup) of 104~ (40~ degree of elasticity. cracks can be repaired by using these materials with either tion that can be applied at ambient temperatures with good fiberglass or polyester reinforcements. 50 to 60 lb (22. and pitch. The predominate solvent has common roof gravels are river-washed gravel. asphalt emulsions of various solids are is then an adhesive for these gravels. Specifically. are actually closer to adhesives top temperatures. nology which allows the manufacture of relatively stable wa- ciated with roof tear-offs and subsequent reroofing. persion in the asphalt. Various solvents are used to sult in asphalt dispersions of very small particle size. The phosphate passivates tive. being used in conjunction with new aluminum pigment tech- Due to weight limitations on existing roofs and costs asso. restoration instead of replacement is very cost effec. the roof is have been used. including asphalt.

where the asphalt is heated to melting before suspected mixtures (the Oliensis Spot Test and the character- application. and alkyds. The oil-in-water emulsions are formed from the action of a these have been incorporated into the Annual Book of ASTM chemical emulsifier. While quite expen. ways or parking lots. These scribed that were in common use in 1972.01 through 6. most road coating uses asphalt emulsions. either anionic. As their cost decreases.04 of the Annual Book of ASTM Stan- application. soften- The paving industry is probably the oldest using bitumen ing point and penetration are the two major tests routinely and its coatings. which uses block. One disadvantage of this sition.18 PAINT AND COATING TESTING MANUAL modification similar to other emulsion systems is also used in nature. sion in which the dispersed phase shows a definite charge. istics of bituminous samples dispersed in solvent). The anionic and cationic emulsifiers form an emul- these coatings. for these membranes. The most common Other types of bituminous coatings used in the paving substrate is poured or cast concrete or mortared "cinder industry include slurry seals and micro surfacing. In the home construction and repair Coal tar is not used in this application because the resulting industries. Once the coating has dried. These emulsions are said to "break" upon contact with a ter have recently been introduced. higher tech systems are beginning to be seen. sive. dards. These Paving sealers are used to protect new or old asphalt drive- types of coatings will be discussed elsewhere in this manual. They also can distinguish mix- tures of bitumens and their purity. yielding the exclusion of one phase from is used to passivate the aluminum [13]. In coating structural steel and steel reinforcement bars. Newer technologies to stabilize aluminum pigments in wa. sol. Asphalt sealers Waterproofing Membranes can also be used. Today. the other. ASTM Standards. Environmen. the waterborne bituminous aluminum market. their improved performance have The following test methods are used to differentiate one made them of interest. www. The bitumen of interest in these markets has predomi- nately been coal tar pitch and petroleum asphalts. or slow setting emulsions. available through ASTM for characterization of bituminous tion and purpose is similar to that of pipe coatings used for paints and coatings. cationic. or nonionic in Standards and will not be described in detail. break occurs when emulsions de- Other technologies exist that are nonbituminous in compo. water is no longer a prob- are usually pigmented with either titanium dioxide (TiO2) or lem. since by is referred to as chip and seal. and Bituminous Materials. walls." For years these solvent cut materials were used to ent bitumen classes. Among the tests are generally chemically stabilized emulsions. but they must be latex or polymer modified Bitumen-modified waterproofing membranes are used ex. aluminum pastes to give thermally reflective coatings. tensively in the construction industry. adhered to another. epoxides. stabilize due to water loss on drying. to improve solvent resistance. The emulsion described were the solubility of bitumens in carbon disulfide is prepared beforehand and mixed with aggregate on site and (CSa) to identify the purity of a bitumen sample. making it much easier than the use of hot were tests to determine the presence of asphalt and tar in mix paving. and latex or polymer-modified asphalts with fine aggregate filler roof decks of high-rise buildings is also a suitable candidate as a surface treatment for repair of minor damage to roads. As bitumens are consid- Coatings for Paving ered pseudo-plastic materials. several tests were de- Today.04 of the Annual Book of tal issues aside. Their composi. oil-in-water emulsions predominate. Waterproofing. These coatings include elastomeric acrylic latexes. the use of aromatic coal tars is slowly D 8 on Roofing. Many of these methods are familiar to the prevention of underground corrosion. perhaps they will be available for preferred because the coating formed does not re-emulsify. being replaced by safer soft petroleum asphalts. Viscosities at elevated temperatures are seal roads as well as coat aggregates for application to the also very important with several instruments and their meth- road surface. Also listed this application. is the possibility of re-emulsification in the early stages of vent and waterborne urethanes. In earlier editions of this manual. Hot asphalt is not required in definition only CS2 soluble matter is bitumen. The speed of break can be modified. new paving as well as to repair damaged or worn areas. these products are finding use in the automotive indus. These methods appear in Volume 4. The aromatic polyurethanes MATERIALS are frequently used for this purpose. Asphalt cutbacks have also been known as performed to identify differences within grades of the differ- "road oils. While much more expensive than bitumen-modified systems. The sealers are generally coal tar in nature due to good resistance to gas and oil. cinder block foundations and concrete footers are coating is too slippery. These cure. This section will catalogue several test methods currently coal tar epoxies have been extensively used. medium. The cationic versions are try. Tack coats consisting of asphalt commonly waterproofed with bitumen-modified polymeric cutbacks are also used when one layer of asphalt needs to be coatings. With anionic emulsifiers. In paving. Today. hot asphalt or cutback is used to prime ods listed. Their composition the coatings chemist as standard paint-related tests found in can be modified to conform to a particular steel coatings Volumes ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . yielding rapid.iran-mavad. Water- proofing membranes are generally composed of bitumen in I D E N T I F I C A T I O N OF B I T U M I N O U S an elastomeric polymer matrix. Several others are under the jurisdiction of Committee As in other markets. with no true melt point. Other types of coatings for rebar in the last five years have included fused epoxy powder coatings systems and polyethyl- Tests on Bituminous Materials ene dip coated systems. Chemically bound chrome charged aggregate." Prestressed concrete in the foundations. type of bitumen from another.

and Highly Cracked Petroleum Products D 1669-89 Method for Preparation of Test Panels for D 61-75 Test Method for Softening Point of Pitches Accelerated and Outdoor Weathering of (Cube-in-Water Method) Bituminous Materials D 450-78 Specification for Coal Tar Pitch Used in Roofing. and is highly recommended. nonprofit organization sponsored by members Roofing Bitumens Using the Parallel Plate of the petroleum asphalt industry. A large part of the manual is devoted to practical how-to information E 108-90 Method for Fire tests of Roof Coverings about how to use asphalt.iran-mavad. an D 4989-90 Test Method for the Apparent Viscosity Flow of international. and Waterproofing Accelerated and Outdoor Weathering of Bituminous Materials D 2318-86 Test Method for Quinoline-Insoluble (QI) Content of Tar and Pitch D 4798-88 Test Method for Accelerated Weathering Test Conditions and Procedures for Bituminous D 2319-76 Test Method for Softening Point of Pitch (Cube- Materials (Xenon-Arc Method) in-Air Method) www. Ditch. The Asphalt Institute. CHAPTER 2--BITUMINOUS COATINGS 19 On this note. D 1670-90 Test Method for Failure End Point in Dampproofing. Waterproofing. where ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . other organizations have tried to compile these tests for their members' use. also publishes a handbook Plastometer that has evolved over the past 50 years as the standard refer- ence work in the field of asphalt technology and construction. it is important to point out that each industry D 4799-88 Test Method for Accelerated Weathering Test that uses bitumens has tended to develop their own series of Conditions and Procedures for Bituminous common pertinent tests over the years. as well as comprehensive data on asphalt technology. In Method) addition to ASTM. Specifications and Test Methods for Asphalt D 71-84 Test Method for Relative Density of Solid Pitch and Asphalt General D 312-89 Specification for Asphalt Used in Roofing D 4-86 Test Method for Bitumen Content D 449-89 Specification for Asphalt Used in Dampproofing D 5-86 Test Method for Penetration of Bituminous and Waterproofing Materials D 1328-86 Test Method for Staining Properties of Asphalt D 36-86 Test Method for Softening Point of Bitumen (Ring and-Ball apparatus) D 1370-84 Test Method for Contact Compatibility Between Asphaltic Materials (Oliensis Test) D 70-82 Test Method for Specific Gravity and Density of Semi-Solid Bituminous Materials D 1856-79 Test Method for Recovery of Asphalt from Solution by Abson Method D 88-81 Test Method For Saybolt Viscosity D 2042-81 Test Method for Solubility of Asphalt Materials D 92-90 Test Method For Flash and Fire Points by in Trichloroethylene Cleveland Open Cup D 2521-76 Specification for Asphalt Used in Canal. Today most of the Materials (Fluorescent UV and Condensation pertinent tests have been incorporated as ASTM standards. and Bituminous Materials Specification and Test Methods for Coal Tar. D 95-83 Test Method for Water in Petroleum Products and Pond Lining and Bituminous Materials by Distillation D 3461-85 Test Method for Softening Point of Asphalts and D 140-88 Practice for Sampling Bituminous Materials Pitches (Mettler Cup-and-Ball Method) D 52%90 Test Method for Accelerated Weathering Test D 4402-87 Test Method for Viscosity Determinations of Conditions and Procedures for Bituminous Unfilled Asphalts Using the Brookfield Materials Thermosel Apparatus D 1079-87 Definitions of Terms Relating to Roofing. This reference book Materials cites both ASTM test methods and. E 96-90 Test Methods for Water Vapor Transmission of especially in the paving industry [14]. Ameri- E 102-81 Test Method for Saybolt Furol Viscosity of can Association of State Highway and Transportation Offi- Bituminous Materials at High Temperatures cials (AASHTO) counterparts to these methods. Pitches.

D 2369-90 Test Methods for Volatile Content of Coatings The following methods can all be found in Volumes 6. and Related Products Reflected Light and Determination of Mesophase in a Pitch D 1540-82 Test Method for Effect of Chemical Agents on Organic Finishes Used in the Transportation D 4715-87 Test Method for Coking Value of Tar and Pitch Industry (Alcan) D 1542-60 Test Method for Qualitative Detection of Rosin D 4746-87 Test Method for Determination of Quinoline in Varnishes Insoluble (QI) Content in Tar and Pitch by Pressure Filtration D 1640-83 Test Methods for Drying.01 through 6. Varnish.20 PAINT AND COATING TESTING MANUAL D 2320-87 Test Method for Density (Specific Gravity) of D 555-89 Guide for Testing Drying Oils Solid Pitch (Pycnometer Method) D 562-81 Test Method for Consistency of Paints Using the D 2415-66 Test Method for Ash in Coal Tar and Pitch Stormer Viscometer D 2416-84 Test Method for Coking Value of Tar and Pitch D 609-90 Practice for Preparation of Cold-Rolled Steel (Modified Conradson) Panels for Testing Paint.04 of the Annual Book of ASTM Standards. Curing. D 2370-82 Test Method for Tensile Properties of Organic Coatings Tests and Specifications B 117-90 Method of Salt Spray (Fog) Testing D 2832-83 Guide for Determining Volatile and Nonvolatile Content of Paint and Related Coatings D 522-88 Test Methods for Mandrel Bend Test of Attached Organic Coatings D 3170-87 Test Method for Chip Resistance of Coatings www. Varnish. Conversion Coatings. or Film Formation of Organic Coatings at Room D 4892-89 Test Method for Density of Solid Pitch (Helium Temperature Pycnometer Method) D 1644-88 Test Methods for Nonvolatile Content of D 4893-89 Test Method for Determination of Pitch Varnishes Volatility D 1654-79 Method for Evaluation of Painted or Coated D 5018-89 Test Method for Shear Viscosity of Coal Tar and Specimens Subjected to Corrosive Environments Petroleum Pitches D 1849-80 Test Method for Package Stability of Paint TESTS AND SPECIFICATIONS FOR COATINGS D 2243-90 Test Method for Freeze-Thaw Resistance of Water-Borne Paints General Tests for Coatings D 2247-87 Practice for Testing Water Resistance of Several of the test methods familiar to the industrial paints Coatings in 100% Relative Humidity and coatings chemist can also be used to characterize the performance and physical properties of bituminous coatings. D 4616-87 Test Method for Microscopical Analysis by ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . and Related Coating Products D 2569-89 Test Method for Distillation of Pitch D 610o85 Method for Evaluating Degree of Rusting on D 2764-81 Test Method for Dimethylformamide-Insoluble Painted Steel Surfaces (DMF-I) Content of Tar and Pitch D 662-85 Test Method for Evaluating Degree of Erosion of D 2962-71 Method for Calculating Volume-Temperature Exterior Paints Correction for Coal-Tar Pitches D 714-87 Method for Evaluating Degree of Blistering of D 3104-87 Test Method for Softening Point of Pitches Paints (Mettler Softening Point Method) D 1212-85 Test Methods for Measurement of Wet Film D 4072-81 Test Method for Toluene-Insoluble (TI) Content Thickness of Organic Coatings of Tar and Pitch D 1474-85 Test Methods for the Indentation Hardness of D 4312-89 Test Method for Toluene-Insoluble (TI) Content Organic Coatings of Tar and Pitch (Short Method) D 1475-90 Test Method for Density of Paint.

Dampproofing and Waterproofing D 1187-82 Test Method for Asphalt-Base Emulsions for Use as Protective Coatings for Metal D 1227-87 Specification for Emulsified Asphalt Used as a Protective Coating For Built-Up Roofing D 2939-78 Method for Testing Emulsified Bitumens Used as Protective Coatings D 2823-90 Specification for Asphalt Roof Coatings Clay Stabilized Emulsions D 2824-85 Specification for Aluminum-Pigmented Asphalt D 1227-87 Specification for Emulsified Asphalt Used as a Roof Coatings Protective Coating For Built-Up Roofing D 3805-85 Practice for Application of Aluminum-Pigmented D 2963-78 Test Method for Testing Flow Table Consistency Asphalt Roof Coating of Clay-Stabilized Asphalt Emulsions D 4479-85 Specification for Asphalt Roof Coatings-- D 3320-90 Specification for Emulsified Coal Tar Pitch Asbestos Free (Mineral Colloid Type) D 5076-90 Test Method for Measuring Voids in Roofing and Anionic Emulsions Waterproofing Membranes D 1227-87 Specification for Emulsified Asphalt Used as a Waterproofing Membranes Protective Coating For Built-Up Roofing D 41-85 Specification for Asphalt Primer Used in Non-Ionic Emulsions Roofing. CHAPTER 2--BITUMINOUS COATINGS 21 D 3359-90 Test Methods for Measuring Adhesion by Tape Paving Sealers Test D 3320-90 Specification for Emulsified Coal Tar Pitch (Mineral Colloid Type) D 3960-90 Practice for Determining Volatile Organic Compound (VOC) Content of Paints and Related D 3423-84 Practice for Application of Emulsified Coal Tar Coatings Pitch (Mineral Colloid Type) G 6-88 Test Method for Abrasion Resistance of Pipeline D 4866-88 Performance Specification for Coal Tar Pitch Coatings Emulsion Pavement Sealer Mix Formulations Containing Mineral Aggregates and Optional Polymeric Admixtures Solvent-Thinned or Cut-Back Coatings General Specialty Coatings D 255-70 Method for Steam Distillation of Bituminous D 41-85 Specification for Asphalt Primer Used in Roofing Protective Coatings and Waterproofing D 402-76 Test Method for Distillation of Cut-Back D 43-73 Specification for Creosote Primer Used in Asphaltic (Bituminous) Products Roofing.iran-mavad. Dampproofing and Waterproofing D 1227-87 Specification for Emulsified Asphalt Used as a D 43-73 Specification for Creosote Primer Used in Protective Coating For Built-Up Roofing ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . Dampproofing and Waterproofing D 529-90 Test Method for Accelerated Weathering Test D 1187-82 Specification for Asphalt-Base Emulsions for Use Conditions and Procedures for Bituminous as Protective Coatings for Metal Materials (Carbon-Arc Method) D 3105-90 Index of Methods for Testing Elastomeric and Emulsion Coatings Plastomeric Roofing and Waterproofing General Materials D 466-42 Method of Testing Films Deposited from Bituminous Emulsions Roof Coatings D 41-85 Specification for Asphalt Primer Used in Roofing D 529-90 Practice for Accelerated Weathering Test and Waterproofing Conditions and Procedures for Bituminous Materials (Carbon-Arc Method) D 43-73 Specification for Creosote Primer Used in Roofing. Dampproofing and Waterproofing Cationic Emulsions D 5076-90 Test Method for Measuring Voids in Roofing and D 1227-87 Specification for Emulsified Asphalt Used as a Waterproofing Membranes Protective Coating For Built-Up Roofing www.

a n d Waterproofing [4] Martin.. Ed.. Peche Vol. 1991. 1962. [9] Bennett. pp. Patent No. Roofing. New Orleans. Practical tions. 1991. Manual Series No.. Gordon and Chlorosulfonated Polyethylene used in Roofing Breach Science Publishers. Vol. H.L. E. B i t u m i n o u s coatings are still used extensively today.W. 2.. 1962... Aluminum Paint and Powder. nism or Reality. CONCLUSION McGraw-Hill Book Co. E. New York.. New York. Bishop. Asphalte.iran-mavad. 1988. Chemical Publish- tively inexpensive costs for m o s t b i t u m i n o u s materials. J. American Society for Synthetic Resins Testing and Materials. [13] Chapman.. [5] Barth. Volume 4. Chemical Publishing Company.J. New York. The Asphalt Insti- Breach Science Publishers.. "Aluminum Flake in Waterborne Coatings: Antago- still growing. pp. 18th REFERENCES Annual Higher Solids and Waterborne Coatings Symposium. and Wray. 18th Annual Higher Solids and Waterborne Coatings Symposium. p. J.. and Bituminous Materials. 285. p. Gordon and Breach Science Publishers. E. 1968..J. Philadelphia. U. E.. Teere.S. New York. M. Inc. New Orleans. 1. [1] Barth. 1962. O. 11. 471-558. Asphalt: Science and Technology. C. R. New York. 2nd ed. p. 1951. D 3468-90 Specification for Liquid-Applied N e o p r e n e a n d [3] Barth. M. D. New York. pp. 4 (MS-4). Gordon and [14] The Asphalt Handbook. The [8] Bennett. H. E.. con. 4.J. Asphalt: Science and Technology. u n d e r s t a n d i n g of the c h e m i s t r y a n d uses of b i t u m i n o u s coat. tinue to drive their use in m a n y diverse industrial applica. Asphalt: Science and Technology.P.22 PAINT AND COATING TESTING MANUAL Resin Modified Bituminous Coatings [2] Annual Book of ASTM Standards. Bishop. Vol.. I. Inc. 1986. New York. LA. 141-151. ings in i n d u s t r y a n d a realization that even several t h o u s a n d [10] Edwards.. Bukowski. Reinhold Publishing Corp. 1968... J.F. R. 100. ing Company. 1982. D.. LA. and Wulfinghoff. Waterproofing.565. New York. 64-69." ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . J. www. Practical waterproofing a n d adhesive properties. The p r e c e d i n g i n f o r m a t i o n will give the r e a d e r an Emulsions: Applications. and Wulfinghoff. J. "Aluminum Pigment Technology for Wa- terborne and Powder Coatings in the 1990's. Manual of Built-Up Roof Systems.L.. [6] Griffin. years after t h e i r discovery a n d first use the usage of these [11] Williams.. 7-9.. R. pp. Bitumen. Section 4.. tute. [7] Barth. Emulsions: Materials and Equipment. Gordon and Breach Science Publishers. F. b i t u m i n o u s r a w m a t e r i a l s as an engineering r a w m a t e r i a l is [12] Besold. Asphalt: Science and Technology. 1955.. 1962." Proceedings.J. 3.716. 1989. coupled with the rela.

Generally. Building 230. compatibility. three hydroxyl. compatibility with other resins. which contain three hydroxyl groups. As butyryl increases. Increasing the viscosity of a particular ester by increas- quent processing steps are required in the manufacture of ing the molecular weight slightly lowers its solubility and cellulose esters including filtration. TN 37662. printing inks. but does not affect hardness free-flowing powder in most instances. organic proved with increased molecular weight and viscosity. The esterification of the cellulose with the acids and anhydrides occurs quite rapidly and if allowed to proceed FACTORS A F F E C T I N G P E R F O R M A N C E OF to completion. Because the triester is of little practical use. grease resistance. Unlike cellulose nitrate. and various fabric coatings. although other physi. Cellulose acetate is the sim- 5%. cellulose esters are included value are produced. At plest cellulose ester since only acetic acid and acetic anhy- higher hydroxyl levels. solubility. Both types of coatings can be applied over a monly used organic cellulose ester for coating applications. flexibil- bility and compatibility with other coating polymers. G. but are not suited for coating applica. which affected by the chemical composition and the viscosity of the affects various properties of the cellulose ester such as solu- ester. Eastman Chemical Com. The final product is a dry. Table 1 shows the types of cellulose esters commer. If two different linking capability with amino and isocyanate resins. as either a modifying resin to impart a specific property to the tions. Some areas in which cellulose esters are used include produced because of the acetylbutyryl combinations that are automotive OEM and refinish. higher levels decrease resultant product is referred to as a mixed ester. either separately or in ited but improves as the hydroxyl increases. APPLICATIONS F O R CELLULOSE E S T E R S IN COATINGS T Y P E S OF CELLULOSE E S T E R S Protective and decorative coatings for various substrates Several types of cellulose esters are commercially available. and screening. precipitation. variety of substrates ranging from paper products to automo- and there is an almost infinite number of types that can be biles. several characteristics are also affected. toughness and flexibility are im- cal forms can be produced. providing cross- dride are used in the esterification reaction. In many such coatings. esters of cellulose are low in flammability and present no handling hazards. ings. ity. cable lacquers. solubility in lower molecular weight alcohols occurs. properties of the ester as well as coatings formulated with In addition to esterification and ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . reactivity increases.astm. 1995 Cellulose Esters by L. mixed cellulose esters are cellulose acetate butyrate and cel- The viscosity of cellulose esters also influences physical lulose acetate propionate. the Copyright9 1995 by ASTMInternational www. Curtis 1 CELLULOSE ESTERS ARE THE reaction product of combining possible. Cellulose acetate butyrate is the most com. coating or to function as the primary film-forming resin in cially available. aircraft coat- ~Principal Technical Representative. hardness. diluent tolerance. wood furniture coatings. Below 1% For the production of coating-grade cellulose esters. can be formulated either as air-dry lacquer systems or as including cellulose acetate. drying. cellulose acetate propionate. Lower butyryl levels are associated with decreased water tolerance. lea- ther coatings. plastic coatings. and moisture resistance are increased. hydrolysis is Performance properties of cellulose acetate buytrate are necessary to restore desired levels of hydroxyl content. Examples of moisture resistance due to increased hydrophilicity. As the hydroxyl content of cellulose acetate butyrate varies. and density. the ever. found on the anhydroglucose repeating units of a cellulose molecule. and converting or curing types often referred to as cross-linked cellulose acetate butyrate. forms a triester with each of the an- CELLULOSE E S T E R S IN COATINGS hydroglucose units. and increased melting P R O D U C T I O N OF CELLULOSE E S T E R S range. MNL17-EB/Jun. washing. solubility in common coatings type solvents is lim- organic acids and anhydrides are used. esters are used in coatings to impart such properties as rapid- 23 www. At levels around combination with each other. dewatering. How- organic acids and anhydrides are used simultaneously. Hydroxyl content and molecular weight possibili- organic acids and acid anhydrides with the hydroxyl groups ties expand this range even further. Other esters of lesser commercial enamels. Cellulose pany. Kingsport. in noncross-linking systems. several subse- them.

.7 to 44..5 .5 0.00 2. . and the p r i m a r y yellowness index and p r i m a r y haze v i s c o s i t y t e s t i n g ..001% acidity calculated as HCL c o m e t e r is u s e d i n m o s t v i s c o s i t y d e t e r m i n a t i o n s w i t h r e s u l t s r e p o r t e d in ASTM seconds.5 . . 36. . 4..1%) containing 0. 81 a n c e w i t h A S T M T e s t M e t h o d s f o r C e l l u l o s e A c e t a t e s (D 871).com ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ .5 .00 39... ~ Celhtlose Acetate CA-394-608 60.8 130-140 CAB-551-0. 230-250 Cellulose Acetate Propionate CAP-482-0.8 .2 0.0 1.0 . Cellulose ester 20~ 20 ~ 20 b 15c 20~ l(F Acetoned 70 80 . CFor cellulose acetate having 42.8 150-160 ~ASTMTest Method for Cellulose Acetate Proprionate and Cellulose Acetate Butyrate (Formula A) (D 817) and Test Methods for Viscosity of Cellulose Derivatives by Ball-Drop Method (D 1343). . ...5 230-250 CA-398-10 10. . values are s i m u l t a n e o u s l y displayed by t h e i n s t r u m e n t .0 1.2 to 40. .7 135-150 CAB-551-0. 9 Methylene chlorideg . a n d t h e a n a l y s i s is p e r f o r m e d w i t h a G a r d n e r m i n e t h e p o s s i b l e p r e s e n c e o f i n s o l u b l e gel p a r t i c l e s . . aFor cellulose acetate having a max of 40. M o d e l XL-385 c o l o r i m e t e r . fibers. d r y i n g . .785 to 0. 51... .0 1.5 230-250 CA-398-6 6.3 155-165 CAB-381-0. . esters having less than about 40% acetyl and more than about 8% propionyl or butyryl. 52. .1 230-240 CAB-321-0.01 0.0 1. % Hydroxyl. . . 37..0 1..2 0.0 240-260 CA-398-3 3. . ..b % Propionyl.. Typical Solution Densities. . w h i c h c o v e r s c o l o r a n d h a z e .5 --.. Viscosity aAcetone (99. .171-158 15.8 . . . o n d a r y haze.. c o m b i n e d acetyl. . l o s e D e r i v a t i v e s b y B a l l .0 -. . .50 13. 0. m o i s t u r e 0.0 4. 46.00 29. cellulose acetate propionate.. 8 8.~ s Acetyl. A p r e c i s i o n H o e p p l e r vis. . .-. .3 to 0.7% acetyl and for most of the haze.0~ and less than ball d r o p o r f a l l i n g ball p r i n c i p l e .0 0. .8 . C e l l u l o s e a c e t a t e is t e s t e d b y t h e m a n u f a c t u r e r i n a c c o r d .8 185-195 CAB-500-5 5. 96/94 .. .0 1.. u s i n g s o l u t i o n s p r e p a r e d for tion.5 127-142 CAB-553-0.5 . . 36. . 52. p i g m e n t c o n t r o l .0 . T h e m a t e r i a l t o b e t e s t e d is a d d e d t o 16 oz. .5 46.. .5% water and under 0. .5 to 42.5% acetyl and for most mixed C o a t i n g s m a n u f a c t u r e r s u s u a l l y r e s t r i c t t h e i r t e s t i n g t o vis. o r o t h e r c o n t a m i n a n t s .. 3. .0 188-210 Cellulose Acetate Butyrate CAB. 50. 72 76. Ethyl alcohoF 8 -.-. solubility a n d a p p e a r a n c e .00 13. .. a n d sec- reference standard.90 3.4 -+ 0.00 4. Color and Haze m i n a t i o n a r e s h o w n in T a b l e 2.. % Melting Range. or 30 denatured ethyl a c c o r d a n c e w i t h A S T M T e s t M e t h o d s f o r V i s c o s i t y o f Cellu.23 0.24 PAINT AND COATING TESTING MANUAL TABLE l .1 0.. 3A. acetate. .10 18. .S o l u t i o n s for viscosity measurement of cellulose and polishability.. 31.3 165-175 CAB-381-0.86 1. . .0 1.8 175-185 CAB-381-20 20. .8 195-205 CAB-381-20BP 16...0 1. . TABLE 2 .00 13.2 1.0 165-175 CAB-531-1 1.5 .10 13. 2. h y d r o x y l c o n t e n t .0 -. F o r m u l a t i o n s for viscosity deter.iran-mavad. v i s c o s i t y c o n t r o l . 80 . b a s e d o n p l a t i n u m / c o b a l t s t a n d a r d s . and cellulose acetate butyrate.1 0. .5 -.5 0. m m .00 39. alcohol may be used.00 15. .00 39.5 . .25 1. . .6 42. 16. % Butyryl. f r e e acidity.5 . film t o u g h n e s s . .. . Type Viscosity. TESTING OF CELLULOSE ACETATE Acetone/water. . i n t r i n s i c v i s c o s i t y . g per mL at 25~ h e a t stability. .. .00 39. 230-250 CA-398-30 30.s q u a r e cell. .3 175-185 CAB-381-20BP 2.5 45.5 --. T h e s o l u t i o n is t r a n s f e r r e d t o a s p e c i a l 33- T h e s o l u b i l i t y a n d a p p e a r a n c e t e s t is p e r f o r m e d t o d e t e r . . .20 14.3 155-165 CAB-381-2 2.. .8 188-210 CAP-504-0. . L i g h t p a s s e s t h r o u g h t h e s o l u - flock. particularly good for esters containing more than 40% acetyl. . 3.00 39.. . Methyl alcoholf ..0 .0 . V i s c o s i t y m e a s u r e m e n t o f c e l l u l o s e a c e t a t e is c a r r i e d o u t in eEthyl alcohol (95% by volume). 5. 37. a n d color a n d bFor cellulose acetate having 40.5 . Sec- (454 g) F r e n c h s q u a r e b o t t l e s a n d v i s u a l l y c o m p a r e d t o a o n d a r y c o l o r .5 .8% acetyl and for most of the commercial cellulose acetate propionate and acetate butyrates. .4 0. .6 188-210 CAP-482-20 20. .-. . fMethyl alcohol (sp gr 20/20~ = 0.20 2.8 .40 2.85 0.0 1. a n d solution viscosity.3% ethyl alcohol. cosity of the ester.50 2.-.86 1.24 content.795). The same solutions used for ASTM viscosity and solubility and a p p e a r a n c e testing are normally used for color and haze Solubility and Appearance m e a s u r e m e n t s . b a s e d on scattered light f r o m a m o n o d i s p e r s e www. 36.. bASTM D 817. 1.0 1. 37.C o m m e r c i a l cellulose esters (Eastman Chemical Company). . commercial cellulose acetate propionate and acetate butyrates.. . Formulas 2B. sulfur or sulfate content.20 0. . .D r o p M e t h o d (D 1343) b a s e d o n t h e gMethylene chloride having a boiling range of 39.01 2..0 .

The test methods are the P R O P I O N A T E A N D CELLULOSE ACETATE same as those used in the testing of cellulose acetate. free acidity. tyl content. are calculated. apparent ace- ASTM haze are predicted from the secondary values. Usually color and haze and viscosity are the only tests T E S T I N G OF CELLULOSE ACETATE run by the coatings manufacturer. and vis- cosity. CHAPTER 3--CELLULOSE ESTERS 25 polystyrene latex suspension. color and haze. BUTYRATE ASTM Test Method for Cellulose Acetate Propionate and Cellulose Acetate Butyrate (D 817) contains the following www. hydroxyl content. heat stability. APHA color and tests: acetyl and propionyl or butyryl contents. sulfur content. ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ .iran-mavad. moisture content.

Dou- CH~--O--OC--Ra I ble bond position is also important because conjugated bonds. The printing 1. has the highest expected growth rate sults in separation into glycerol and the fatty acid. of double bond unsaturation controls the drying rate. the faster the drying or polymerization of the oil. The ture higher the degree of unsaturation or iodine number (see he- low). are more susceptible to autooxidation [4]. 2 In 1987 there were 81 000 metric tons ( . In simple of unsaturation present. cal composition are given in Table 2.and nonfood fats and oils national market. the drying oils listed in Table 3 contain less than about Chemically. 1995 Drying Oils by Joseph V. This reaction is reversible Such consumption represents about 3% of the total nonfood and when the oils are heated they can transesterify with Ra. Hydrolysis of drying oils re- relatively very small. petroleum-derived oligomeric and polymeric binders Rheineck and Austin [2] defined the classes as given in Table carried in a variety of media or in a neat manner. and other end use markets. Often times the terms most widely distributed saturated fatty acids found in drying "fats" and "oils" are used interchangeably within the industry.140 Nondrying < 125 that is usually a few years out of date. Drying oils used in iodine values.1 7 8 Glycerol Fatty Acid million pounds) of drying oils consumed in the United States RxCOOCH2--CH(OOCRx)--CH2OOCRx + 3 H20 [1]. CH2--O--OC--R c Physical characteristics of some typical commercial drying Generalized Triglyceride oils are given in Table 4. Depart- ment of Commerce. The degree glycerides of long chain fatty acids with the generalized struc. With an expected annual average growth rate of 2. semidrying. The is an indication of fatty-acid chain molecule weight. 1513 Brentwood Oil Class Iodine Value Road. linoleum. acid. Triglyceride or Drying Oil Water there should have been 92 000 metric tons consumed in 1992. over the above five-year period. though polymerization phenomenon. which terms.. but one princi- try's need for drying oils is in an overall decline along with ple way is to divide them into drying. The oils are particularly character- where R a. temperature are referred to as fats. except for fish oil. whose growth is about the same as the population relatively low levels and they do not participate in drying or growth of the United States. 26 www. products solid at room ponent content of selected drying oils was given in Table 3. WV 25314-2307. Rb. and core oils. thetic.S. plasticizers. Consolidated Copyright9 1995 by ASTMInternational www. Drying oils also contain saturated mature with relatively little growth expected. and Saponification Number. The paint and coating indus. nondrying (an oxymoron term) oils in accordance with their ants. paints and coatings are being replaced with oil-free. The nature of this market results in information Semidrying 125. fats and oils market and about 1% of the combined food and Rb. drying oil consumption. unsaturated 10% of any particular saturated fatty acid residue. The unsaturated-com- Usually in the fats and oils industry. where R x is anyone of R a. syn. K o l e s k e I D R Y I N G OILS REPRESENT A SMALL PORTION of the huge fats and HOCH2--CH(OH)--CH2OH + 3 RxCOOH oils industry. Drying oils can be classified in many ways. and R~ are the same or different and represent ized by their Iodine Value. oils. drying oils are water-insoluble. which is a measure of unsaturation content.astm. seal. and products liquid at Stearic (18-carbon) and palmitic (16-carbon) acids are the room temperature are termed oils. but these are usually present at industry. Although such classification has been rather arbitrary.iran-mavad. Charleston. The industry is very an intramolecular sense. are of vegetable origin. which contains 29% palmitic Drying oils. which is a measure of the amount the hydrocarbon chain residues of fatty acids. MNL17-EB/Jun. Inc. ink market is the only one expected to have small growth in The main fatty acids found in drying oils and their chemi- the area of drying oils. such as binders for ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . ISenior Consultant. Rb. or R~. Drying oil > 140 2Information about this industry is developed by the U. which is the term used to described two carbon-car- CH--O--OC--Rb I bon double bonds separated by one carbon-carbon single bond. this means that most oils are mixed triglycerides. Selected triglycerides are produced by the condensation reaction that property requirement ranges or minimum values for various occurs between a glycerol molecule and three fatty acid mole- cules: TABLE 1--Classification of drying oils by iodine value. Within this glycerides of fatty acids. and Rc capable of changing their positions in an inter.6%. Except for cottonseed oil.

. it has low residual u n s a t u r a t i o n after materials. . . a n d un- is as a source of fatty acids that are used in the m a n u f a c t u r e saponifiable c o m p o u n d s such as higher alcohols. . . . . Linseed oil. . . This relatively high viscosity a n d re- oil. Tall Oil Fatty Acids 3 41 46 . .D R Y I N G OILS 27 TABLE 2--Main unsaturated fatty acids found in drying oils. . The oil differs f r o m the o t h e r oils in t h a t it is p l a n t Soja hispida. of sulfate or Kraft pulping of pine a n d certain o t h e r soft- Cottonseed oil is o b t a i n e d from the p l a n t Gossypium w o o d s such as spruce a n d h e m l o c k that are p u l p e d in Scandi- malvaceae. P o l y m e r i z e d linseed oils of F i s h oils are the only nonvegetable oils in the drying oil various acid values a n d viscosities are available. I n addi- c o n j u g a t e d d o u b l e b o n d s of this acid result in r a p i d drying tion to 16 a n d 18-carbon fatty acid residues.3] (remainder of oils is essentially all saturated fatty acid residues). . The ASTM meth. . Because of its low the m o s t i m p o r t a n t m e m b e r s of this class of coating r a w linolenic acid content. 87 Linseed 52 16 22 . fish oils c o n t a i n TABLE 3--Weight percentage of major unsaturated fatty acid residues in selected drying oils [2. . chi- tions including alkali-refined. It is often u s e d as an alternative or supple- cation p r o p e r t i e s are d e l i n e a t e d in Table 5. . Crude tall oil is an a p p r o x i m a t e l y 50/40/10 u s e d as a n oil in the p a i n t a n d coating industry. . . Soybean 9 51 25 . It has a wide variety of uses o t h e r t h a n as a drying oil. C H A P T E R 4 . Fatty Carbon Double Acid Atoms Bonds Structural Formula Linolenic 18 3 HOOC(CH2)7CH=CHCHECH~CHCH2CH=CHCH2CH 3 Linoleic 18 2 HOOC(CH2)7CH~CHCH2CH~CH(CH2)4CH3 Oleic 18 1 HOOC(CH2)7CH~---CH(CH2)TCH3 Eleostearic 18 3 HOOC(CH2)7CH~CHCH~--~-CHCH~---CH(CH2)aCH3 Licanic 18 3 HOOC(CH2)ECH(O)(CH2)4CH--~CHCH--~CHCH--~CH(CH2)3CH3 Ricinoleic 18 1 HOOC(CH2)7CH~---CHCH2CH(OH)(CH2)5CH 3 drying oils a n d the ASTM m e t h o d t h a t contains o t h e r specifi. Tung 3 4 8 80 . a n d m u oil.-. .. . linoleic triglycerides. w h i c h i m p a r t s a fractive index oil is r a p i d drying a n d is used in varnishes a n d short drying time. . . . cure a n d very g o o d anti-yellowing characteristics. . . Safflower 1 75 13 . this oil is widely u s e d as a reactive oil c o n t a i n on the average only a single d o u b l e b o n d a n d for plasticizer a n d as an acid scavenger. No. . . aThere is wide variation in reported values for sunflower oil. Unsaturated Fatty Acid Drying Oil Linolenic Linoleic Oleic Eleostearic Licanic Ricinoleic Cottonseed . . . . . This oil is also k n o w n as w o o d oil. . . . Sunfloweff 2 75-52 34-14 . Castor . . Both epoxidized soy- this r e a s o n c a s t o r oil is essentially a n o n d r y i n g oil. . The p r o d u c t is o b t a i n e d as the m a j o r b y p r o d u c t tics.c u r e coating systems that are initi- m o v e d as w a t e r to form a double b o n d conjugate to the previ- a t e d with free radicals. . ricinoleic acid residue. . . . . . It is m a r k e t e d in a n u m b e r of ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . ods cited in Table 5 c o n t a i n references to o t h e r ASTM meth. n a w o o d oil. . o t h e r h y d r o c a r b o n s . w h i c h is o b t a i n e d f r o m seed of the flax p l a n t Tung oil is o b t a i n e d from seeds of the trees Aleurites fordii Linum usitatissimum. Oiticica . . Its m a i n use by weight mixture of fatty acids. . . a n d the three a significant a m o u n t of s a t u r a t e d fatty a c i d residues. Safflower oil is o b t a i n e d from seed of the p l a n t Carthamus ods a p p r o p r i a t e for o b t a i n i n g the i n d i c a t e d p r o p e r t i e s a n d tinctorius.. it is not a as d e h y d r a t e d castor oil. 40 24 . . blown. The resultant p r o d u c t is k n o w n Although tall oil is classified as a drying oil. due to its large percentages of linolenic a n d alkyds w h e r e w a t e r resistance is of p r i n c i p a l i m p o r t a n c e .iran-mavad. is the m o s t c o m m o n a n d widely used a n d Aleurites montana. a n d p o l y m e r i z e d linseed oil [2]. www. w h i c h has g o o d drying characteris- triglyceride. . r o s i n acids. Although the fatty a c i d residues in this I n a n epoxidized form. These acrylated oils have been used as c o m p o n e n t s in r a d i a t i o n . Chinese w o o d oil. ously existing double bond. It has a high degree of u n s a t u r a t i o n . . They are p r i n c i p a l l y o b t a i n e d from m e n h a d e n (Alosa Oiticica oil is o b t a i n e d f r o m the nuts of the tree Licana m e n h a d e n ) . . . Its m a i n use is in the p r e p a r a t i o n of m a d e u p of a very high p e r c e n t a g e of the hydroxyl-containing alkyds. No. . waxes a n d of alkyd resins. . The following drying oils are t w e e n those of linseed a n d s o y b e a n oils. . Although it is a drying oil. . characteristics. . 6 . a n d sterols. . boiled. This s e m i d r y i n g oil has drying characteristics be- for o t h e r p e r t i n e n t properties. It has a very high licanic acid content. m e n t to tung oil. . .. Castor oil is o b t a i n e d from b e a n s of the p l a n t Ricinus S o y b e a n oil is o b t a i n e d from the seeds of the widely g r o w n communis. .-. cottonseed oil is s e l d o m navian countries. These oils are s e m i d r y i n g in n a t u r e a n d c o n t a i n rigida. class. acid-refined.. 3 7 . . . 78 -. it can b e b e a n a n d linseed oil have b e e n r e a c t e d with acrylic acid to converted into a drying oil b y a d e h y d r a t i o n process in w h i c h form p r o d u c t s with residual acrylate functionality a n d m a r k - its hydroxyl group a n d a n a d j a c e n t h y d r o g e n a t o m are re. . edly higher viscosity. .

drying oils u n d e r g o in the drying or p o l y m e r i z a t i o n process ASTM D 1640 S t a n d a r d Test Methods for Drying.478 Oiticica 0. deals with d e t e r m i n a t i o n of f o r m e d w h e n oxygen was r e a c t e d with the methyl ester of the gel t i m e of oiticiica a n d tung oil. weight cleavage p r o d u c t s including c a r b o n dioxide a n d w a t e r Reaction with oxygen is the m o s t i m p o r t a n t r e a c t i o n that are formed. Value.920 135 190 2. W h e n Although r a w drying oils are used in coating formulations. they are not widely used in the coatings' cules results in a crosslinked p o l y m e r i c network. In this step. A different r e a c t i o n p a t h was involved when lin.931 135 190 5.938 163 I89-195 5. Value. F a r m e r a n d coworkers [9] were times.28 PAINT AND COATING TESTING MANUAL TABLE 4--Physical characteristics of some typical drying oils [5]. a n d oxidation o r blow.5/25.5 1.1) a p a r t i c u l a r p r o c e d u r e first to describe the m e c h a n i s m of a u t o o x i d a t i o n w h e r e i n is specified for drying oils. Specific Iodine Acid Gravity.957-0. the drying oil is exposed to air.473 Tall oil .0 1.474 Soybean 0. Polymer.915 170 192 0. Currently. a n d polymerization.0 D 1392 Soybean.933-0. t i m e required for the oil to congeal a r o u n d glass r o d relative peroxides a n d one cyclic d i p e r o x i d e were formed. During the r e a c t i o n scheme.-. dry-through. d r i e r addition.517 30 to 40% of a r a c h i d o n i c (20-carbon with four double bonds). a n d by w o r k results. h e a t d a n t s p r e s e n t in the system. p o l y m e r i z a t i o n of the u n s a t u r a t i o n and a crosslinked net- m e r i z i n g with vinyl m o n o m e r s such as styrene. dry-to- with h y d r o p e r o x i d e s a n d o t h e r peroxides that are f o r m e d in touch. i n d u s t r y with use often d i c t a t e d b y relative price of linseed Solidification o r p o l y m e r i z a t i o n o f a d r y i n g oil such as a n d s o y b e a n oils. Because of chain p r o p a g a t i o n in w h i c h free radicals react with oxygen to the presence of acid residues with high degrees of u n s a t u r a . low m o l e c u l a r epoxidation. dehydration. by copoly. raw 0. print-free.iran-mavad.c a r b o n chain along with f o r m a t i o n of vola. which" involves heating the oil in a test tube a n d observing the oleic esters were autooxidized since two m o n o h y d r o . dry-hard. These reactions can be stages a n d rates of film f o r m a t i o n in the drying o r curing of catalyzed with metallic salts such as cobalt n a p t h e n a t e (see organic coatings that are to be used at r o o m t e m p e r a t u r e .481 Fish 0. ASTM Oil 25/25~ Wijs Value max Method Castor.926 180 190 3.2 1.917-0.967 150 190 4. Drying oils are form free radicals. there is very little p o l y m e r i z a t i o n that involves heating an oil to selectively ad. ization is initiated by r e a c t i o n of oxygen with an u n s a t u r a t e d c l u p a n o d o n i c (22-carbon with five double bonds).0 -.926-0.922 145 192 2. a n d nisinic fatty acid residue a n d free radical f o r m a t i o n followed by (24-carbon with five d o u b l e bonds) acid residues.0 D 12 www.0 1.0 1. Availability of m u l t i p l e d o u b l e b o n d s in s o m e of the mole- ble oils.927 140-150 189-195 3. refined 0.465 Dehydrated castor 0. Curing.0 1. Specific Iodine Refractive Gravity. [6. Fish oils do r e p r e s e n t a source of tion of various free radicals that exist in the r e a c t i o n mass. the very long chain fatty acids that are not p r e s e n t in vegeta. raw 0. Tung 0. The p o l y m e r i z a t i o n is t e r m i n a t e d by c o m b i n a - to residual u n s a t u r a t i o n .0-195.0 1.0 D 601 Safflower 0. Oil 25.0 1.510 Safflower 0. raw 0..926-0.972 (min) 135 (min) None 8. linseed oil can be t h o u g h t of in the following m a n n e r . S u c h process.937 125-145 188-195 6 D 961 Linseed. This s i m p l e test method.917 135 192 2. next chapter) that p r o m o t e free radical f o r m a t i o n by r e a c t i o n I n c l u d e d are m e t h o d s for d e t e r m i n i n g tack-free. ASTM S t a n d a r d Test M e t h o d for they found that four different m o n o h y d r o p e r o x i d e s were Gel Time of Drying Oils (D 1955). This is vance m o l e c u l a r weight a n d viscosity.925 158 187 4. followed by a p e r i o d in which there is a m a r k e d oxygen ing w h e r e i n air is b u b b l e d into h e a t e d oil a n d oxygen is t a k e n u p t a k e a n d an a p p e a r a n c e of peroxides w h i c h d e c o m p o s e to up with a resultant m o l e c u l a r weight increase. there is an i n d u c t i o n p e r i o d the oils are often further p r o c e s s e d before use. d u r i n g w h i c h oxygen is a b s o r b e d a n d it c o n s u m e s antioxi- ing includes alkali refining.931 177 (min) 189.922-0. o r F i l m F o r m a t i o n of Organic Coatings at R o o m Tempera- age of the c a r b o n . The free radicals then initate a n a d d i t i o n also modified b y r e a c t i o n with maleic anhydride.5~ Wijs Value Value 25~ Cottonseed 0. can be used for o t h e r oils TABLE 5--Selected property requirements for drying oils (indicated ASTM method has other requirements).0 D 234 Oiticica 0. Saponification Acid Index. fish oils have a strong t e n d e n c y to yellow after cure due tion sites [10].0 4. oleic acid.961 83-88 176-184 2. cleav. 133 196 194. to a s t a n d a r d of k n o w n ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ .0 D 960 Dehydrated castor 0. In one instance (Section 7.919 105 192 1. a p p a r e n t change in physical or chemical properties.473 Sunflower 0. 7].485 Linseed 0.5. Oxidation can result in trans i s o m e r formation.3 D 1462 Tung. form peroxy radicals w h i c h in t u r n react with o t h e r u n s a t u r a - tion.924 126 (min) 189-195 0.0 1. a n d dry-to r e c o a t the oxidation process [8]. Saponification Value. ture has p r o c e d u r e s r e c o m m e n d e d for d e t e r m i n a t i o n of the tile byproducts.

A. E. p. Journal of the Chemical Society. "Oils for Organic Coatings. F. E. 1959. W. Nov.R.. p. New York. Ed. Sward.. R.. Eds. No. [3] Gunstone. "Drying Oils... Long. ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . Fuller. [2] Rheineck. ASTM S t a n d a r d G u i d e for Testing Drying Oils (D 555) Kreiger. Vol. 1962. R.. J. 10. The Chemistry of Organic Film Formers. 62. Philadelphia. Ltd. G. 130-150. H. 2nd Ed. 13th ed. A. pp. cal Technology. Chapman and Hall. New [9] Farmer. York. Vol. 1979. is an overall guide to selection a n d use of p r o c e d u r e s for [5] Gallagher. and Austin. J. R. 8. istics. C.. and Sutton. 36. www. D. Chemistry and Biochemistry of Fatty Acids and [10] Cowan. Vol. p. Philadelphia. testing drying oils that are c o m m o n l y u s e d in coatings.. 99. No. 3. REFERENCES [7] Fox. CHAPTER 4 ." Paint Testing Manual. 1.. Myers and J. SRI International.. 1972. [4] Solomon. 3d ed. "Drying Oils. [6] Harwood. O.. 1968.G. book. Ed. G.iran-mavad. Societies for Paint Technology." Kirk-Othmer Encyclopedia of Chemi- Their Glycerides. 53. 1965. 1967. Unit Three. L. Inc. S. 1977. Chemical Reviews.. Federation of [1] "Fats and Oils Industry Overview.." Federation Series on Coatings Technology.." Chemical Economics Hand. [8] Russell. D.. F. Marcel Dekker. Film Forming Compositions. p. R..D R Y I N G OILS 29 t h a t have c o n j u g a t e d double b o n d or o t h e r gelling character. 1946. 111. The American Society for Testing and Materials. Journal of Chemical Education. 2. D. C. A. 1990.. Vol..

dry by oxidation according to the following steps: Naturally occurring antioxidants may be considered as 1. naphthenates. counteracting the effects of the antioxidants. Peroxide formation. This chapter concentrates primarily Catalysts Potassium. synthetic acids. as well as adverse effects on film hard- The induction period occurs because most drying oils con- ness and resistance properties. cerium. The applications of metallic soaps in coatings include their zinc. Flatting agents Zinc. tin. 2. use as driers. oils. Tallates. FLATTING AGENTS mercury phenyl acetates. bismuth.5] 1. sium and lithium soaps have limited water solubility. 620 Airport Copyright9 1995 by ASTMInternational www. be a key factor accelerating oxygen absorption in the film. on metallic soaps used as driers. lithium. but driers accelerate the process by means of the following mechanisms T H E O R Y OF O X I D A T I V E D R Y I N G A N D [1. and calcium laurates. octoates. bodying and flatting applications is ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . neodecanoates. Their agents linoleates advantages include fairly high efficiency and ease of incorpo- ration. the effects of which must be over- organic wax derivatives [2]. Acceleration of oxygen absorption. pigment-suspending agents in solvent-based coatings. These steps will occur in the absence of driers. precipi. Induction period.5]: F U N C T I O N OF D R I E R S [1. zinc. An overview of metallic soap applications is presented in Table I.iran-mavad. 3. calcium Stearates. rare earth. catalysts. negative catalysts for oxidation. metals and monobasic carboxylic acids containing from 7 to Applications Metals Acids 22 carbon atoms. It is generally accepted that vehicles based on unsaturated 3. particular interest to the coatings industry. lead. Free radicals promote cross-linking. Acceleration of peroxide decomposition. aluminum octoates.rosinates vanadium. catalysts. MNL17-EB/Jun. back to the divalent form. as the absorption continues. tin. phenyl oleates. butyl oxides linoleate pulp were at one time widely used as bodying and Bodying Aluminum. naphthenates. The multivalent nature of the drier metal is considered to 4. cadmium. 5. Oxygen is then Zinc and calcium stearates are used on occasion as flatting absorbed from the air at the unsaturated sites on the oil additives in clear solvent-based coatings. molecules at the unsaturated sites. they have been replaced to a considerable extent by the bentonite clay and tain natural antioxidants. sulfates. biocides. This action accelerates the process 30 www. Schnall I METALLICSOAPSARE COMPOUNDSof alkaline metals or heavy TABLE l--Coatings applications of metallic soaps. although a brief review of cobalt. includ. forms peroxides. iron. linoleates. Peroxide decomposition to free radicals. Octoates. octoates. NC metal then releases the oxygen to the film and is converted 27514. The water-insoluble metallic soaps are of Driers Cobalt. octoates. 1995 Driers and Metallic Soaps by Marvin J. The 1Coatings consultant. calcium Stearates ing sensitivity to variations in the formulation and in the processing of paints. tated and fumed silicas are now more commonly used for this These peroxides then decompose to form free radicals which purpose. Proprietary. However. whereas driers are positive 2. molecule. manganese. lead carbonates. Chapel Hill. resulting in dried films. tin. calcium. calcium. Naphthenates. including alkyd resins and oleoresinous varnishes. aluminum and flatting agents. copper. Zinc stearate is also used to facilitate sanding of act as catalysts to promote cross-linking of the oil or resin primers and sealers for wood furniture finishing [2]. they have a number of deficiencies. As a result. stearates M E T A L L I C S O A P S AS B O D Y I N G A N D Biocides Copper.. potassium. Suite 304. barium. stabilizers. zinc. manganese neodecanoates Stabilizers Barium. Oxygen absorption. Removal of natural antioxidants. come before the drying process can begin. The drier metal is initially in a divalent state and is converted to a trivalent state by the presence of oxygen in the film. zirconium. Aluminum stearates. bodying agents. although potas. zinc. However. laurates.astm. and.

Some typical examples are shown in Table 3. which is responsible for oxidative film drying. Tallates Naphthenates Tallates Lin-All Mooney Chemical. They are usually while manganese affects both surface and through drying. creased recently with the advent of high-solids alkyd resins. film hardness with these resins but may at times adversely division of OMG affect viscosity stability and promote gelation. particularly carbon black and organic red pig- quently employed auxiliary drier. CHAPTER 5 . Another class of metallic compounds closely related to The auxiliary driers are seldom used alone. Alter- native drier compounds. In the process of formulating these coatings. Rare earth and cerium driers are recommended occasionally for im- proved through drying and as oxidation catalysts for baking.D R I E R S AND METALLIC SOAPS 31 of oxygen ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . proprietary cobalt and manganese drier com- pounds are available that are purported to be more suitable DESCRIPTION OF DRIER METALS for water-based coatings. active drier metals. vehicles to which they are added. Octoates (2-ethyl hexanoates) division of OMG Synthetic acids Water dispersible Hydro-Cem Mooney Chemical. Zinc is used primarily rather than immediately. Their functions compounds designed to prevent loss of drying efficiency of are to increase the efficiency of the active drier metals and to paints on aging resulting from the adsorption of driers by increase film hardness. A more recent development is the synthetic acid Troykyd WD Troy Corp. are currently being offered [6]. Calcicat Ultra adhesives The synthetic acid and neodecanoate driers can be prepared Aquacat Ultra adhesives at higher metal concentrations than the other types and are Magnacat Ultra adhesives gradually replacing the older acids. followed by the naphthenates and division of OMG Nuocure Huls America the octoates. which is proprietary but closely related to the octoates. and peroxide de. However. lead was the most fre. ionic surfactants to naphthenate or synthetic acid driers. D E S C R I P T I O N OF D R I E R ACIDS division of OMG Octoate Huls America To perform their function. Solubility is achieved by division of OMG reacting the drier metals with organic acids to form metallic soaps. including both organics and propri- Cobalt and manganese. Octoate Hex-Cem Mooney Chemical. Trade names of the various commercial drier types avail- The metals that act as catalysts to promote oxidation and able are listed in Table 2. In the past. NuXtra Huls America Troymax Troy Corp. rosinates. the first types developed. driers should be soluble in the Neodecanoate Ten-Cem Mooney Chemical. In this manner. Linoleates division of OMG Nuodex Huls America Rosinates Troykyd Troy Corp. they replace the for improved film hardness and to prevent wrinkling of thick drier metals that have been adsorbed by the pigments. pigments. peroxide formation. Neodecanoates division of OMG Chronologically.. are the most etary metallic complexes. Calcium and zirconium driers are most vehicle so that the metals are available over a period of time frequently used as lead replacements. The most commonly employed acids are as follows: Naphthenate Nap-All Mooney Chemical. Water-dispersible driers may be prepared by adding non- composition. TABLE 2--Commercial drier types [3].iran-mavad. Iron driers are used mainly to improve drying of baking systems when their dark color can be tolerated. Type of Drier Trade Name Supplier Aluminum compounds are being recommended to improve Synthetic acid Cem-All Mooney Chemical. films. but it is presently out of ments. recommended in combination with conventional metallic Vanadium has been mentioned in the literature as an active soap driers for improved drying efficiency. drier but is seldom used in coating formulations. Zircat Ultra adhesives www. These are combination with cobalt and/or manganese. but rather in driers are loss of dry inhibitors or "feeder" driers. and tallates were Hydro-Cure Mooney Chemical. They function by dissolving gradually into the coating favor due to toxicity. Interest in aluminum compounds as auxiliary driers has in. Cobalt promotes surface drying of films. particularly cobalt. type. the linoleates. which may be used in driers are indicated below: Cobalt Manganese t Active Lead Calcium 1 MISCELLANEOUS DRIERS Vanadium Zirconium Zinc Auxiliary Restrictions on solvent emissions have stimulated the de- Iron velopment of both higher-solids and water-reducible coat- Rare Earth ings. chemists Cerium are experiencing difficulty obtaining satisfactory drying Aluminum properties with the conventional metallic soap driers.

This drier as supplied) functions by moving a Teflon stylus over the applied film in a circular path. 7. when the thumb is applied to it in a specified manner and 3. 12.9 KPa no longer marks the film as determined by photographic standards shown in ASTM (10% calcium drier required) = (0. through-dry times may he noted.2% cal. nonvolatile. T E S T I N G OF D R Y I N G E F F I C I E N C Y Trade Name Company Composition The procedures used to determine the stages of film forma- Activ-8 R.5 or 6. Print-Free-Time--army duck or cheesecloth applied at a Calcium metal required = 0. 3. (b) fine calcium carbonate All are lead-free metal complexes except for the last item [3].iran-mavad. 6. extender dropped on the film can be completely removed by blowing gently and wiping with a cloth or brush. Set-To-Touch-Time--no transfer of the coating upon but have been replaced by lead-free compounds based pri. Tack-Free-Times--a specified type of paper or aluminum foil will no longer adhere to the film when applied under D R I E R L E V E L S IN COATINGS specific conditions. without development of lifting or loss of adhesion of the per 1000 g of paint: first coat. (0. 6.32 PAINT AND COATING TESTING MANUAL TABLE 3--Alternate drier compounds.6 g calcium metal) = (6 g Test Method for Print Resistance of Lacquers (D 2091) [4]. a number of me- drier as supplied) chanical drying time recorders are available. shown in Table 6.10-phenanthroline Co.12 g metal/g drier) Gardner Improved Circular Drying Time Recorder [7]. In a 1000-g paint formulation. Cobalt drier used is 12% metal by ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . through 6H (hardest) are pushed into the film. Required for optimum drying: 0. The instrument (12% cobalt drier required) = (0. and common vehicles are indicated in Table 5. Dry-Through-Time--the film is not distorted or detached 2. be removed by blowing lightly. Coatings at Room Temperature (D 1640) [4]. are complex usually specified but are subject to agreement between the purchaser and the seller.T. The methods used to determine the various stages of drying thereby maintaining satisfactory drying on prolonged stor. Cobalt metal required = 0. marily on less soluble forms of cobalt and other drier metals. Test Method for Hardness of Organic Coatings by Pendulum Huls America Nuact Cobalt 254 Damping Tests (D 4366-87)--either a Konig or a Persoz Huls America Nuact NOPB Pendulum Hardness Tester is employed with the time. there are 300 g of vehicle ished lightly with a soft cloth. lightly touching the film with the finger. Dry-To-Touch-Time--the film no longer adheres to the fin- Drier requirements for coatings are usually expressed in ger when pressed firmly and does not rub up when rubbed terms of percent drier metal based on oxidizable vehicle non. Dust-Free-Time--(a) cotton fibers dropped on the film can Commercially available feeder driers are listed in Table 4.25 g referred to most frequently in recent literature is the Byk- (0. 4. 2. or Film Formation of Organic Chemicals Inc. Vanderbilt 1. The pattern left in the film by the stylus after a The optimum levels of drier metal required will vary de- complete revolution is observed. were used formerly 1. or 24-h. surface dry. in Huls America Nuact Paste (lead-based) seconds.0005 x 300 g = 0. The drying conditions. Recorders are available pending on the type of resin system employed and the condi- which make complete revolutions in 1.05% cobalt plus 0.002 x 300 g = 0. Calcium drier used is 10% metal by weight. and the Hydroxy Ten-Cem division of OMG Cobalt hardest pencil that will not penetrate the film is noted.6 g pressure of 3. With coatings Drymax Huls America 2. Test Method for Film Hardness by Pencil Test (D 3363)--a Mooney Chemical.15 g cobalt metal) = (1. may be summarized as follows: age. including litharge. it is recommended that the paint Nutra ADR 10% Huls America proprietary metal complex samples age overnight following the drier additions before Nutra LTD 18% Huls America proprietary metal drying tests. tion during the drying of coatings are described in ASTM Test Dri-RX Mooney 2. lightly. volatile content. 4.15 g 8. rotated through a 90~ angle. Dry-To-Recoat--a second coat or top coat can be applied cium (percent metal based on vehicle nonvolatile).2'-dipyridyl containing metallic driers. noted for the swing amplitude of the pendulum to www. Troy Corporation Troykyd Perma Dry 2. Dry-Hard-Time--a thumb print applied under specified Assume: conditions is completely removed from the film when pol- 1.10 g metal/g drier) In addition to the above subjective tests. Development of film hardness is also an important crite- rion of drier efficiency. Typical metal concentrations for a number of the use of a plastic template. set-to-touch. Tests [4] used to measure hardness TABLE 4--Commercial feeder driers. Hex-Cem LFD series of pencils varying in lead hardness from 6B (softest) division of OMG Mooney Chemical. With tions of drying.2'-dipyridyl Methods for Drying. Curing. Lead compounds. include: Company Trade Name 1. A typical calculation is as follows [1]: 5.

02 0.08 0.I-0.04-0.02-0.3 0.2-0.3 decrease b y a specified degree w h e n set into oscillation on S P E C I F I C A T I O N S F O R LIQUID P A I N T the d r i e d film.2-0.02-0.2 Linseed oil 0.15 Epoxy Ester 0. www.3 Alkyd-oil house paint 0.5-0.3 0.1-0. TABLE 6--Standard drying conditions.2 0.03 0..2 Short off alkyd air-dry 0.3 0. I-0.9 0. Liquid Paint Driers (D 600) involve the following classes: tion is m e a s u r e d with the a i d of a microscope.04-0.1-0.03 0. Class F Other unidentified acids a n d acid blends.06 0.08 0.02-0.04-0.15-0.03 0.1-0.06 0.1 Medium oil alkyd-bake 0.05 0. a n d G a r d n e r .10-Phenantbroline 30% Long oil alkyd-air dry 0.02-0.06 0. The typical p r o p e r t i e s of Lighting No direct sunlight the driers listed a n d r e p r o d u c e d in Table 7 include p e r c e n t Applicators Doctor blades m e t a l concentration.3 0.05-0.06 0.06 0.1-0.03-0.1 High solids alkyd 0.1-0.06 0. percent metal based on vehicle nonvolatile. Cobalt Manganese Zirconium Calcium Zinc 1.04 0. p e r c e n t nonvolatile content.02-0.2 0.D R I E R S AND METALLIC SOAPS 33 TABLE 5--Typical drier recommendations. converted to either a K n o o p or a Pfund H a r d n e s s N u m b e r Class B N a p h t h e n i c acids in p e t r o l e u m spirits.02-0.1 0.1-0.1-0.H o l d t viscosity.3 dry 0.1-0.04-0.5-0. plus additives to m a k e the Condition Typical Value driers w a t e r dispersible.1-0.2 0.1-0.iran-mavad.4 Water-based alkyds 0.05-0.1-0.4 0. DRIER 3.04 0.06 0. The d e p t h is Class A 2-ethyl hexanoic acids in p e t r o l e u m spirits.2-0.02-0.1-0.2 0.04-0. Class E Any of the above.06 ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ .06 0.3 0.1-0.04 0. Ambient temperature 23 + 2~ Relative humidity 50 + 5% A c o m p r e h e n s i v e table of liquid p a i n t driers of the above Film thickness (dry) 12.2 Acrylic Modified alkyd 0.1-0. Test Methods for Indentation Hardness of Organic Coatings (D 1474)--either a K n o o p or a Pfund I n d e n t e r is a p p l i e d to Drier specifications as described in ASTM Specification for a film u n d e r a specified loading.04-0.2 0.04-0.05 0.04 0.04-0.3 0.2 Medium oil alkyd-air 0.1-0.9 0. a n d the d e p t h of indenta.06 0.1 Oleoresinous varnish 0.2'-Dipyridyl.04-0.3 0.2 0.04-0.04-0.04 0.02-0.1 0.1 0.3 driers) 0.08 0.06 0.1-0.1-0.1-0.2 0.02-0.1-0.04 0. Class C N e o d e c a n o i c acids in p e t r o l e u m spirits.2 0.04-0.1-0.06 0.1-0.02-0.03-0.1-0.1-0.3 (water dispersible 0. 2.2 0.0 I-0.3 0.03 0.2 0.1-0.2-0.2 0.3 0. CHAPTER 5 . using the equations in the standard. Class D Tall oil fatty acids in p e t r o l e u m spirits.06 0.04 0.15 0.3 0.1-0.06 0. G a r d n e r Color.02-0.05-0.2 Chain-stopped alkyd 0.03 O.04-0.5 to 45 ~m Substrate Clean glass classes is given in ASTM D 600 [4].3 0.04 0. specific Coating viscosity Close to normal application gravity.06 0.02 0.5 Oil-modified urethane 0.02-0.04 0.2 Vinyltoluene alkyd 0.02-0.04-0.15-0.1-0.02-0.1 0.04-0.2 0.

1 57 0.918 0.34 PAINT AND COATING TESTING MANUAL TABLE 7--Typical requirements of liquid paint driers.090 1.1 50 0. T a b l e 8 . This m e t h o d is a p p l i c a - m i x e d w i t h 19 v o l u m e s of r a w l i n s e e d oil.2 90 1. T h e excess of E D T A is t h e n t i t r a t e d to a n e n d p o i n t 4.888 . Stability--The d r i e r s a m p l e is s t o r e d for 7 days at 25~ P a i n t D r i e r s by O x i d i m e t r i c D e t e r m i n a t i o n (D 3970)]. hydrate).970 11 T C Calcium 4.9 5. T h e E D T A m e t h o d is u s e d for m o s t d r i e r d o n o t fit i n t o this scale a n d are r e p o r t e d descriptively.958 --.984 . o u t l i n e s t h e A S T M d e s i g n a t i o n s ..030 7-8 K A Cerium 5.1 76 0. Blue A D Cobalt 5.8 24.9 5.9 6.1 50 0.100 1. w h i l e M e t h o d B specifies 150~ for 10 m i n . a Metal Typical Specific Colorb Gardner G-H Viscosity Concentration. a n u m b e r of C h e m i c a l analysis is u s e d to d e t e r m i n e t h e m e t a l c o n t e n t of driers. n o w i n d i c a t e d d i r e c t l y in stokes. 2.9 6.945 0.873 0.9 6.1 67 0.20~ a n d 50~ a n d e x a m i n e d for i n d i c a t i o n s of clotting. a n d c h e m i c a l tests.9 6.2 75 1.2 61 1. % Nonvolative Gravity. %.920 Red/brown A B Manganese ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . n o t to d r i e r blends.2 66 1.9 5.2 67 1.8 12..393 8 H A Manganese 5. T h e p h y s i c a l tests i n c l u d e : This involves c o m p a r i n g t h e t i m e of travel of b u b b l e s in t u b e s of t h e s a m p l e v e r s u s G a r d n e r .960 Blue/purple I F Cobalt 5.905 0.9 4.9 4.888 0.965 17 D Continued T E S T I N G OF LIQUID P A I N T D R I E R S 6..9 6. a n d t i t r a t i n g so- gelation. w h i c h e m p l o y s t h e G a r d n e r n u m e r i c a l c o l o r scale..9 6. a n d a n o x i d i m e t r i c 24-h period. Red/purple A E Cobalt 5.014 1.930 Brown A F Iron 8.985 Brown A F Iron 11. Miscibility with Oil--One v o l u m e of t h e d r i e r s a m p l e is d e t e r m i n e d b y a specified i n d i c a t o r .1 78 0.902 0..1 66 0.9 4.000 1..1 45 0.H o l d t s t a n d a r d tubes.930 0.9 4..956 Purple C E Cobalt 4.930 Dark brown A B Iron 5.8 24.9 8.9 4.9 6.937 10 D B Calcium 4.1 72 0.890 0.1 50 0.8 24.2 80 1. Appearance--observations for clarity a n d c l e a n n e s s in ac.9 6.140 10 A F Lead 35.2 81 1.9 4.925 .9 6. m e t a l s (Table 8). Color--according to A S T M D 1544.1 46 0.856 .1 60 0.1 70 0.900 0.008 1.125 1.1 65 1.9 6. m a n g a n e s e .1 60 0.912 0.9 5. H o w e v e r .110 3 A B Lead 23. www.8 24.1 67 0. i n c l u d i n g cobalt.9 10.1 70 0.905 0. i n d i c a t o r s .-.350 1.125 10 A2 E Lead 23. cates t h e c o n v e r s i o n f r o m letters to stokes.1 50 0.9 6. 3 A A Calcium 4.2 65 0. nickel.918 9 B E Calcium 3.900 0.948 6 N F Calcium 7.1 50 0. 2 A D Calcium 3.900 Blue/purple A A Cobalt 11. o r p r e c i p i t a t i o n .8 12.1 74 0.9 6. 7.2 67 1.950 0. Max Min Max D 1544) D 1545) A Calcium 3.. T h e s t a n d a r d s w e r e f o r m e r l y d e s i g n a t e d by l e t t e r b u t are c o r d a n c e w i t h A S T M Test M e t h o d for Clarity a n d Clean.2 71 1.958 Blue/violet A F Cobalt 11.932 0.1 30 0.1 63 0.. M e t h o d solvents a n d t h e n t r e a t e d w i t h a n excess of s t a n d a r d E D T A A o r B.912 5 C B Calcium 3.1 60 0. Brown A A Lead 23.1 85 0. A table in D 1545 indi- ness of P a i n t L i q u i d s (D 2090).040 Blue/violet J A Iron 5.1 66 0.8 24. 2 B D Lead 23. Viscosity--According to A S T M T e s t M e t h o d for V i s c o s i t y lines t h e test p r o c e d u r e s e m p l o y e d .1 70 0.9 9.926 -.960 0. T h e l i q u i d d r i e r is d i s s o l v e d o r d i g e s t e d in 3. 1.2 65 1.970 Blue/purple B C Cobalt 11.iran-mavad. T h e m i x t u r e is ble to single m e t a l d r i e r s only. Drying power--As d e s c r i b e d in t h e s e c t i o n e n t i t l e d "Test- ing of D r y i n g Efficiency.080 1.1 71 0. 8 A B Cerium 5.9 6. l u t i o n s for analysis o f d r i e r m e t a l s by E D T A titration. M e t h o d A involves h e a t i n g s a m p l e s at 105~ for s o l u t i o n ( d i s o d i u m salt of e t h y l e n e d i a m i n e t e t r a c e t i c a c i d di- 10 m i n ..060 Blue/purple J B Cobalt 5.930 8 G E Calcium 5. a n d r a r e earth.150 7 A F Lead 23.068 .884 3 A F Calcium 4.9 6. l i q u i d p a i n t driers.936 4 B F Calcium 5.. 17 A1 A Cobalt 5.875 0.8 12. An E D T A o b s e r v e d for a n y signs of s e p a r a t i o n o r c l o u d i n g o v e r a m e t h o d is n o t yet a v a i l a b l e for c e r i u m .922 0.100 . Nonvolatile Content--According to A S T M D 1644.894 0..990 Dark brown M F Iron 5.160 11 B C Lead 23.870 0.8 12." A S T M Test M e t h o d for L i q u i d P a i n t D r i e r s (D 564) [4] out.125 1.850 0.8 36. i n c l u d i n g b o t h p h y s i c a l o f T r a n s p a r e n t L i q u i d b y B u b b l e T i m e M e t h o d (D 1545). d e t e r m i n a t i o n is specified [ASTM Test M e t h o d for C e r i u m in 5.. 5 B F Calcium 9.884 C .8 24. 25/25~ (Test Method (Test Method Class Metal Min Max Matter.960 5 N F Calcium 3.

8 12. 1987. W a s h i n g t o n .630 0.100 3 B A Zirconium 5.976 . "Use of Metallic Driers in Organic Coatings.942 0..855 0.074 3 A A Zirconium 23.9 6. "Drying Time. ..8 18..090 1.1 50 0. [1] Hurley. 752." Handbook The Next Generation of Driers. 33-34. as well as minor amounts of other rare earth metals.1 35 0.876 .240 -. 2 A E Zirconium 5.965 Brown E F Manganese 5. 2-11 Inc.977 -.2 90 1." Handbook of Coatings Additives.2 56 0.130 7 Z B Zinc 7. Paint India. 4 A E Zirconmm 11.9 10.070 1.9 9.8 12. %.1 31 0. Philadelphia. . Marcel Dek. A. 485-509.911 .855 0.032 .9 6.9 8. "Multi-Metallic Complexes: [2] Schnall.9 10.992 4 A A Zirconium 17. pp.03.. ASTM Titrating Metal Method Solvent Indicator Solution Cobalt D 2373 Glacial acetic acid PANa Cupric sulfate Lead D 2374 Glacial acetic acid PAN~ Cupric sulfate Manganese D 2375 Toluene-ethanol E r i o c h r o m e hlack-T Zinc chloride Calcium or zinc D 2613 Toluene-ethanol E r i o c h r o m e black-T Zinc chloride Iron D 3804 Isopropanol E r i o c h r o m e black-T Zinc chloride Zirc D 3969 HSO-HO Xylenol orange B i s m u t h nitrate Vanadium D 3988 Isopropanol-HCL Xylenol orange Zinc chloride Total rare earth D 3989 Isopropanol-HCL Xylenol orange Zinc chloride a1(2-Pyridylazo)-2-Naphthenol. April 1986... 16 C A Nickel 9.. 1990. Section 9.8 12. Yellow/green C B Rare earth 3.855 10 A C Rare earth 5. Inc.1 69 0.1 42 0.. aThe metal content represents total rare earth metals calculated as cerium. .9 8. Inc.880 6 E A Rare earth 11. REFERENCES [4] Annual Book of ASTM Standards.980 1.. 2 A F Zinc 7.8 18.. ker.1 55 0. New York.240 1. 3. Raw Material Index.M e t a l analysis by EDTA titration.960 9 A B Zinc 9.9 8..D R I E R S AND METALLIC SOAPS 35 TABLE 7--Continued Metal Typical Specific Colorb Gardner G-H Viscosity Concentration. 11 D E Zinc 7.." Byk-Gardner.2 55 0. Books 6. .2 80 1. 59. Chemical Specialties Section. . Max Min Max D 1544) D 1545) C Manganese 5.020 4 A F Zirconmm 5.9 8.9 6. Chap. www.-.1 70 ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ ." pounds.960 0.8 12. .. % Nonvolative Gravity.044 8 L D Zinc 7. Silver Springs. DC. 8 A5 A Zinc 7.1 23 0.9 6.1 72 0. April 1978 edition per Gardner Method D 1544. 13.. pp.9 6.915 0.. S.8 18.975 1.840 0. [5] Godbole. MD. .130 4 Z F Zirconium 23..2 55 0. 10 A D Manganese 5. Vol.260 6 J "Source: National Paint and Coatings Association.1 70 0. National Paint & Coatings Association. New York. 1987. March 1989.880 0.8 12..963 7 C F Zinc 15.860 0.1 50 0. 101-108.2 46 0.946 .9 5. American Society for Testing a n d Materials.008 .068 1. Chemical Specialties Section. [6] Belletiere.1 75 0.9 6.9 6.906 6 G A Zinc 17. 28-25.870 .8 12.020 1. 2 J C Zirconium 5.8 24.950 1.942 0.9 8." Journal of Coatings Technology.972 Brown E E Manganese 4.870 1.2 55 1. of Coatings Additives...870 2 A5 F Zirconium 11.864 . 1990.. Green A A Rare earth a 5. [7] Instrument Catalogue.-.. Brown E E Manganese 5. M. Marcel Dekker.2 75 1.044 . F Zirconium 17.8 16.9 4. R.1 30 0. a n d Mahoney. as observed by the unaided eye.. M. S e p t e m b e r 1987.864 . . pp. 2 A5 C Zirconium 11. V. 25/25~ (Test Method (Test Method Class Metal Min Max Matter. pp. . .2 77 1.1 42 0. Chap. [3] Raw Materials Index. .1 60 0.. TABLE 8 .8 24.2 55 . pp.1 35 0.1 80 0. D. CHAPTER 5 .9 6. J.864 2 A A Zirconium 11. but the drier contains cerium and lanthanum.020 18 H F Manganese 11.iran-mavad.9 6.2 80 1.020 18 A F Manganese 8.. a n d pp. blf off the scale..1 28 0. 22-27. "Metal Soaps: Drier Stabilizers a n d Related Com.1 30 0.01 a n d 6. No.9 6.1 70 1. "Thickeners for Solvent-Based Coatings.-. ~'Only one drier was listed in this category.2 93 1. ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ .Part 3: Synthetic Materials www.

and (2) ther- interlayer for laminated safety glass. The acrylics gained widespread market ac. latexes) have become one of the major binder types in use in craft canopies.) to form a cross-linked network. the acrylic monomers are emulsified and then polymerized as try in the form of acrylic solution polymers. --(--CH2--C--)-- A wide range of properties can be built into an acrylic I I coatings binder by careful selection of the type and level of C ~0 C=0 the acrylic monomers used.astm. There are two types of acrylic solu- methyl and ethyl acrylate in the United States [1]. fac- Dr. % Acrylic solution polymers (often referred to as acrylic res- ins) are generally copolymers of acrylate and methacrylate Polymethacrylate esters prepared by direct solution polymerization in a solvent Methyl 9000 4 that has a solubility parameter similar to that of the polymer. 39 www.. Rohm and Haas Co. MNL17-EB/Jun. they are also used to for- ering and aging. 100% solid-grade versions became popular since that are polyrnerized by additional polymerization. in this chapter. Research ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . the coatings industry today. The advan- advent of World War II. aerosol lacquers. the use of acrylic emul- polymers is primarily due to their resistance to hydrolysis sions in industrial applications is expanding at the expense of and their lack of absorption of ultraviolet (UV) light. Some of the principal applications for Interest in acrylic technology dates back to the 1920s when acrylic solution coatings include automotive finishing. with quality architectural coatings. epoxy. Since it could be formed easily and had excellent Acrylic emulsion polymers (often referred to as acrylic optical properties. tages and disadvantages of each are discussed in detail later able as a tough. In fact. thereby having greater control I I over the formulation ingredients. The good weathering resistance of acrylic mulate industrial coatings. degradation. typically stabilized by surfactants. which harden commercial use of an acrylic polymer was as an adhesive-like simply by loss of solvent through evaporation. Shortly afterwards.. and resistance to weath. Acrylic resins are typically Polyacrylates supplied at about 30 to 50% solids by weight.22 = k g / c m 2. transparency. Architectural Coatings Re. 727 Norristown NOTE:Psi + 14. To form an emulsion polymer. which contain functional groups that profile use of an acrylic began in 1936 with the introduction react with another functional material (i. and clear coatings for a Otto Haas. his associate. Road. PolymerTypes Tensile Strength.. of thermoplastic. The droplets are acrylic emulsions. The coatings manufacturer is then able to dissolve the solid-grade acrylic H CH 3 in a wide range of solvents. Spring House. methacrylate sheet became invalu. While acrylic emulsions are generally associated ties as color stability. with viscosities Methyl 1000 750 Ethyl 33 1800 1Group leader and research fellow. PA 19477. general-purpose pig- rylate esters from ethylene. and farm implement coatings. OR OR Coatings for a wide range of applications can therefore be An acrylate A methacrylate custom designed. 1995 Acrylic Polymers as Coatings 6 Binders by John M. Some of the important properties I t for several acrylic homopolymers are shown in Table 1 [3]. Acrylic technology soon expanded into the coatings indus. (Reprinted with permissionof Modem Paint and Coatings. followed later by small droplets in a continuous water phase. Otto Rohm developed a practical process for making ac. psi Elongation. and gun turrets [2]. transparent methacrylate sheet. bomber noses.) . In comprised chiefly of esters of acrylic and methacrylic acid later years. With the isocyanate. WHICHARE USED as coatings binders. and usually no solvent is ceptance as coatings binders due to such outstanding proper. mented coatings. the high- energy portion of the light spectrum most responsible for TABLE 1--Properties of polymethacrylates and polyacrylates [3]. as well as ketones and esters. usually they reduced the cost and safety concerns associated with using a free radical mechanism: shipping resins containing high solvent levels. present.. Probably the highest mosetting polymers. are ranging from a few hundred to a few thousand centipoise. tary aircraft. etc. tory. (--CH2--C Copyright9 1995 by ASTM International www. Ethyl 5000 7 Butyl 1000 230 Typical solvents include aromatics such as toluene and xy- lene. weather-resistant glazing material for mili.iran-mavad. melamine. Copyright1973). established the first commercial production of multitude of substrates. the transparent plastic was used for air. The first tion polymers: (1) thermoplastic polymers. Friel I ACRYLICPOLYMERS. Butyl 3 2000 search.

Copyright 1957. This is particularly true for polymer hardness as deter- mined by the glass transition temperature (Tg) of the 0 0. They do not discolor powdered C18 / / " " metals.1" "" Acrylic resins generally make excellent grind media for dispersing pigments.40 PAINT AND COATING TESTING MANUAL solvent-based systems because of the industry's need to con. at Tg. 1.21 . free volume accounts for 11% of a polymer's total volume [7]./ .97 monomers that make up the homopolymer (only one mono- 0. and colors. a desired level of performance. sion manufacturers have made great strides in improving the Since thermoplastic acrylics are not cross-linked to achieve properties of acrylic emulsions so that they now offer per.. quently polymer characteristics of the acrylics. The arrows Thermoplastic Resins ( T ) in Fig. Above this tem- perature. E 1. styrene-butadiene and poly(vinyl acetate) emulsions. 1 and 2 in degrees absolute.// . unoccupied space contained within the polymer) to replace solvent alkyds as the dominant binder in the exte. unreactive and consequently are stable when mixed with pig. 1. the polymer is a glass. by Fox and Flory [5] and later refined by several others.e.01 .05 mer) or copolymer (two or more monomers). nently soluble. "" . Acrylic resins are usually supplied in strong solvents such as toluene. . In Fig.91 C ~ ~ ~ ~ + ~ above the Tg the polymer is a rubbery material.) www.. acrylic emul. Over the past 20 years. changed as temperature decreases below Tg."/". and easy cleanup features of its water-based competi.. (Reprinted with permission from the spectively. Simha and Boyer have independently calculated that at Tg.. the free volume increases. but they remain perma.. The but..87 the relationship proposed by Fox [4]. They are clear.iran-mavad.-" ture... it offered excellent exterior durability that free-volume theory states that the Tg for any given polymer allowed use in exterior paints. crucial in designing polymers that meet the needs of the When the first acrylic emulsion designed for use in house coatings market. permitting sufficient molecular motion so polymer flow can ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ .o3 Each acrylic monomer brings to the polymer its own individ. ."" . it is useful to utilize 0.93 range where the polymer undergoes a second-order transi- tion. 1. nologically be explained by the free-volume theory proposed tors.. the concept of Tg and the formance similar to the solvent-based coatings they are re. From the graph. alkyl methacrylates). This is the solely by evaporation of the solvent. it can be calculated that. or methyl ethyl ketone. Acrylics are a uniquely versatile family of polymers since 0 1. m ments. They do not need to be Tg..05 .1~ unpigmented form as protective finishes over vacuum metal- ized plastics and polished metals such as brass. To approxi. Rogers and Mandelkern have plotted specific volume versus ACRYLIC SOLUTION POLYMERS temperature for a series of methacrylates as a means of estab- lishing the relationship of Tg to free volume [6]. . can phenome- drying. 1 -Specific volume-temperature relations for the poly-(n- W1 and W2 = the weight ratios of Monomers 1 and 2. and conse- paints was introduced in 1953. re. Also. but 0. colorless films. / ' ~ j 11"111"1~. -"" down to clear. are fast-drying lacquer materials. extenders. resistant finish..89 mate the Tg for a copolymer composition. No external pigment wetting agents are required to make finely dispersed pigment grinds for high- gloss lacquers. Tgl and the Tg's of the homopolymers of Monomers Tg 2 = trol organic emissions. They are often used in 1. * / " - ual performance characteristics based on its molecular struc. free oxidized or cross-linked to form a hard. it had the low-odor. it has occurs at that temperature where the fractional free volume been good exterior durability that enabled acrylic emulsions (i. During the past 40 years. reaches some universally constant value that remains un- rior house paint market. They volume accounts for 15% of the total polymer volume [6]. 1. 0. At temperatures below the Tg. '12 ~ . 1 indicate the temperature at which there is an Thermoplastic acrylic resins are acrylic polymers that are inflection in the specific volume curve indicating a sudden polymerized directly in a suitable solvent and form a film increase in free volume (as temperature increases).22 colorless solutions and.. such as aluminum. quick. / f/ selecting combinations of the various acrylic monomers. an infinite array of properties can be achieved by carefully . xylene.. thermoplastic acrylic polymers are quite 09 . will also dry 1. American Chemical Society.83 ~ t t t t t t t f t + (1) -80 -60 -40 -20 0 20 40 60 80 100 120 140 Temperature.85 1 _ W 1 W2 0. The Tg of a polymer is a softening point: it is actually a temperature 0. The marked difference in Tg's. in addition. ability to manipulate Tg as a means to control properties is placing. ~ where FIG.. if left unpigmented. 0.

5 poly(hexyl acrylate) po]y(2-ethylbutyl methacrylate) 11 (brittle pt) . high of the ester side chain becomes larger.20 poly(heptyl acrylate) . higher in tensile strength. As the alcohol moiety if the molecular weight becomes too high. as well as by the interaction Mark-Houwink equation [9]. 57 poly(n-octyl methacrylate) . The acrylates where have an alpha-hydrogen atom next to the carbonyl group.. As molecular weight increases. 50 poly(lauryl methacrylate) . 38 poly(n-decyl methacrylate) . reducing the a m o u n t of low-molecular-weight fractions. giving them more rotational freedom and hence greater seg.5-trimethylcyclohexyl- methacrylate) 79 NOTE:The brittle point measured by a fracture test often approximates Tg. elongation. strength. The lower the molecular thereby encouraging greater molecular rotation.72 poly(dodecyl acrylate) poly(hexadecyl methacrylate) (brittle pt) . of the polymer and solvent.43 poly(t-butyl methacrylate) 107 poly(t-butyl acrylate) 43 poly(n-hexyl methacrylate) . the viscosity of a solution polymer is propor. thereby methacrylate in toluene.73). Tensile also helpful to narrow the molecular weight distribution.30 poly(octadecyl methacrylate) . viscosity. longer chain length). the polymers b e c o m e increasingly soft (as the ester content. 50 poly(tetradecyl methacrylate) .com ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . rior durability are all dependent on molecular weight. resin are largely controlled by the physical characteristics of tional to the molecular weight of a polymer according to the the solvent contained in the resin. It is MW of about 100 000 and then tend to level off. Table 2 dem. harder. which increase viscosity and cause application greater n u m b e r of chain entanglements (which act almost problems such as cobwebbing of spray-applied acrylic auto- like cross-links). Consequently. while also minimizing high-molecular-weight acrylic polymer on molecular weight is primarily due to the portions. whereas high molecular onstrates the large range of Tg's that exist for the acrylate and weight is needed for good film properties. and resistance of the properties. e c o n o m y and emissions concerns. polymer/solvent combination (for polymethyl hydrogen atom. For example.1 and a increasing chain stiffness.20 poly(isobutyl methacrylate) 53 poly(isobutyl acrylate) . elongation than analogous acrylate polymers. The methacry. ~ Polymer Tg. the Tg differences for the acrylic n = K(MW) a (2) family of polymers can also be easily explained. This which have a deleterious effect on resistance and strength dependence of strength. From Encylopedia of Polymer Science and Engineering. Conse. solvent resistance. anchoring the polymer chains at higher mo. 60 poly(2-ethylhexyl methacrylate) . motive lacquers. elongation. New York. the higher the spray solids at spray side chain becomes larger) until the effects of side-chain crys. and exte. the solution viscosity also Equally important to Tg and polymer hardness is the length increases. weight of the polymer. The methacrylates are therefore -. The obvious answer to the viscosity versus film property The second most important parameter governing the film dilemma is to reach an o p t i m u m balance by producing an properties of a thermoplastic acrylic polymer is molecular intermediate molecular weight polymer. toughness. Copyright 1985). it is essential to carefully select TABLE 2--Tg for methacrylate and acrylate homopolymers [8]. methacrylate family of homopolymers [8]. 2nd ed. and lower in determining the constants should be specified. www. which hinders molecular rotation.3 poly(n-butyl methacrylate) 20 poly(n-butyl acrylate) .65 poly(2-ethylbutyl acrylate) . 91 = solution viscosity mental chain motion than the methacrylates. The type molecular weight used in higher in Tg.60 poly(2-ethylhexyl acrylate) . the polymer chains are spray solids are desirable for acrylic lacquers because of pushed further apart. K and a = constants derived experimentally for a specific lates have a bulky methyl group substituted for the alpha. For this reason.50 poly(cyclohexyl methacrylate) 104 poly(isobornyl acrylate) 94 poly(isobornyl methacrylate) 170(110) poly(cyclohexyl acrylate) 16 poly(phenyl methacrylate) 110 poly(benzyl methacrylate) 54 poly(ethylthioethyl methacrylate) -20 poly(3. Since the application and drying properties of an acrylic However. or conversely. K • l0 s = 7. l.24 poly(n-propyl methacrylate) 35 poly(propyl acrylate) -45 poly(isopropyl methacrylate) 81 poly(isopropyl acrylate) .. Most dry film properties for thermoplastic most thermoplastic acrylic solution polymers have weight- acrylics improve with increasing molecular weight up to a average molecular weights in the 75 000 to 100 000 range. low molecular weight is beneficial to tallization causes additional hardening effects. solids and application concerns. weight (MW). Polymer Tg.100 poly(hexadecyl acrylate) 35 poly(stearyl methacrylate) poly(2-ethoxyethyl acrylate) .3.iran-mavad. Inc.55 poly(sec-butyl methacrylate) 60 poly(sec-butyl acrylate) . lecular weight (i. the lower the viscosity at a given solids quently. Vol. creating additional free volume.0. ~ poly(methyl methacrylate) 105 poly(methyl acrylate) 6 poly(ethyl methacrylate) 65 poly(ethyl acrylate) . (Reprinted by permission of John Wiley & Sons.10 poly(2-heptyl acrylate) . CHAPTER 6--ACRYLIC POLYMERS AS COATINGS BINDERS 41 On a molecular level.e. thereby posing handling and application problems of the ester side chain of the monomer.

major automotive coating in use. and dirt pickup. that are capable of reacting with another polymeric or mono- merizing combinations of methyl methacrylate (MMA). such as toluene or acetone. For spray application. therefore. Burrell has published the solubil. they retain Thermosetting acrylic polymers offer the following advan- enough flexibility and elongation to have some impact resist. therefore. weight. route to improved film properties is to use a thermosetting At a Tg of 50~ these acrylic polymers are intermediate in acrylic polymer. extremely slow-drying solvents. flow that would be expected of softer/lower-molecular-weight phobic materials. however..42 PAINT AND COATING TESTING MANUAL the solvent in which the acrylic is dissolved (see Chapter 18 Up to the mid-1950s. tive acrylic lacquers. ethyl acrylate (EA). use of the more modern eye-catching metallic pigments [13]. ity parameters for an extensive list of solvents [11]. The acrylic lac- parameter concept was defined by Hildebrand [10] and ap. the acrylic lacquers require factory drophobic acrylics (with low 8 values) will have better buffing and or baking to obtain the kind of m a x i m u m gloss resistance to polar materials. or oil. Conversely. as indicated in Table 2. which retard development of properties.e. the also be carefully chosen to accommodate the expected appli- spray solids percent is tow. dry by evaporation of solvent alone. should be avoided. they are permanently subject to softening by strong ately fast evaporating solvents are needed to avoid running solvents. quers gave significantly better durability and allowed for the plied to coatings by Burrell. (2) better resistance to softening at elevated tem- ings to the Effects of Rapid Deformation (Impact) (D 2794)]. print [see ASTM linked. stains. heat. grease. Consequently. The solubility parameter is an particularly gloss retention. hence the term "thermosetting. leaving no "two-coat" effects or intercoat adhesion prob- during application of the paint. block reactive sites. such as carboxyl or hydroxyl. In general. peratures. This disadvantage was The evaporation rate of the solvent or solvent mixture must shared by the older nitrocellulose lacquers. tages over thermoplastic acrylics: (1) improved hardness and ance [see ASTM Test Method for Resistance of Organic Coat. often by the application of tack-free state that allows early handling of the coated prod.. While many other acrylate mechanical properties of thermoplastic acrylic polymers for and methacrylate monomers exist. one of the reactive species must have at least two Test Method for Print Resistance of Lacquers (D 2091)]. such as is done with detergents. Small has published a table of m o n o m e r (i. Nitrocellulose finishes gave it is important to match the solubility parameter of the sol. 100 000). Also. and consequently their Tg is approxi- ity parameters [12]. moder- plastic. a would contact the automotive finish. vent to that of the polymer. converting linear. They are hard enough to dry rapidly to a has been applied to the substrate. while the other species has at least three reac- [see ASTM Test Method for Blocking Resistance of Architec. Since these lacquers are thermo- cation method and conditions. the most economi. tural Paints (D 4946)]. an excellent original appearance but had poor durability. To ensure good solubility of the polymer. moderate-molecular- hardness. and required frequent polishing estimation of the polarity of a solvent or polymer and is by the car owner for the finish to took good. polymers." To be truly cross- uct and also hard enough to resist marring. www. This problem was related to the intermolecular energy of the molecule (see eliminated in 1956 when General Motors adopted acrylic lac- Chapter 35 entitled "Solubility Parameters"). As has already been discussed. No internal plasticizing cording to Small's method.. the solubility Since they are very hard and fairly high molecular weight parameter concept is helpful in predicting the resistance of (i. nitrocellulose lacquers were the entitled "Solvents"). the and ethylhexyl acrylate (EHA). such as gasoline. This cross-linking reaction takes place after the coating Coatings (D 1474)]. the solubility parameter can be calculated by such as the phthalates. tion solids. with the exception that metal furniture and product finishing) and have a Tg of ap- they contain functional groups. the thermoplastic solution polymers designed polymers to solvents or other organics. butyl acrylate (BA). The acrylic lacquers generally contain external plasticizers. tive sites per molecule or chain. and (4) lower applied molecular weight. because of hardness and high molecular weight. trim pieces. in lower solution viscosity and consequently higher applica- etc. sional network structure. The solubility quers based on poly(methyl methacrylate). proximately 50~ This Tg is generally obtained by copoly. much higher viscosity coating would be used. required for the new car showroom. coatings are generally improved by increasing molecular these few are the primary acrylic monomers that are com. For polymers. having a Tukon hardness of about 11 to 12 [see weight polymer chains to an infinite molecular weight struc- ASTM Test Methods for Indentation Hardness of Organic ture.iran-mavad. For roller coating. the more for automotive use are not capable of the excellent molecular polar acrylic polymers will have the best resistance to hydro.e. Yet. acrylates) is generally contained in automo- molar attraction constants used to calculate polymer solubil. Since thermoplastic acrylics lems. the thermoplastic acrylic lacquers can be easily repaired by slower evaporating solvents are required to avoid skinning on an additional coat of paint which "melts" into the original the roller and to allow for flowout of roller pattern created coat. Thermosetting Acrylic Resins The majority of thermoplastic acrylic solution polymers Thermosetting acrylic resins are compositionally very simi- are designed for general-purpose industrial finishing (i.e. which contribute to improved chip knowing the molecular structure of the repeating unit ac. lar to the thermoplastic-type acrylics. but polymers with overly high molecular weight pro- mercially available and that are. resulting coil coated stock to produce aluminum gutters. such as water and alcohol. resistance and cold crack resistance. More hy. ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . mately 105~ with a Tukon hardness of about 22. An alternate cally feasible. and and some can even be post-fabricated. duce solutions of unworkably high viscosity. if for some reason they and sagging of the low-viscosity paint. butyl meric multifunctional material to produce a three-dimen- methacrylate (BMA). Besides being helpful in estimating solubility. (3) improved resistance to solvents.

Where this i~ a problem. an aliphatic epoxy can acrylic backbone. which restricts I I their use to interior applications. can be cross-linked with amino resins such as: urea. we will elaborate on some of Styrene or vinyltoluene are often incorporated into the the more commercially significant thermosetting acrylics. epoxies.C H 2 . In some instance. entitled "Epoxy Resins in Coatings"). Even with catalyst. grease resistance. The primary uses for acid-functional acrylics cross-linked . sufficiently basic to be used as catalyst and have the addi- the epoxy resin is a condensation product of Bisphenol A and tional advantage of entering into the cross-linking reaction epichlorohydrin (see Chapter 10 entitled. when cured under suitable conditions. it is preferable Coatings").. acrylic polymer as "honorary" acrylic monomers because namely those cross-linked with nitrogen resins. To ###BOT_TEXT### / determine the optimum conditions for a given system. scratch resistance. melamine-formaldehyde resins are functionality and are reacted with an epoxy resin. and adhesion to metal. mela- The carboxyl-functional acrylic resins typically have a mo.. however. with 15 to 30 min at I 150 to 190~ being typical.C H . epoxy to reduce sensitivity to UV radiation (see Chapter 10 phenol A type epoxides.iran-mavad. the higher the bake CH2--C--CH2-.C H2 \ / I \ / \/ (D 2248-89)]. or tri(dimethylaminomethyl) thermosetting acrylic solution polymers that contain acid phenol. E P O X Y . Typical properties for an enamel based polymers: on an acid-functional acrylic resin cross-linked with a Bisphenol A based epoxy are shown in Table 3. &..--. the aro- OH OCO--ACRYLIC matic Bisphenol A portion of the epoxy would degrade rap- An alternative reactant to epoxies based on Bisphenol idly. Their most signifi- EPOXY--CH--CH2 cant limitation is poor resistance to UV light. as well as flexibility. offer an excellent balance of these with the epoxide to form ester linkages between the two important properties. epoxy resin required to react with the acrylic to achieve a ous functional groups have been devised as a means to cross. However. numerous chemical reactions utilizing vari. on the whole. the baking or stoving requirements H for acid/epoxide systems are fairly high. in recent years. turers have developed many aliphatic epoxides in an attempt to mimic the benefits of the workhorse Bisphenol A based Acrylic Polymers Cross-Linked with Amino Resins products (i. mine. resistance properties) without the accompany.. and their reaction kinetics with acrylic monomers are fairly good isocyanates. Typically. Also.e. and because they often improve alkali resistance and are low in cost. If used outside.. The acid content AMINO RESIN--NHCH2OR + ACRYLIC--COOH > of the acrylic polymer determines the equivalent weight of AMINO RESIN--NHCH20CO--ACRYLIC + ROH www. it is best to cure that system at a variety of baking conditions and ~----~ ~H~ 7 / then measure properties to determine the temperature and time required for m a x i m u m performance. the epoxy content is very high and ide sites have been incorporated by polymerizing glycidyl can therefore cause discoloration problems even indoors due acrylate. The cross-linking reaction between the carboxyl Acid-Functional Acrylics Cross-Linked with Epoxy group on the acrylic polymer and the epoxy resin is fairly Resins sluggish and requires a base catalyst such as dodecyl tri- Possibly the most resistant acrylic enamels are based on methyl a m m o n i u m chloride. and benzoguanamine formaldehyde condensates (see lecular weight in the 10 000 to 50 000 range and a carhoxyl Chapter 8 entitled "Amino Resins") as follows: content of 5 to 20%.O . however. poor resistance to UV light). or allyl glycidyl ether into the to UV light. epoxy manufac. the shorter the bake time required for cure.C H . it reacts enamels.. Acrylic polymers containing acid or hydroxyl functionality ing disadvantages (i.--. glycidyl methacrylate. Acrylic/epoxy enamels fill the needs of the appliance industry primarily because of their excellent alkali/detergent resistance [see ASTM Practice for Detergent Resistance of Organic Finishes --O--(z x)--C--(/ \ ) . im- ply by incorporating acrylic or methacrylic acid into the pact resistance. to add the base catalyst to the other components just prior to use. temperature. Other properties that are important to the appliance industry include: hardness. Some higher solids acrylics are lower in molecular weight with higher acid ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ .C H 2 + ACRYLIC--COOH The disadvantages associated with acrylic/epoxy coatings \/ are usually concerns brought about by the aromatic nature of O the Bisphenol A based epoxy cross-linker. be substituted for at least some of the Bisphenol A based because both economics and performance favor the Bis. which is critical to the performance of washing \~/ CH~ \ ~ / O machine coatings. "Epoxy Resins in [13].e. For improved package stability. link acrylic polymers. & with epoxy resin are as appliance enamels and coatings for interior metal furniture and equipment. Acrylic/epoxy backbone. high-solids acrylic/epoxies. stain resistance. CHAPTER 6--ACRYLIC POLYMERS AS COATINGS BINDERS 43 Over the years. thoroughly cross-linked system.. In some of the newer A/epichlorohydrin is another acrylic polymer wherein epox. and early chalking would occur. Of course.. The acrylic solution polymer is made acid functional sim. This approach is limited in use.

where coatings often m u s t be c u s t o m t a i l o r e d to the specific end use.. it does not require factory buffing to achieve high 1% detergent..48) Bonderite 1000 15 (1. favored POLYMER--CO--NH--CH2--O--CH2-- over acid-functional p o l y m e r s a n d are m o s t often used in N H .. ~ASTMblister rating. This detracts from the overall toughness a n d resistance properties. 2 POLYMER--CO--NH--CHzOH ) The hydroxyl-functional acrylics are. 15 min 5B g o o d hardness. 9 = delamination. CRS "H" Value 22.C O ..70) sulting in a cross-linked structure without the need for a n external cross-linking agent. 15 rain 6B Cellosolve acetate. This is very i m p o r t a n t in general indus- Color after 16 hr at 178~ 13. m a n i p u l a t i o n s in c o m p o s i t i o n [17].96 + ) Bonderite 1000 50 + (5..C O . 2 psi light print lacquers b u t with b e t t e r resistance to solvents a n d elevated t e m p e r a t u r e s . 30 min trace a n d general industrial finishing.65 +) c a r r i e d out in alcohol or a c o m b i n a t i o n of alcohol and aro- m a t i c solvent. the AM m o n o m e r can be meth- resins is a p p r o x i m a t e l y 30 m i n at 150~ while for an analo- ylolated before being polymerized. A rating of 10 means no blistering. Meth- Reverse impact... Acrylic/amino t h e r m o s e t t i n g e n a m e l s Stain resistance. Hydroxyl functionality is i n c o r p o r a t e d into the Pencil hardness 2H acrylic p o l y m e r b y c o p o l y m e r i z i n g m o n o m e r s such as hy- Solvent resistance. The p o l y m e r i z a t i o n is usually a conventional free-radical.N H .0 trial finishing.f o r m a l d e h y d e c o n d e n s a t e s are less d u r a b l e a n d Tukon hardness 16.. the r e a c t i o n is m o r e facile. The finalized meth- gous hydroxyl functional acrylic. As in most t h e r m o s e t t i n g acrylic polymers. cold-rolled steel were..2 linker type a n d level. 60 rain 6B rylic/amino e n a m e l s with o u t s t a n d i n g exterior durability.N H .f o r m a l d e h y d e conden- epoxy [14] (baked 30 rain at approximately 180~ sate.44 PAINT AND COATING TESTING MANUAL T A B L E 3--Application properties for a white enamel based on an c o m b i n a t i o n with a m e t h y l o l a t e d o r b u t y l a t e d m e l a m i n e - acid functional acrylic resin cross-linked with a Bisphenol A based f o r m a l d e h y d e or b e n z o g u a n a m i n e ..N H C H 2 O--ACRYLIC + ROH [18]: Reactions with a m i n o resins containing an -NH-CH2OH P O L Y M E R .C O . re- Cold-rolled steel 22 (2.8 of variation in p e r f o r m a n c e w h i c h can be o b t a i n e d by a few Mandrel Flexibilityb 1/2 in.iran-mavad.. ylolated a m i d e acrylic p o l y m e r s condense readily w h e n acid requiring 30 m i n at 125~ with an acid catalyst [15]. Since the catalyzed at bake conditions of 30 m i n at 150~ The conden- acid-methylol r e a c t i o n is relatively slow. Initially.. a rating of 0 means very large blisters. and the resulting p o l y m e r can self-condensate.P O L Y M E R + H20 www.. 1/4 in.C H 2 O R + H20 quired for acid functional acrylics cross-linked with a m i n o As an alternative process.. it allows significant sation process is a two-stage r e a c t i o n [19]: self-condensation of the a m i n o resin [16]. Over the years. therefore. the a u t o m o - tive i n d u s t r y has relied heavily on this type of t h e r m o s e t t i n g Print resistance. The curing c o n d i t i o n re. 74~ 200 h Few--6 gloss as do the acrylic lacquer coatings. with intermediate ratings judged by ASTMphoto standards. 1/8 in. The conversion p r o c e e d s as follows AMINO R E S I N . as well as excellent resist- ance to solvent attack. ~ = no cracks. w h e r e b y p r o p e r t i e s can be readily altered b y varying acrylic Original 60~ gloss 95.. the p o l y m e r is t r e a t e d with f o r m a l d e h y d e to convert it to the methylol amide. A n o t h e r r e a s o n that acrylic/amino resin t e c h n o l o g y be- Optical properties. m e r c a p t a n is usually included to control m o l e c u l a r weight. 30 min no stain a l k y d / m e l a m i n e systems in a u t o m o t i v e t o p c o a t applications. CRS (two coats) c a m e so p o p u l a r is b e c a u s e of the versatility of the chemistry. acrylic functionality level. acrylic m o n o m e r s . Xylol. P O L Y M E R . the methylol e t h e r (when c a p p e d with alcohol) is m o r e reactive P O L Y M E R .O H ) present. usually butanol.N H 2 + HCHO ) group are possible b e c a u s e this group differs from a simple POLYMER--CO--NH--CH2OH alcohol in that it is far m o r e acidic a n d reactive.2 have been f o u n d to have lower gloss a n d p o o r e r c h e m i c a l resistance. inch-lbs (Joule) 31101 or methylol e t h e r groups c a n be a t t a c h e d to an acrylic ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ .4 Tg. cold-rolled steel acrylic b e c a u s e it offers the o u t s t a n d i n g d u r a b i l i t y of acrylic 82~ 30 min. An acid catalyst will b r i n g a b o u t etherification with the alcohol AMINO R E S I N . Ink. a n d m a r resistance. solution p o l y m e r i z a t i o n Cold rolled steel 35 + (3.N H C H 2 O R + A C R Y L I C . inch-lbs (Joule) m a d e containing a c r y l a m i d e (AM). It also offers significantly higher a p p l i c a t i o n Detergent resistancea solids. Also. therefore. An alternate a p p r o a c h to a t h e r m o s e t t i n g acrylic p o l y m e r is Cold-rolled steel 0-0-0 to p r e p a r e an acrylic p o l y m e r w h i c h contains functionality Bonderite 1000 0-0-0 a n a l o g o u s to a m e l a m i n e / f o r m a l d e h y d e condensate. glass droxyethyl acrylate (HEA) o r hydroxyethyl m e t h a c r y l a t e (HEMA). After the p o l y m e r i z a t i o n is complete. Likewise.C O . U r e a . Table 4 briefly d e m o n s t r a t e s the kinds Microknife adhesion. very successful in replacing the less d u r a b l e Mustard. This type of c o m b i n a t i o n p r o d u c e s cross-linked ac- Cellosolve acetate.5 Gloss after 16 h at 178~ 95. a n d cross- Original color 9.C H a O H + ROH ) t h a n a conventional dialkyl ether. an acrylic p o l y m e r is Direct impact.

high-perfor- (HEMA) into the acrylic backbone. .5 BA 22.6 . f o r m a n c e m a i n t e n a n c e coatings are also areas w h e r e acrylic thanes. Acrylic u r e t h a n e s are.e. .com ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . no isocyanate react faster t h a n the aliphatic types. in. mandrel 0 0 0 0 Knife scratch 7+ 7 7 7 Resistance to: 20% NaOH. r a i l r o a d cars.6 10. .1 Gloss (60~ initial 98 98 94 98 After 4 h/219~ 84 92 84 74 Front impact. . lower-molecular-weight. a n d n o w the e m p h a s i s is on resistant hydroxyl functional acrylics p r e d o m i n a t e . The hy. . triethylene diamine. % by wt 47.0 . heavy e q u i p m e n t coatings. a d d u c t of h e x a m e t h y l e n e d i i s o c y a n a t e (HMDI). . VOC regulations..-. % by wtb 30 30 30 30 Film Properties Color or yellowness factorb Initial . 50. While the a r o m a t i c varieties of b u t usually there is no justification for so doing (i. R--NH--COO--ACRYLIC POLYMER + H20 (a urethane) If the m e t h y l o l a t e d a m i d e has b e e n etherified b y b u t a n o l The preferred isocyanates are usually aliphatic. Acrylic solution p o l y m e r s cross-linked with aliphatic isocy- Isocyanate-Reactive Acrylics anates are ideal for a p p l i c a t i o n s w h e r e a durable.2 . .5 22. (Reprinted with permission of the Journalof Coatings Technology.4 49. . buses. . .N = C = O) is extremely reactive a n d will n e e d e d for aircraft. a wide range i m p r o v e m e n t s in performance). The short "pot life. . .0.3. . .5 27. alcohols. These types of self. A few such catalysts include m a k e very g o o d g e n e r a l . . . 50. ureas. A u t o m o - cross-link with any type of functionality having a labile hy. Lacquer. therefore. The acrylic u r e t h a n e s c o m b i n e designed to be cross-linked with isocyanate resins generally the i n h e r e n t UV resistance a n d exterior d u r a b i l i t y of acrylics contain hydroxyl functionality i n c o r p o r a t e d b y p o l y m e r i z i n g with the a m b i e n t cross-linking ability of aliphatic isocyanates hydroxyethyl acrylate (HEA) o r hydroxyethyl m e t h a c r y l a t e to p r o d u c e hard.4 48. % by wt HEMA 27. etc.4. high-per- Acrylic solution p o l y m e r s t h a t are cross-linked with isocya.8 49.../lb to fail 2 0 0 0 Flexibility.5. a n d Related Products (D 16-75)]. .t h e y don't require baking. This includes amines. invaluable in the u n d e r a m b i e n t c o n d i t i o n s . .5 22. tough. . ure. 7-h exposure 10 10 10 10 Butyl acetate.5 . bile refinishing. chemical-resistant." two-package polyisocyanate/polyhydroxyl coatings m a k e up Over the years. The strength of the methylol of catalysts are available w h i c h can be used to speed u p the a m i d e acrylics is that they have no glaring weaknesses a n d cure of aliphatic isocyanates. m a n c e coatings. 22. . a n d high-per- d r o g e n atom. viscosities. 9 9 9 after 4 days of immersion ~Allcopolymers were <1 in Gardner Holdt color. b e c a u s e of nol a n d dibutyl ether w o u l d be obtained.3 Cross-linking agent. that they are a two-package system a n d c a n n o t be m i x e d until t h a n e coatings [see ASTM T e r m i n o l o g y Relating to Paint.Copyright 1961. . EtSt . and film properties of HEMA-based copolymers containing a variety of other monomers a [17].2. a mixture of b u t a ." Of this class.4 . the hydroxyl-functional acrylics have b e e n "Type V.0 After 4 h/219~ 6. such as the capping. I n c r e a s i n g www. i m p r o v i n g in p e r f o r m a n c e . Films baked for 30 rain.iran-mavad. bButylatedbenzoguanamine formaldehyde.p u r p o s e resins.. 12-day exposure 10 10 10 10 50% HAc. To meet m o r e stringent droxyl functional acrylic reacts with isocyanate resin as fol. l/s-in.5 St 50. a n d amides. .0 50..5 27. . Acrylic p o l y m e r s u r e t h a n e s are a p p r o p r i a t e . 0 = complete failure. at 149~ Ratings: 10 = best or no failure. the p o o r e r color a n d exterior d u r a b i l i t y a s s o c i a t e d with the condensing acrylic resins will also react with a m i n o resins. The t r a n s p o r t a t i o n i n d u s t r y w h e r e high-quality coatings are isocyanate g r o u p ( . CHAPTER 6--ACRYLIC POLYMERS AS COATINGS BINDERS 45 TABLE 4--Compositions. higher solids content for lower VOCs. MeSt . 4-h exposure 6 10 10 3 0. . . The m a j o r d r a w b a c k of acrylic u r e t h a n e s is There are six basic types of curing m e c h a n i s m s for ure. a n d dibutyl tin-di- l a u r a t e [20]. a r o m a t i c types of isocyanates.5 27. r e a d y for a p p l i c a t i o n b e c a u s e they are so reactive a n d have a Varnish.5% Rinso at 74~ blisters 9. f o r m a n c e coating is r e q u i r e d b u t where b a k i n g is not feasible nates (often referred to as acrylic urethanes) are u n i q u e b e c a u s e of the size or t e m p e r a t u r e sensitivity of the object to a m o n g the various cross-linking systems b e c a u s e they cure be coated.2 . higher-solids hy- lows: droxyl functional acrylics have b e e n developed. . zinc n a p h t h e n a t e . trucks.0 . BMA . Acrylate Methacrylate Methacrylate Methacrylate Styrene Styrene Methyl Styrene Ethyl Styrene Copolymer Composition. carboxylic acids.9 0.) further h e a t > ACRYLIC--OH + R--N = C = O > POLYMER--CO--NH--CH2--NH--CO-.0 Viscosity in 1/1 xylenefoutanol U-V W+ X+ X+ Solids content. i n s t e a d of w a t e r as a by-product. acrylic u r e t h a n e s b a s e d on weather.

the p r o p e r t i e s of acrylic e m u l s i o n p o l y m e r s in the in- with acrylic solution polymers. then cool to room temperature. Stir 15 min after adding the initiators.6 1. Because it has four reactive sites p e r properties of these emulsions were: molecule. The maximum temperature H2C CH2 H2C CH2 of 77~ is attained in 12 to 15 min. bMeasurement at 2% solids. There are three underlying reasons for the takeover of size.9~ 10. %--Calculated 35. a i r quality. One such diluent is a low. usually with the a i d of a n emulsifier (i. w h i c h are emulsified as preexisting resins.0 g Ammonium persulfate in 5 mL of water 0. A typical acrylic e m u l s i o n p o l y m e r i z a t i o n recipe is ket.. difunctional oxazolidine w h i c h is non. the viscosity of an dustrial coatings m a r k e t has i m p r o v e d so that they n o w offer e m u l s i o n is unaffected b y p o l y m e r m o l e c u l a r weight since p e r f o r m a n c e s i m i l a r to their solvent-borne counterparts. the solvents in oil-based p a i n t s have m o v e d p e o p l e t o w a r d s www. this m a r k e t has evolved F o r example.iran-mavad.8 b 12. for the b e s t possible physical properties. d u r a b i l i t y is so i m p o r t a n t .5 with HO HN--R--NH OH 28% aqueous ammonia. and filter. In this case.1g Surfactant 100. p a r t i c u l a r l y in exterior p a i n t s w h e r e their o u t s t a n d i n g given in Table 5 [23]. c o m m e r - The particle size of an e m u l s i o n is also very i m p o r t a n t in cial. Architectural coatings are generally c o n s i d e r e d to be coat- sus 75 000 to 100 000 for a solution polymer. However. p a c k a g e stable with isocyanates as long as m o i s t u r e is ex. Transfer this solution into the reaction flask. 375. % 22. with s m a l l e r particle size being b e t t e r t h a n large particle the architectural coatings m a r k e t b y e m u l s i o n polymers. one w a y to i m p r o v e p e r f o r m a n c e is to increase hydroxyl Materials: content. adjust to pH 9. with large health. The cluded from the paint. is d e p e n d e n t on particle sions. add the monomers and ferrous sulfate. the period of purging with nitrogen after charging the monomers should not This type of functionality has the advantage that it is one exceed 15 min before the addition of initiators to avoid the formation of polymer emulsion product with excessive viscosity.0 g Glacial methacrylic acid (100 ppm MEHQ) the cross-linked n e t w o r k [21]. The size.e.05% gums.0 --Found 34. Therefore. while it decreases solvent emissions. the film-forming ability of a n emulsion.6 pH at 25~ 5. 1. The use of m u c h the s a m e as for their solution p o l y m e r analogs. 5 drops t-butyl hydroperoxide (70%) Procedure: In a beaker. stir the surfactant with the water until dissolved R" H H R" and adjust the pH to 9.5a ACRYLIC EMULSION POLYMERS Particle size (light scattering). rinse the O/C ~N--R--N/C ~O beaker with a small amount of deionized water.0 mL Ferrous sulfate solution (0. releasing b o t h hydroxyl a n d a m i n e functionality [22]. have long b e e n a m a i n s t a y of the architectural coatings m a r - ized.5 before measurement.0 g Ethyl acrylate (15 ppm MEHQ) is to m o d i f y the acrylic u r e t h a n e with a reactive diluent w h i c h 100. TABLE 5--Copolymerization of ethyl acrylate.p h a s e system in w h i c h acrylic ~Emulsion adjusted to pH 9. Surfactant Form Sodium Salt Free Acid Solids Content. surfactant). usually at the expense of solvent alkyds. such as alkyds o r epoxides. and stir 15 min with flow of I I I I + 2H20 > nitrogen before adding the initiators.17%. it increases cross-link density for m a x i m u m per- formance. Particle size does affect e m u l s i o n viscosity. they are also k n o w n as t r a d e d e t e r m i n i n g p e r f o r m a n c e a n d m u s t be carefully controlled.3 35. p o l y m e r droplets are d i s p e r s e d in an external w a t e r phase. Filtration of the finished emulsion gave only 0. the gums amounted to ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . w h i c h in t u r n requires higher levels of isocyanate. s o m e p o l y m e r emulsions. methyl m u l a t e d coating. acrylic e m u l s i o n s are m a d e b y a n e m u l s i o n p o l y m e r i z a t i o n process w h e r e i n the Acrylic e m u l s i o n p o l y m e r s (also k n o w n as acrylic latexes) m o n o m e r droplets are emulsified in w a t e r a n d then p o l y m e r . I I I I + 2R'CHO The free acid (unneutralized) surfactant can also be used as an H2C CH 2 H2C CH 2 emulsifier for the above copolymerization. a n d the acrylic e m u l s i o n s in industrial coatings a p p l i c a t i o n s has also film p r o p e r t i e s of the e m u l s i o n s can be controlled by m a n i p u - g r o w n as a result of solvent e m i s s i o n restrictions. Over the last 40 years.15%) molecular-weight. ~ 22~ 3tY An acrylic e m u l s i o n is a t w o .0 by adding 50% sodium hydroxide \ / \ / solution. sales coatings. safety. as well from an entirely oil-based m a r k e t to one d o m i n a t e d b y emul- as its p i g m e n t b i n d i n g capability. the m o l e c u l a r weight of Acrylic E m u l s i o n s for Architectural Coatings acrylic emulsions is generally h i g h e r t h a n t h a t of acrylic solution polymers: 100 000 to 1 000 000 for an e m u l s i o n ver. To c o m p e n s a t e for lower m o l e c u l a r weight.0 g Methyl methacrylate (25 ppm MEHQ) is fluid a n d acts like a solvent b u t t h e n reacts to form p a r t of 4.3r Minimum film-forming temperature.7 g Sodium formaldehyde sulfoxylate in 5 mL of reactive with isocyanates until a m b i e n t m o i s t u r e opens the water ring. cP 7.46 PAINT AND COATING TESTING MANUAL the solids of the acrylic r e d u c e s solvent levels in the for. methacrylate. At the s a m e lating p o l y m e r c o m p o s i t i o n a n d m o l e c u l a r weight just as time.4% solids. ings i n t e n d e d for on-site a p p l i c a t i o n to residential. clean air The physical c h e m i s t r y of acrylic e m u l s i o n p o l y m e r s is regulations have further s t r e n g t h e n e d the p o s i t i o n of acrylic emulsions.0 g Deionized Water An alternative a p p r o a c h to r e d u c e d solvent o r higher solids 5.8 Viscosity (Brookfield). 4. Unlike CMeasurement at 0. in recent years. and methacrylic acid [23]. or institutional buildings.0 36. a n d o d o r concerns a s s o c i a t e d with particle size generally being a s s o c i a t e d with low viscosity. solution principles do not p e r t a i n to e m u l s i o n s (the p o l y m e r is insoluble in the c o n t i n u o u s w a t e r phase). However.

while eliminating the problem of roller spatter. in this regard. when used in combination Interior gloss and semigloss paints have much more de. outstanding appearance has been possible in recent years formance requirements for this market are fairly modest. The tradi- with decorative features such as color. overall ap- The high-volume. and doors. Consequently. commercially film build. damp substrates. paints provide excellent performance but require consider- vent marring and film damage associated with softer poly. were out of the question. A major breakthrough in latex adhesion lower-performance emulsions such as vinyl acetates. the morphology of emulsion particles has become cabinets. Since the gloss paints are often used in wet areas such as a such as for exterior flat and gloss paints. gloss. vinyl/acrylics per. merization is to incorporate the best characteristics of the ally have a Tg in the range of 20 to 50~ The harder polymers different phases. more nonhomogeneous phases. it variety of application conditions and can even be applied over must all come from the polymer. The one resistance property demanded in this usually produces poor flow and gloss. hydrophobic interactions. loosely bind to the surface of the latex particles through form satisfactorily. they are copolymers of a hard methacrylate mono. The adhesion promoter partic- performance is not critical. There. They also improve brushability and mer such as methyl methacrylate with a soft. Overall. acetate copolymers plasticized with a soft acrylate monomer. segments where performance and durability are essential. butyl acry. Interior Coatings Applications Since interior trim paints are so highly visible. In fact.e. They gener. tion with the new thickeners. film build. which are The hard acrylic emulsions typically used in interior gloss needed to keep doors and windows from sticking and to pre. the appearance properties of the newer small parti- late. such as for interior flat paints. acrylic emulsions bathroom.iran-mavad. and hiding tional thickener for latex paints has been hydroxyethyl cellu- being the more infuential factors determining consumer lose (HEC). The goal of this type of poly- usually harder than emulsions used in flat paints. The Tg is generally around 10~ cle-size hydrophobic acrylics. Smaller particle-size emulsions have greater surface acrylic latex particles with the new associative thickeners. Also. molecular weight. the water resistance of the dry film is also an control a very large portion of the market both in the United important property. This level of flat paints are aimed primarily at broadwall applications. latex paints are more tolerant of a wide ment does not contribute significantly to film ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . are necessary to build in block and print resistance. Interior are expected to be similar to oil-based enamels. To ensure good water resistance. adhesion to aged oil-based paints is long-term performance and protection in most applications. stage polymerization process sometimes referred to as a se- Acrylic emulsions used in gloss and semigloss paints are quential emulsion polymerization that results in various copolymers of acrylate and methacrylate monomers and are types of core-shef structures. emulsion/thickener systems. In the past few years. or ethylhexyl acrylate.. required. as it might in a bathroom. The degree of market occupied by all acrylic latexes. forming a network structure There is a small. ularly is needed to improve adhesion and blister resistance acrylic emulsions . which are made up of two or important variables contributing to performance: composi. rivals that of oil-based enamels. acrylic States and abroad. hydrophobic acrylic emulsions have been designed spe- lose (HEC) thickeners. and film build usually butyl acrylate at about the 15% weight level. and features such as flow and levelling. before these new this market tend to be fairly soft with good binding capacity. new this market. 10 mers. emulsions. size. technology came about with the development of ureide func- fore. Associative thickeners m a r k e t is scrub resistance. emulsion polymers. brushability. They are composite acrylic emulsions have been introduced. manding requirements than flat paints since they are used for In an effort to further improve the performance of acrylic more diverse and challenging substrates such as windows. with the introduction of associative thickeners. More hydrophobic latexes have stronger associa- dramatically enhance flow. in when the paint film becomes wet. and one of the key interaction between the thickener and the latex particle is features which they offer is improved rheology and applica. the acrylic polymers used in duce exceptional flow and gloss. which thickens by a flocculation mechanism and preference. in segments of the architectural coatings market where tional acrylic monomers [24]. Per. small-particle- ter resistance compared to conventional hydroxyethyl cellu. and particle size. area and therefore have more interaction with associative Associative thickeners (also referred to as rheology modifiers) thickeners. have surpassed oil-based paints for old oil-based enamels. Thirdly. and spat. However. especially at the high-performance end. Acrylic emulsions play a major role in an additional important variable. Since gloss and semigloss paints are formulated at low to 20% by weight on polymer solids). emulsions used in this market often contain hydrophobic monomers such as styrene. their cost is somewhat higher than mer backbone. truly high-gloss latex paints Typically. particularly Since these gloss and semigloss latexes are often used over quality acrylic emulsions. able amounts of coalescent to achieve film formation (i. These newer Since interior flat paints contain a high pigment loading to acrylic emulsions optimize thickener interaction and pro- increase hiding and reduce cost. cifically for use with associative thickeners. sheen level. CHAPTER 6--ACRYLIC POLYMERS AS COATINGS BINDERS 47 water-based latex paints whenever there is not a large penalty pigment volume concentration (PVC) to obtain gloss. hardness. available acrylate m o n o m e r such as ethyl acrylate. with associative thickeners. They are prepared by a two- tion. largely a result of the surface chemistry of the emulsion parti- tion characteristics resulting from the better interaction of cles. premium segment of the interior flat which accounts for their thickening action. the pig- in performance.are not a dominant binder. This may be accomplished by copolymerizing adhe- Although acrylic emulsions generally provide a superior sion promoting functional monomers into the acrylic poly- level of performance. particu- tailored to the specific needs of this market by optimizing the larly into the interior gloss area. This is undesirable both www. interior-flat market is dominated by vinyl pearance properties are critical to the success of the paint job.

which may be as By far the most challenging application for any coating is high as 60% by weight compared to 40 to 50% for unimodal as an exterior paint required to protect a multitude of sub. with a Tg in also contains small particles. but it has an effective hydro- paints is the need to withstand the freeze-thaw type of expan. In an attempt to combine these can also be used to achieve a desired surface chemistry while seemingly mutually exclusive properties. many exterior grade acrylic emulsions have been designed at a fairly small particle size of about 100 nm [25]. dirt resistance is enhanced by the pigment loading.e. MMA/BA polymers are better than MMA/EA the optimum range to balance grain-crack resistance with polymers. Since in its commercial form this technology sions designed for flat house paints are fairly soft. good adhesion characteristics the range of 10 to 15~ A coalescing solvent is usually used in are retained while film build is optimized. For this reason. it is now possible to make hard.iran-mavad. smaller particle-size emulsions when thickened with ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . An additional benefit of Exterior Coatings Applications these polymers is their high supplied solids. One primary reason for their success. 60%). so that high PVC flat paints are generally poorer than harder and embrittle on exposure as they continue to cross. the improved adhesion enhances crack resistance over dimensionally unstable wood sub- strates. The lobes of One of the toughest demands facing exterior flat house this polymer are about 350 nm. This type of polymer has a lobed incorporating elements designed to address essentially every morphology that is grown out during the polymerization pro- major challenge experienced by an exterior paint. as men. The adhesion promoter greatly improves blister resistance. Small-particle-size. For exterior flat house paints. The primary concern with making the acrylic polymer binder is still a controlling factor. www.. the acrylic paint tion and resistance to chalking. which are less aggregated by particles (courtesy of Rohm and Haas Co. Studies have shown that smaller particle-size acrylic emulsions are much more effective than larger particle-size emulsions for filtering down through the chalk and obtaining adequate adhesion. 2-Scanning electron micrograph of Multilobe | acrylic larger particle-size emulsions. cess. Painting over a degraded chalky surface is a common practice that can be a potential disaster if sufficient adhesion is not obtained. These properties are made film remains pliable and able to withstand substrate swelling worse by the catalytic degradation effects of TiO 2 on the and freezing. with the introduction of a Multilobe | acrylic emul- poor adhesion or low film build. emulsions that were designed to have improved chalk adhe- block-resistant acrylic emulsions that are also flexible and sion sacrificed some of the flow and film build of large parti- require lower coalescent levels.). Since flat house excellent resistance to sunlight and erosion. The chalk acts like a powdery barrier.e. strates in diverse and extreme weather conditions. Furthermore. Using a the flocculating mechanism of HEC. Film build is particularly important to an exterior paint be- tioned earlier for solution acrylics. and higher methacrylate containing binders are dirt resistance. the inherent durability of the link. Therefore. is their lack of absorption cause the durability of the film is usually proportional to the of ultraviolet light coupled with their inherent hydrolysis film thickness. acrylic emulsions have evolved strate. pre- venting the emulsion binder from penetrating to the real substrate and establishing an adhesive bond. It also reduces the level of thickener needed to achieve a that often occurs over this type of substrate. dynamic volume of about 1000 nm and is. which contribute paints contain a fairly high pigment content (i. to sophisticated systems sion. given viscosity. latexes. When the coalescent leaves. particle-size distri- not disturbing the bulk composition of the latex particle. have poorer flow and film build than FIG. how much paint is applied to the sub- resistance. However.. PVC = 40 to to their very good chalk resistance and color retention. 2 [26]. particularly at lower Other important aspects of weatherability are color reten- temperatures. shown in Fig. and acrylic polymers have too soft is that dirt pickup would worsen. low PVC gloss paints. To avoid the grain cracking HEC. It is in this Wide particle-size distribution acrylic emulsions do n o t demanding role that acrylic emulsions have met virtually all significantly address the low film build associated with requirements and impressed the industry by their outstand. ing durability. therefore. surfaces and large particles that help to improve flow in formulations thickened with HEC. the formulation to assist film formation. Among the common acrylic copolymer compositions in use Experience over many years indicates that a Tg of 10 to 15~ is commercially. the inclusion of an effective adhesion promoter in the acrylic backbone is crucial for good adhesion. acrylic emul. This type of polymerization cle-size (500-nm) emulsions. when thickened with HEC.48 PAINT AND COATING TESTING MANUAL from a cost and an organic emissions perspective. large-surface-area emulsions. This butions have been carefully controlled to ensure a tailored can be useful in optimizing rheology or improving adhesion mixture of small particles that give good adhesion to chalky characteristics of an acrylic latex. This was addressed in the 1980s by the Rohm and from simple polymers troubled by shortcomings. 100-nm two-stage polymerization. it does not result from particle aggregation. such as Haas Co. Over the years. unlike oil-based house paints which become binder. very sion and contraction of dimensionally unstable substrates effective at imparting high film build in paints thickened with such as pine or other soft woods. i.

have responded to the needs of these coatings users by devel- Over the past ten years. in tection. are small in particle size (i. the Philippines to the Scandinavian regions of Europe. For general industrial finishing over metal sub- These acrylic latex maintenance coatings had the usual strates. good flow and levelling is much more HEC [27]. The small particle used for interior gloss paints (i. HEC. technology to give tight water-resistant films. so that low-temperature film formation is generally not aggravate corrosion. have complied with the stricter environmental legislation by 100 nm) to take advantage of the excellent flow. Like the Acrylic Emulsion Maintenance Coatings newer gloss enamel emulsions for trade sales use. acrylic maintenance emulsions often outperformed Exterior gloss and semigloss paints are required to with. particularly on grain-crack resistance. How- generally determined by the Tg required to achieve the de.e. often in harsh chemical and corrosive envi. and they remain sufficiently in environments as diverse as the tropical regions of Asia and pliable to expand and contract with the substrate. and other decorative qualities. This is particularly true in day. Maintenance coatings differ substantially from decorative latexes aimed at industrial coatings applications have evolved coatings since they are used primarily for their protective into hard.e. coatings applications generally have to be harder and faster cially in 1964. at least in areas subject to ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . resistant binders that match the performance of features. Consequently. These hard latex binders used in interior and exte- good dirt resistance at low PVC. Maintenance coatings are generally used to protect performance. tions were offshoots of architectural coatings technology and were often too soft for industrial coatings uses. above Tg 35~ would not size of these binders fits perfectly with associative thickener be appropriate outside. The first acrylic latex binders for corrosion. Acrylic emulsions do not continue to signed that meet all of these challenges and perform very well harden once the paint film is dry. the acrylic emulsions used in rior gloss paints were fine tuned to maximize corrosion resist- these paints are harder than those used in flat paints and ance and overall protection. Commercialized in the mid- generally have a Tg in the area of 20 to 35~ This Tg range can 1980s. the decorative as well as protective oping more sophisticated emulsions capable of meeting the capabilities of exterior gloss paints have improved signifi. Of course. who have traditionally applied best be described as fair. leaving the substrate exposed and sub- lower pigment loadings. these coatings users to as acrylic enamel vehicles. which are an because they would be more prone to grain crack. which has historically been at the forefront of gloss paint applications. they are often able to be removed by the development of aqueous gloss enamel used outside as well. critical for a gloss paint than for a flat paint. storage tanks. to the surprise of some segments of the maintenance sired balance of crack resistance and dirt pickup. particularly those generally referred clean air legislation. and switching over to water-based systems. This is partly because the alkyds continue to harden addition. alleviated by the controlled application conditions in the fac- tenance acrylic emulsions are carefully selected so as to not tory. Early emulsions aimed at industrial coatings applica- ing alkyd enamels as the preferred coating for exterior trim. ever... They are similar in hardness and composition drying than architectural emulsions and have better corro- to exterior flat house paint binders with the exception that sion and chemical resistance. high gloss was not possible with these older emulsions. improvement over HEC-thickened paints that can have mi- Since brush marks are much more obvious in a gloss paint croscopic defects as a result of the flocculating mechanism of than in a flat paint. ject to the elements. it is unlikely that industrial coatings users metal surfaces such as bridges. would switch to latex coatings even with the more severe dustrial facilities. required. The flow of these systems could Industrial coatings users. The typical Tg range for such they are formulated with reactive pigments and additives acrylics is about 30 to 70~ The film formation problems which help prevent rusting. Without this evolution in elements. This limitation was of good adhesion even in wet areas. industrial acrylic emulsions have borrowed tech- advantages in application of water-based paints over solvent nology from maintenance finishes and have optimized sur- www. reduce volatile organic emissions. have recently been under pressure to an admirable balance of properties and are still popular to. and other in. Acrylic emulsions have been de. Since The one weakness of the acrylic latexes in the area of the acrylic emulsion engineered for interior gloss/semigloss maintenance coatings was their low Tg. However. however. but overall they have demonstrated solvent-based polymers. Since exterior gloss paints must have binders. color retention. demanding performance requirements of many different end cantly to the point where acrylic emulsions are rapidly replac. In many instances. industry. this new generation of maintenance vehicles has provide acceptable dirt resistance while still having good proved very successful in extensive field tests. older acrylic emulsions intended for semigloss paints (there Acrylic Emulsions for Industrial Coatings were no high-gloss latex paints until about 1980) are of large particle size to have the best possible flow with the prevailing Nonreactive Emulsions thickener of the day. which prevent substrate deterioration by corrosive their solvent-based counterparts. The very hardest acrylic emulsions bridges in the southeastern United States. The surfactants and other "salt usually associated with such hard emulsions are somewhat and pepper" ingredients used in the polymerization of main. must provide equally good dirt resistance at much and eventually crack. the methacrylate/acrylate levels are ance. newer acrylic emulsions intended for exterior California. ronments. Also. gloss.iran-mavad. CHAPTER 6--ACRYLIC POLYMERS AS COATINGS BINDERS 49 better than acrylics containing higher levels of acrylate alkyd paints along with expected advantages in chalk resist- monomers. users. which reflected a paints are intended to be high-performance systems capable lower hardness than the alkyd paints. Thermoplastic acrylic emulsions designed for industrial resistant maintenance coatings were introduced commer. solvent alkyds for corrosion resistance and overall metal pro- stand similar tortures as their flat paint counterparts and. emissions regulations. Acrylic producers rheology available by using associative thickeners.

None White rust . These p r o p e r t i e s allow the m a n u f a c t u r e r to stack. leveling. " W a r m t h " is a quality w h i c h refers to the feel a n d line speeds up to 137 m / m i n with g o o d transfer.b a s e d coatings c o m p a r e d to solvent-based as g o o d roll coatability. Mini-Spangle Substrate Aluminuma Galvanized Steel~ Primer thickness 0 0. a n attractive feature of this system is its excellent ins. excellent durability. These e m u l s i o n s have b e e n a p p l i e d at materials. This n e w for solvent-based acrylic resins. No. w h i c h provides a m p l e resistance character- is identical to the cross-linking c h e m i s t r y discussed earlier istics until the epoxy cross-linking is complete. a system c a n be trial coatings industry. pack. can be i n c o r p o r a t e d into the p o l y m e r b a c k b o n e of an acrylic A recent d e v e l o p m e n t in cross-linking acrylic e m u l s i o n e m u l s i o n so that it can react with a n o t h e r functional m a t e r i a l technology is an epoxy cross-linking. Typically hydroxyl o r hydroxyl/acid functional ularly useful in m a i n t e n a n c e coatings. 1/16in. a m b i e n t cure system after a p p l i c a t i o n to the substrate. flow. Blistering~ None Mod-Dense. One such type of h e t e r o p o l y m e r . mandrel bend Blistering~ . el-9: Higher numbers indicate srnaller blisters. additives. such as over technology. these e m u l s i o n s offer c o m p a r a b l e cure speed p e r f o r m a n c e of traditional.. g o o d c o r r o s i o n protection. acrylic e m u l s i o n s have been able to rival the w o o d paneling. a n d p e r f o r m a n c e to solvent-based alkyd/urea systems. No. or dense. After the e m u l s i o n is cross. Usually these systems are catalyzed with an a c i d catalyst to achieve the fastest/lowest t e m p e r a t u r e cure.9 to 1. 10 = no blisters. the a m o u n t of cross- o r m o r e phases have recently b e c o m e i m p o r t a n t in the indus.. % removed 0 0 Lifting None None Undercutting 1/16 in. core-shell polymer. 4 1/8-in. a n d m e t a l coil. the infinite m o l e c u l a r weight provides for solvent a n d d e t r a c t from c o r r o s i o n resistance. By N e w e r heterogeneous acrylic e m u l s i o n s c o m p r i s e d of two a d j u s t i n g the level of functionality. In i n t e r i o r applications.. the c u s t o m designed for a specific application. No.iran-mavad.2 Topcoat film thickness 0. in. a n d the Tg of the acrylic emulsion. w o o d panels. A very Thermosetting Emulsions g o o d p r o p e r t y b a l a n c e is d e m o n s t r a t e d in Table 6 for a n Just as is the case with solution acrylics. Pass Pass 200 h at 60~ After 1000 h Salt Spray Exposure X-scribed area Tape adhesion.. m e l a m i n e to coat p r o d u c t s such as h a r d b o a r d . 6. The coating applications. a n d c o m p o s i t i o n s to i m p r o v e r a t h e r t h a n linked. high-solvent-content nitrocellu. in.8 Gloss 20~ ~ 65/89 -/80 b Image clarity Very good Good Tukon hardness (KHN) 9 9 Pencil hardness Initial H H Wet 16 h. as well "warmth" of w a t e r . 4/16 in. 8 Exposed edge Undercutting . Blistering~ . curing. a n d ship coated parts m o r e quickly [28]. the t h e r m o s e t t i n g acrylics offer high m a j o r deficiency of acrylic emulsions in these areas is the gloss. bG1ossdependent on smoothness of substrate. moderate.. Using core-shell ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . None Flat Blistering~ None None ~Commercial chromate pretreatrnent. functional groups aqueous acrylic m e l a m i n e coil coating e n a m e l [29]. No. the c o n s t r u c t i o n i n d u s t r y has relied on d e v e l o p m e n t with i m p r o v e d block a n d p r i n t resistance at low hydroxyl functional acrylic e m u l s i o n s r e a c t e d with u r e a o r VOC. Acid functional acrylic e m u l s i o n s can be cross-linked early p r o p e r t i e s resulting from the high-molecular-weight with emulsified epoxy resins. a n d a p p e a r a n c e of the coated wood.0 0. Besides being a m b i e n t acrylic emulsions are cross-linked with u r e a o r m e l a m i n e res. along with h a r d n e s s a n d toughness. linker. The c h e m i s t r y of these systems acrylic emulsion. is being used to achieve r a p i d h a r d n e s s F o r m a n y years.-lbs 15 10 Metal mark resistance Excellent Excellent Rheology Excellent Excellent MEK rubs 200 200 Cleveland condensing cabinet.-lbs 20 to 25 35 Reverse impact. acrylic/epoxy system is c o m p a r e d to an e p o x y / p o l y a m i d e TABLE 6--Properties for an aqueous acrylic/melamine coil coatings enamel over aluminum and galvanized steel [29]. f o r m i n g a cross-linked w h i c h has m a n y a p p l i c a t i o n s b u t has been f o u n d to be partic- polymer.50 PAINT AND COATING TESTING MANUAL factants. I n coil lose lacquers in w o o d coatings a n d furniture finishes. www. Mod. 38~ H20 B B Flexibility--X30 microscope 2-3T 3T Direct impact. 2. c h e m i c a l resistance.... Blister density is rated as few.

E. New York. R. soft Mod. 1959.881. t991. H. 1961.. and Boyer. 1955. Journal of Applied Chemistry. NY. 985. 15 rain. Krosckwitz. pp. [5] Fox. E. 1959.. Vol. F.. Journal of Applied Physics. M. 19 Aug. 3 Weeks. F. MEK Mod." Official Digest. t 962. p. p. Krieger Publishing Co. 20. soft Butyl acetate Lt. p. R.. R. 129. p. Huntington. Official Digest. 301. Journal. = medium. CHAPTER 6--ACRYLIC POLYMERS AS COATINGS BINDERS 51 TABLE 7--Resistance characteristics of acrylic/epoxy water-borne coatings versus conventional controls [30]. The Chemistry of Organic Film Formers. 729. [2] Chemicals for Industry. pp.. R. C. E.. Spring House. M. [17] Petropoulos. p. REFERENCES Rohm and Haas Company promotional literature C-170. The strong [9] Rodriguez. Copyright 1992. p e r f o r m a n c e [31]. Robert E. [13] Solomon. 1985. PA. Spring House. p. [18] Solomon. Principles of Polymer Systems. 1977. D. N. soft Lt. 37. B. and c h e m i c a l resistance. tion of Societies for Paint Technology. Bikales. Chicago. 1991. Vol... "Fundamentals of Acrylic Polymers... R.. B. D. 300 h of QUV Exposure Gloss retention. PA. McGraw-Hill Book points of the acrylic emulsion/epoxy system are its stain. Official Digest of the Federa- 1950. 47. weathering. H. Schall.. G. soft Butyl cetlosolve Lt. soft Lifted Toluene Mod. Air Dry Acrylic/Epoxy Epoxy/ Formulation Polyamide Alkyd Solvent Resistance MEK rubs to remove >300 >300 120 Lifted Spot tests. p. Co.. on concrete HCI No effect No effect No effect NaOH No effect No effect Dissolved Accelerated Exposure. New York. Journal of Paint Technology. 475. and Schall. Vol. U. No less a key feature is its very good co r r o si o n Rheinhold Publishing Corp.. Vol. 5. Robert p. NY. and Lestienne. [21] Watson. 21. p. Overberger. 3rd ed.. D. D.. and Novak. % 49 2 10 NOTE:Lt. 1977. along with o ut st an d i n g [10] Hildebrand and Scott. [14] "Acryloid Thermosetting Acrylic Resins. Eds. 1957. and ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . Frazier. John Wiley and Sons. p. soft Mod. 1971. Jr. 24 h Mustard OK Lt." Product Bul- and J. Mod. L. and Hart. Vol. Vol. solvent. = moderate. 27. Journal of Applied Polymer Sci- The Lakeside Press. D.. G. 1953. 43. S. July 1973. [4] Fox. J. pp. L. p. [11] Burrell. soft Lt. [7] Simha. [24] Hankins and Melamed. F. mosetting Acrylic Resins. 1003.. C. percent 63 4 4 Fade resistance (green coatings) Good Very poor Poor 800 h of Fade-O-Meter exposure Gloss retention. A. Hvy. Vol. A. Vol. p." Encyclopedia of Polymer Science and Engineering.iran-mavad. T. H. soft Lt. C. p. M. Vol. 71. [6] Rogers.. IL. D. 1959. P.. soft Gasoline Lt. 1977. G. Med. [19] Christenson. York. The Chemistry of Organic Film Formers. "Acrylic and Methacrylic Ester [22] Private communication. 1949. G. 154. T. [15] Solomon.." revised October 1966. G. 1970. soft Lt. 123. Vol. 696. ence. R. H. NY. 33." Paint Coatings Cross-linked with Amino Resins. 1. No. stain Coffee OK OK OK Red ink OK Lt. 283. www. p. = light. R. D. The Chemistry of Organic Film Formers. = heavy. W. Spring House.. R. [16] Saxon. PA. C. C. 257-258. Huntington. 8. Rohm and Haas Company 1909-1959. Jr. Rohm and Haas Co. I. "Acrylic [3] Brendley.. stain Cola OK OK OK Grape juice OK OK OK Acid/Base Resistance 24-h immersion. P. soft Mod. [12] Small. 61. [23] "Emulsion Polymerization of Acrylic Monomers. soft Mod.) coating and an alkyd coating in Table 7 [30].S. 1956. 1964. Vol. 581. (Reprinted with permission of the American Paint and Coatings Journal. Krieger Publishing Co. stain Hvy. 273. I. 33.171.. Rohm and Haas Co. C. R. The Solubility of Non-Electrolytes. stain Med. soft Stain Resistance Spot tests... Bulletin of the American Physics Society.. Symposium on Ther- and Varnish Production. [8] Kine. 726. soft Lt. 3. Donnely & Sons Co.. Mark. No. and Mandelkern. [20] North. 2nd ed. Menges. J. American Paint and Coatings No. 58.. Rohm and Haas Company 1909-1959.. W. [1] Chemicals for Industry. Huntington. 557. Journal of Physical Chemistry. H. H. F. 277-281. Journal of Chemical Physics.. p. Robert The Lakeside Press. Patent 2. P. Polymers. IL. Krieger Publishing Co. Chicago. New letin CM-104 A/cf. p. 21. Donnely & Sons Co. 369. and Cadwell..

Seymour and H. Seymour and H." R. R.. Eds. A. pp. New York. Pittsburgh. 43. N. 1991. "82C2. p. 309. promotional literature. B. p. 38.. p. Co. [29] Rohm and Haas Co. B. PA. 297. E. p. Mark.. Elsevier Science Publishing 1980.. [31] Klepser.. R. Inc. Elsevier Science Publishing Maintaining Structures with Coatings. Eds.. Steel Structures Painting Council. Modern Paint and Coatings. www. "Water-based Maintenance Coatings Systems." October R. F.52 PAINT AND COATING TESTING MANUAL [25] Harren. 96- [28] Roman. Mark. November 1991. ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . Organic Coatings: Their Origin and Development. 1990. 20 Jan. 1992. [26] Rohm and Haas Company photograph. Co. 1990.iran-mavad. J. Organic Coatings: Their Origin and Development. [30] Mercurio. Proceedings of SSPC 91. 97.. American Paint & Coatings Journal... New York. 2. Inc.. E.. R. p. [27] Harren.

com Copyright9 1995 by ASTM International www. 9 Monobasic fatty acid or ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . 53 www. Kienle coined the term transesterify back into the alkyd and change characteristics. 1028 South Third Street. wall paints.e. 1995 7 Alkyd and Polyesters by Al Heitkamp ~and Don Pellowe 2 ALKYD RESINS. and the solvent evaporation rate from dicarboxylic acids were known at the start of the 20th Cen. maintenance paints. and phthalic anhydride. composite. The early condensation tween hydroxyl and carboxyl groups of the chemical interme- products were not soluble in common solvents and did not air diates. ALKYD SYNTHESIS. formerly employed by Frost Paint. and baked industrial and maintenance coat. The early spelling of"alcid" was later changed to and these include dimerization of fatty acids or vegetable oils the current form. and printing ink and fatty acids as coreactants with the early developed poly- industries. tury. an alkyd could be based on glycerin as the polyol. performance. nomical alkyd manufacture. plastic. ids and water-borne types. and it dry until monofunctional acid or fatty acids were incorpo. undercoatings. whereas fatty acid blends are 55415. soya fatty ments. oil fatty acids or special blended fatty acids are commonly tile type of polymers for coatings and printing inks. m o n o m e r s . Minneapolis. lized in the manufacture of alkyd resins: rior trim paints. MNL17-EB/Jun. and other new. The sol- vent selection and quantities used influence the viscosity. acids or soya oil The stoichiometric proportions and the equivalent weight of these monomers lead to the desired physical properties and HISTORY molecular weight distribution of the resulting alkyd. and soya or linseed conventional solids. phthalic an- polyhydric alcohols and polybasic acids. and ap- MANUFACTURE plication characteristics. Three major classifications of alkyds are those designed for phthalic anhydride as the polybasic acid. topcoats. alkyds modified with drying oils were developed in the Alkyd processing is mainly a condensation reaction be- late 1920s by Kienle et al. The main by-product of the reaction is water. i. metal. Alkyds are a special class of polyesters that often have products such as new techniques for the production of vegetable oil or fatty acids coreacted into the polyester. they continue to be the most versa. coating films. 9 Polyhydric alcohol--example. resins being the predominate binder for organic coatings. Alkyd and chemically modified alkyd polymers esters was the technological breakthrough that led to alkyd find use in most types of liquid organic coatings for architec." Air-dry films were the result of depending on their unsaturation and the alkyd processing temperature. Typically. and other substrates such as Three major categories of chemical intermediates are uti- primers. Polyesters for coatings are based on a coreaction of 9 Polybasic organic acid/anhydride--example. and water-borne coatings. Monofunctional fatty acids such as tall the preparation of alkyds. air-dry. used in high-performance alkyds--particularly in higher sol- 2Retired.. Such polyesters may hydride be prepared from one or more polyhydric alcohols and poly. many of these compounds. "alkyd" from the alcohols ("al") and acids ("cid") used in their Other chemical reactions are possible during preparation. exte. coating.f o r drocarbon solvents. oil as the vegetable oil. COMMONLYKNOWN AS "ALKYDS. [1-5]."are synthetic oxidative polymerization and cross-linking that took place polymeric materials that have been used in the coating in. must be removed during the polymerization process or it will rated into the polymeric material. PROCESSING AND ings with a wide range of appearance. Today they continue to be the unsaturation part of the fatty acids.e. "alkyd. below 0~ They are easily pigmented and readily accept additives to form coat. tural.. These compounds are coreacted and Because there are a large variety of commercially available then reduced with aliphatic or aromatic petroleum-based hy- intermediates and chemical modifiers--i.. Although condensation products of dihydric alcohols and nonvolatile content. synthetic glycerin. Vegetable oils (triglycerides) are used for eco- iMcWhorter Technologies. through coreaction of oxygen and the carbon-carbon bond dustry since the 1930s. novel these compounds provide the distinctive air-cure feature of polyhydric alcohols. found in alkyds as alternatives to vegetable oils. higher solids. preparation. Other developments contributed to the general interest in the ings. glycerin basic acids to meet particular coating performance require. and similar end uses. Alkyds are extensively used on wood. The use of vegetable oils "workhorse" polymers for the paint.iran-mavad. Most alkyds are film-forming polymers with a relatively low glass transition temperature (Tg).

In this method of manufacture. the condensation reaction.:"~. Vigorous mixing and agitation are 9 Isocyanates required throughout the process to insure uniformity of the 9 Paramethyl styrene final resin (Fig. and the azeotrope sol- vent is returned to the reaction vessel (Fig. Water of condensation exits from the top 9 Epoxides opening of the ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . U L HEATING MANTLE FIG.) www. The product provided by this process 9 Phenolics depends greatly on the procedure conditions followed in tem- 9 Polyamides perature and timely removal of water-of-reaction by-product. Then an inert gas. ~ L 13 L A ~ . The purpose of the More than one of the above compounds are often used to azeotropic solvent is to aid in removal of water formed during impart particular characteristics when an alkyd is modified.'J THERMOMETER GLASS BEARING MM O.IVll ~ I-" r-II:: I . These meth- reaction vessel.L . A separator or Dean-Stark trap below the ods are the fusion and solvent reflux processes. such as and viscosity are measured until the final desired values are MOTOR g~ i'~ ~'.t l L . (Diagram courtesy of ICI Hercules Alkyd Reports. 2). 1-Apparatus for fusion cooking of alkyds. condenser collects this liquid mixture. the alkyd intermediates are In both fusion and solvent reflux processes. The choice of Fusion P r o c e s s azeotrope solvent affects the temperatures maintained dur- ing the reaction. acid number charged into the reaction vessel.iran-mavad. The reflux solvent and water vola- There are two major methods of preparing or processing tilize together and liquefy in a condenser placed above the alkyds for both laboratory and production scale.54 PAINT AND COATING TESTING MANUAL An alkyd resin can be modified with a number of intermedi. an azeotropic solvent such as xylene is commonly used in the reaction. 9 Rosin 9 Silicone 9 Styrene Solvent Reflux P r o c e s s 9 Vinyl toluene In the solvent reflux process. The reaction mixture is heated from 350 to 500~ (175 to 260~ 9 Acrylates The main polymerization occurring is by condensation to 9 Benzoic acid form ester groups. dry nitrogen or carbon dioxide. Some of the more common types are: vapor space above at the top of the reaction vessel. TUBING C NIUM FOIL RS ALL CORKS I-1 r. 1).D. is introduced to "blanket" the ates.

Also. Typical polybasic acids. usually less The viscosity of alkyds covers a wide range and must be than 3% by typically 1% of the total weight.) reached. Only a small amount. The solvent reflux used. The nonvolatile content of alkyd solutions is determined with ASTM D 1259: Test Method for Nonvolatile Content of PHYSICAL PROPERTIES Resin Solutions. CHAPTER 7 . SAMPLE HEMISPHERICALGLAS-COL HEATINGMANTLE FIG. and and percent nonvolatiles. a greater variety and measured times in seconds are easy to run with proper of alkyds can be made by this process. Then the alkyd is thinned with the desired type and Viscosity amount of organic solvent. ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . This method is sometimes varied to a higher characteristics of alkyd resins are determined by ASTM oven temperature of 150~ and a shorter dwell time in resin methods. 2. of the reflux or compared to the nonvolatile content and type organic solvent azeotrope solvent remains in the alkyd. (Diagram courtesy of ICI Hercules Alkyd Reports. and the final coating application properties. acid number.. viscosity. testing equipment and a constant temperature set at 25~ tion properties are measured at 25~ Typical tests include Viscosity is important in reflecting alkyd molecular weight color. Relatively high-molecular-weight alkyds need to be reduced RAW MATERIALS (INTERMEDIATES) FOR to application viscosity with a greater amount of solvent or ALKYD RESINS solvent mixture or with solvents that have a particular sol- vency for the specific alkyd. 2-Laboratory apparatus for solvent cooking of alkyds. hydroxyl number. thickness. processing use. ASTM D 1545: Test Method for Viscosity of Transpar- process advantages are less emission of by-products to the ent Liquids by Bubble Time Method [6].iran-mavad. hardness.. The final alkyd solu.A L K Y D AND P O L Y E S T E R S 55 ALLEQUIPMENTHAS29/42JOINTS . and mono- basic fatty acids or oils are given in Tables 1. The numerous possible raw materials available and economic NONVOLATILE CONTENT considerations of these lead to versatility of alkyds and to a wide range of commercially available products. polyhydric alcohols. The bubble tubes atmosphere and faster processing time.EDRICH'S NDENSER MOTOR TRUBORESTIRRER4 SOLVENT THERMOMETER II LAYER L E T ~ WATEF SEPARATORY CO2IN TRAP . Alkyd specifications are designed to show a 1 or 2% variation from an agreed on nonvolatile by weight The most common physical properties used to identify requirement. and 3. minimizing batch-to-batch variation of each specific alkyd.

the flash point of an alkyd solution reflects the flash point of the The color of alkyd solutions is determined by comparison solvent used to dissolve the ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . and Related Products [9]. synthetic acid-based metallic ~Pentaerythritol Methyl glucoside driers have gained popularity for two main reasons: (1) Dipentaerythritol higher metal concentration in the drier. The color different from that of the actual solvent or solvents incorpo- or degree of yellowness of the alkyd solution may or may not rated into the solution. to form aNeopentyl glycol soaps. However. ASTM D 3278: Test medium-oil alkyds) to 100% nonvolatile content by weight Methods for Flash Point of Liquids by Setaflash-Closed-Cup (very long oil alkyds for exterior paints. i. The flash point of an alkyd solution is of Transparent Liquids (Gardner-Holdt Scale) [8]. stains. Driers are formulated in combinations or Diethylene glycol blends to maximize desired dry film surface and interior Triethylene glycol characteristics. Alkyd resin solutions vary from 30% nonvolatile (flat wall. Therefore.iran-mavad. calcium. and similar products). Metallic driers are based on cobalt. Color Neat alkyds have low vapor pressure.. Methods associated with deter- aTrimethylpentanediol mining drying are given in ASTM D 1640: Test Methods for Trimethylol ethane Drying. Propylene glycol manganese. Oleic acid Varnish. Drying Properties POLYHYDRICALCOHOLS The drying properties of alkyds are of importance when aGlycerin aEthylene glycol describing the product. Lacquer. they act as catalysts and accelerate the rate of air drying 1. such as vegetable fatty acids. TABLE 3--Vegetable oils used in alkyd manufacture. iron. other ASTM methods are utilized. to bill of lading and other regulations. TABLE 2--Polyhydric alcohols used in alkyd manufacture. Tallow acids aTall oil fatty acids Tertiary-butyl benzoic acid Special blended fatty acids Flash Point aMost commonlyused in commercialalkyds. lead. and rare earths reacted with Trimethylol propane synthetic organic acids. or Film Formation of Organic Coatings at ~Mostcommonlyused in commercialalkyds. latex modi. and (2) greater uni- Sorbitol formity of drier performance. ASTM D 1544: Test Method for Color ratory determination. Apparatus [10] is the most common test that will provide fiers. bAnonvegetableoil derived from fish. conformance with Department of Transportation regula- tions.56 PAINT AND COATING TESTING MANUAL TABLE 1--Acids and anhydrides used in alkyd manufacture. In recent years. It is recommended that with a range of color standards referred to as the Gardner- flash points on alkyd solutions actually be measured by labo- Holdt color standards. POLYFUNCTIONAL VEGETABLEOILS Adipic acid Castor oil Azelaic acid aCoconut oil Chlorendic anhydride Corn oil Fumaric acid Cottonseed oil ~Isophthalic acid Dehydrated castor oil ~Maleic anhydride ~Linseed oil aphthalic anhydride Safflower oil Succinic acid aSoybean oil Sebacic acid Tung oil Citric acid Walnut oil aTrimelletic anhydride Sunflower oil MONOFUNCTIONAL Menhadden oilb Abiatic acid Palm oil ~Benzoic acid Caproic acid aMostcommonlyused in commercialalkyds.e. Caprylic acid Capric acid Castor oil acids Coconut oil acids Density Cottonseed fatty acids Lauric fatty acids The density or specific gravity of alkyds is also referred to Linoleic acid as the weight per gallon or density and can be determined by Linolenic acid following ASTM D 1475: Test Method for Density of Paint. www. When these driers are added to the alkyd-based coat- Hexylene glycol Pentanediol ing. Room Temperature [11]. The method utilized depends on flash cup availability and other specified requirements. The flash point of alkyds is mainly of importance as it pertains to shipping the products and formulated paints. Curing.3-Butylene glycol and cross-linking. have an effect on the color of the final coating films.

Organic solvents with greater vis- The hydroxyl value or number is a measurement of the free cosity reduction of the base or neat alkyd are needed to lower hydroxyl groups remaining in the alkyd that have not been coating hydrocarbon atmospheric emissions. When Exterior gloss retention Worst ( ) Best these products are neutralized with an amine. and hardness. and urea-formaldehyde or a melamine formaldehyde resin. use of coupling solvents and amine-neutralized carboxyl lent weight.. Ease of brushing Best < ) Worst alcohols. The design and processing of higher solids ing Materials [12]. ease of of which require baking. thus affording tants. guideline to establishing performance characteristics. these polymers are formulated with a curing Unmodified alkyds are classified into four types that de. hydroxyl groups on primary carbon atoms are decreased atmospheric emissions. or ene glycol monobutyether. Hydroxyl value deter. Tertiary-positioned hydroxyl groups are the most difficult to esterify in this determination. nonvolatility. and typical application is given in The physical properties of these coatings are outstanding Table 5. A narrower molecular weight range of the resin species is necessary to meet air-dry. solvent. Water-borne alkyds are available in groups coreact with free isocyanate functionality. chemical resistance. both short-oil alkyds. melamine formaldehyde. long-oil. Although most classes of "conventional alkyds" such as those shown in theoretical equivalency based on hydroxyl numbers is a good Table 7. hydroxyl group can be sterically hindered or less available Higher solids alkyds can replace their conventional solids within the polymer and thus difficult to reach with the reac. they become www. which in turn is important to determining the groups on the polymer. urethane prepolymer to react with the alkyd. flexibility. In such systems. The curing agent can be a pend on oil content--very long-oil. Polyurethane prepolymers can be brushing. Properties such as speed of drying. nonvolatile. agent or cross-linker and baked.iran-mavad. This is accomplished by the develop- ings. The acid value of alkyds is typically determined with ment of polymers with lower viscosities than so-called con- ASTM D 1639: Test Method for Acid Value of Organic Coat- ventional alkyds. film flexibility. and this factor ALKYD R E S I N CLASSIFICATION results in a polymer that cannot be air dried to a cross-linked coating. and they afford coatings with excellent color retention. industrial primers and topcoats. propylene glycol monoethylether. due to the absence of fatty acids. Water-borne alkyds obtain their water reducibility by the Hydroxyl numbers are important in determining equiva. and air-dry architectural enamels and both air-dry and baking these are more reactive than those located on a tertiary car. the satu- properties are summarized in Table 4. bon atom. counterparts in many coating applications. consideration. TABLE 4--Alkyd resin properties related to oil length. Manufacturers can W A T E R .com ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . Second. Rather. minations are more difficult to perform than acid number The higher solids alkyd resins are available in all classes of determinations. These ings in two-component systems. The release of reacted with carboxyl groups during the condensation stage these solvents during coating film formation is an important of the alkyd resin preparation process. and performance properties of the coatings. a lad- der of co-reactant ratios is important to optimizing particular performance characteristics. Another important Hydroxyl Value factor is solvent selection. Typical coupling solvents are ethyl- amount of urea formaldehyde. medium. Reasonably accurate and consistent re- alkyds result in a lower average molecular weight than con- sults can be obtained with this test procedure. and four-carbon alcohols oil-modified urethanes.A L K Y D AND P O L Y E S T E R S 57 Acid Value H I G H E R S O L I D S ALKYD R E S I N S The free organic acid groups present in the nonvolatile Higher solids alkyds have been developed to reduce organic portion of an alkyd resin is an important property for pig- solvent emissions in those applications under regulatory re- ment wetting and performance properties of organic coat- strictive requirements. The type of resins can be adapted to provide higher solids Very Long oil LongOil Medium Short Oil saturated polyesters by redesigning the polymer and using Oil content Highest ( ) Lowest organic solvents with appropriate solvency rather than the Speed of drying Slowest < ) Fastest customary blends of aromatic hydrocarbons with ketones. Film flexibility Highest < > Lowest Water-borne polyesters are available through design of Chemical resistance Worst < ) Best polymers having acid numbers in the range of 40 to 60. ventional alkyds. acids. and glycolethers. the hydroxyl such as s-butyl alcohol. exterior durability. Such products are used in more reactive than those on secondary carbon atoms. CHAPTER 7 . SATURATED P O L Y E S T E R S Saturated polyesters are also called oil-free alkyds.B O R N E ALKYD R E S I N S often specify methods that can be used for secondary hy- droxyl groups. rated polyester provides the hydroxyl groups for cure with A summary of alkyd resins comparing types of oil/fatty free isocyanate groups on the polyurethane prepolymer. also called uralkyds. There are several reasons for this. and exterior coreacted with polyester resins for air-dry or low-bake coat- gloss retention are all dependent on the oil content. In the case of propylene glycol monopropylether. The oil or fatty acid modification is zero percent. First. the "conventional alkyds" such as those shown in Table 6.

This s u b s t i t u t i o n Short oil General industrial baking enamels. lower solvent hood parts a m o u n t s . of a silicone intermediate incorporated t h r o u g h reaction at a 30 a n d 50% level.58 PAINT AND COATING TESTING MANUAL TABLE 5--Description of unmodified alkyd resins. gloss. Higher Solids Types Type Typical End Use Higher solids silicone-modified polyesters are m a d e by Long oil Stains and enamels (limited lowering the polyester base molecular weight and/or u s i n g package stability) oxygenated solvents such as ketone and ester types as re- Medium oil General industrial air-dry enamels placements for aromatic hydrocarbons. Benzoic acid terminated Implement enamels Phenolic modified Primers prefabricated architectural products. a n d other applications requiring excellent exterior du- Copolymer Aerosol enamels rability and/or good heat resistance.In the 1960s. The end uses are similar to c o n v e n t i o n a l solvent- Phenolic modified Primers b o r n e silicone polyesters. This Type Typical End Use modification improves the weatherability and/or heat resist- Long oil Architectural enamels ance of the alkyd a n d resulting organic coating. The silicone- Medium oil Transportation enamels modified polyesters are available in both self-curing a n d bak- Short oil General industrial air-dry ing ( m e l a m i n e formaldehyde resin cross-linked) types. F o r m u l a t i o n of a coating from these products involves the use of water-borne Conventional Types or water-tolerant ureas a n d melamines. the higher solids.Rule 66 is a 1966regulationfrom California'sSouth CoastDistrictthat restricted the amount of aromatichydrocarbon solventin a coatingformulation.VM&Pnaphtha. a n d w h e n they are reacted TABLE 6--Higher solids alkyd resin types and end uses. Oil or Typical Type Alkyd Fatty A c i d Nonvolatiles Solvent Applications Very long Linseed 85-100% Aliphatic hydrocarbon Exterior latex Soya modifier Tall oil House paint modifier Oil-based stain and ink vehicles and modifiers Long Linseed 60-70% Aliphatic hydrocarbon Architectural coatings Safflower Maintenance coatings Soya One-coat enamels Sunflower Exterior enamels Tall oil acids Primers Topcoats Medium Linseed 45-50% Aliphatic hydrocarbon Farm implements Safflower Aromatic hydrocarbon Railway equipment Soya Maintenance Sunflower Tall oil acids Blends Short Castor 50% Aromatic hydrocarbon Industrial coatings Dehydrated or Rule 66-type castor solvent blenda Coconut Linseed Soya Tall oil acids Blends ~AtypicalRule 66 type solventis isobutanol. Rule 66 legislationwas adopted by many other local and state regulators. The silicone intermediates are of either hydroxy or methoxy functionality. soluble in blends of water a n d cosolvents a n d yield systems SILICONE-MODIFIED POLYESTERS with low-volatile organic c o m p o u n d content. water or m e t h a n o l is eliminated. a n d flexibility. However. metal advertising sign Silicone modified Maintenance topcoats stock. TABLE 7--Waterborne alkyd resin types and end ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . a n d higher nonvolatile c o n t e n t for the polyester Benzoic acid terminated Implement enamels solution. They and bake enamels are used as coil coatings for prefabricated building panels.research indicatedthat these types of solventscontributedgreatly to atmospheric ozone formation. and xyleneat 8% maximumvolumesolids. lower viscosities.iran-mavad. automotive under the yields increased solvency. sili- Silicone modified Maintenance topcoats cone-modified polyester resins do n o t have the self-cross-link- www. The cured films offer Silicone modification of polyesters is accomplished by use excellent hardness. with the polyester.

Oldring. New York-London. Vol. High Solids Alkyd Resins.. 1965. 19. Solutions.. Section 6. Journal of the American Chemi.01. W.. 4th ed. Division of John Wiley (Gardner-Holdt Scale)." Barrett Division of Allied Chemi- Setaflash-Closed-Cup Apparatus.. tion 6. 1992. www. Inc. Vol. Lac. E.. H. 214-215. pp. 1967. Keane. C. Vol. New York. K. R. Alkyd Resin Technology: Fo~7.. urated Polyester Resin Manufacture. 2. Varnish. R. A. SITA Technology. 1. [3] Kienle." Annual Book of ASTM Stan. Resin Section. Holmberg. 1933." Annual Book of ASTM Standards. U. "Fundamentals of Paint. 51. American Paint Journal. 406-412. 6. H. H. Patent 1.01. 3636. p.. Vol. 6. and Ferguson. J. 590. Organic Coating Technology. [2] Kienle. 1992. ogy. 06. tion of Organic Coatings at Room Temperature.. Sec. John Wiley [9] ASTM D 1475: Test Method for Density of Paint. p. pp. "Raw Materials Index. quer. R. A. 06. Reinhold [11] ASTM D 1640: Test Methods for Drying. Vol.. PA. London.nulating Techniques and [8] ASTM D 1544: Test Method for Color of Transparent Liquids Allied Calculations. and Lesek. Payne. 22. Unit 5 of the Federation cal Society. Materials. Systems and Specifications. Patton. 509... 1987. 1930. 10 Jan. 1929. 178-180. Vol. [4] Kienle.893.02. 1957. Steel [6] ASTM D 1545: Test Method for Viscosity of Transparent Liquids Structures Painting Council. Vol. CHAPTER 7--ALKYD AND POLYESTERS 59 ing option available for conventional types a n d are always [12] ASTM D 1639: Test Method for Acid Value of Organic Coating c o m b i n e d with a cross-linking agent. 06. PA.iran-mavad. Section 6. Journal of the American Chemi. Industrial and Engineering Chemistry. Industrial and Engineering BIBLIOGRAPHY Chemistry. Interscience Publishers. Sec-. 212-214. and Hovey. Pittsburgh. Vol. R. and Lacquer Technol- Section 6. [7] ASTM D 1259: Test Methods for Nonvolatile Content of Resin Vol. T.03. G.. 6. 1992. Processes and Equipment for Alkyd and Unsat- tion 6. H. Blegen. [10] ASTM D 3278: Test Methods for Flash Point of Liquids by "The Technology of Alkyd Resins. 349. and Coatings Association. 1929.. et al.03. Alkyd Resins. or Film Forma. 1985. P. pp. 192-193.. Vol. Curing." National Paint ASTM Standards. Philadelphia. and Sons. Chapter IX. p. REFERENCES [1] Kienle. New cal Society. pp." Annual Book of ASTM Standards. P.01. 1948.. Von Fischer. Vol.. Vol. 1991. Vol. and Hovey. 21. by Bubble Time Method. Annual Book of ASTM Standards. 1930. 283-331. [5] Kienle. New York-London.. Washington. OH. 1992. 194-197. Singer. Series of Coatings Technology. pp. J. 06. S. and Fuller. Section 6. dards. Paint and Varnish Technology. F. Publishing Corporation. 1992." Chapter IV. & Sons. T.03." Annual Book of ASTM Standards. 1992.." Annual Book of Zacharias.S. R. Section 6. Toledo. Marcel Dekker. pp. W. p. G. Vol. Kask. Progress in Organic Coatings. 1987. Resins for Surface Coatings. cal.. Chapter 7. R. K. Varnish. H. and Related Products. York." Annual Book of ASTM Standards. Elsevier Science Publishing Co. H. pp. C. 1988. 267-268. 1962. New York. 1958. pp. 1992.873. 52. ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ .

a n d in paper. butanol. film-former. Besides u r e a a n d melamine. such as n. glycoluril. Urea resins are also faster curing t h a n m e l a m i n e resins.o r iso-butanol with xylene are also available which are m a d e exclusively with butanol. o t h e r c o m p o u n d s with s i m i l a r f u n c t i o n a l i t y . Springfield. OR AMINOPLAST. a m i n o resins are usually water-white.or iso-). resin solu. S o m e a m i n o resins are w a t e r soluble or w a t e r reducible with co-solvent. used... conventional resins. . it is m o s t often an alcohol such as n-butanol. resin solutions Amino resins are used in coatings to cross-link the p r i m a r y at ---80% solids (weight/weight). linking r e a c t i o n ("cure") is p r i n c i p a l l y one of trans-etherifica- tion between hydroxyl groups on the p r i m a r y film-former a n d alkoxymethyl groups on the a m i n o resin. They are used widely for w o o d finishing. catalyst m a y be used to accelerate cure. d e p e n d i n g on the d e h y d e w i t h o u t subsequent r e a c t i o n with an alcohol have cure t e m p e r a t u r e a n d the p a r t i c u l a r a m i n o used.S. usually m a d e with higher ratios Urea resins are less expensive t h a n m e l a m i n e resins. e t c . film.a r e also used in specific a p p l i c a t i o n s where certain p r o p e r t y advantages are required. especially for the h i g h e r . no such f o r m u l a t i o n s are for coatings applications.e.astm.w e i g h t resins m a d e with b u t a n o l as a co-reactant.p r o d u c t s of the cure r e a c t i o n include m e t h a - hyde a n d b u t a n o l (either n. 730 Worcester doors. but as far as is known. with U.. c o n s u m p t i o n of a b o u t 100 million lb (45 • 106 kg) p e r year. i. all of w h i c h are excellent solvents for a m i n o resins.. They are a l m o s t al.m o l e c u l a r . a n d (2) conventional resins. kitchen cabinets. An a c i d that resins m a d e by reacting u r e a o r m e l a m i n e with formal. These resins are used as been m a d e for a m i n o resin f o r m u l a t i o n s w h i c h cure at r o o m m o l d i n g p o w d e r s a n d adhesives a n d are generally unsuitable t e m p e r a t u r e . i. a n d sales of a m i n o resins are d o m i n a t e d b y those b a s e d on u r e a a n d mela- mine. The cross- tions at < 8 0 % solids (weight/weight). is u n d e r s t a n d a b l e given that m e l a m i n e is m a d e f r o m urea.s u c h as b e n z o g u a n a m i n e .e. ture. it should be noted ture range to p e r h a p s only 30 s at the u p p e r end. Claims have b e e n available for 70 years o r more. furni- Street. W h e r e a solvent is used. a n d foil applica- 60 9 www.. b u t are m o i s t u r e sensitive a n d therefore not suitable for use out- 1Principal technologist. the r e a c t i o n p r o d u c t s of u r e a o r m e l a m i n e with formalde. 2-Melamine. a n d water. etc.RESINS for coatings are the p r o d u c t s of the r e a c t i o n of either urea (Fig. Cure t e m p e r a - p o l y m e r i c a n d were f o r m u l a t e d at a b o u t 50 to 60% solids in tures are in the range of 180 to 400~ (82 to 204~ for t i m e s butanol/xylene mixtures. Parenthetically. use of these m a t e r i a l s is quite limited. formaldehyde. o r iso-propa- ways m a d e with m e t h a n o l or c o m b i n a t i o n s of m e t h a n o l a n d nol. carrying p r i m a r y o r s e c o n d a r y hydroxyl groups. f o r m a l d e h y d e a n d an alcohol.iran-mavad. w h i c h of r e a c t e d f o r m a l d e h y d e t h a n the older. with Formaldehyde and Alcohols) by J. They have been c o m m e r c i a l l y avail. the a m i n o resin a l m o s t al- Historically. w h i c h vary from 20 to 30 m i n at the lower end of the t e m p e r a - able for a b o u t 60 years. Monsanto Chemical Co. O w e n Santer 1 INTRODUCTION Definition and Description / C=O AMINO. MNL17-EB/Jun. 1995 Amino Resins (Reaction Products of Melamine. the first a m i n o resins used in coatings were ways u n d e r g o e s self-condensation reactions. 2) with FIG. However. e. Urea. As p r e p a r e d . They were substantially nol a n d / o r butanol. iso-butanol. viscous NH 2 m a t e r i a l s which m a y c o n t a i n a d d e d solvent to reduce viscos. including resins which Copyright 1995 by ASTM lntcrnational www. ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . a l t h o u g h a small n u m b e r of high-solids resins are Mixed solvents. 1) o r m e l a m i n e (Fig. FIG. In a d d i t i o n to History the trans-etherification reaction. usually a n acrylic. ity for ease of handling. have been available for a b o u t 35 years.g. The m a j o r b y . Amino resins for coatings are g r o u p e d s o m e w h a t a r b i t r a r - Where Used ily into two classes: (1) high solids resins. o r alkyd resin tain no solvent. polyester. presently c o m m e r c i a l l y available. MA 01151.. High-solids coating resins.

the extent of the reaction is dependent on the charge with unshared electrons on nitrogen and oxygen.5 to 2. and the degree of process. >NCH2OR + HN< ~ >NCH2N< + ROH (5) Melamine resins. metal containers. cess. When formulated and cured. then. cure temperature is at or near ambient. ROCH2/ "CH 2 0 ' ' 9 condensation reactions in which two or more molecules of FIG. which can form strong hydrogen bonds Hence. while the remaining two hydrogens react more slowly and require an excess of formaldehyde to force the reaction. typically 1. In some be written as follows: wood applications. urea. www. how many of each will depend on etc.. Because of the relatively high polymer content. (see E n d U s e s o f A m i n o R e s i n s ) . The reactions leading to self-condensation may tures must be used to avoid damage to the substrate.iran-mavad. 3-Representative structure of a mela- the parent species are joined together through either a mine resin.5 tool for HOCH2NHCONHCH20H + ROH ) melamine resins. With mela.7 for urea resins and 3. two of the four available hydrogens The etherifying alcohol is most often methanol.A M I N O R E S I N S 61 tions. factors such as the composition of the amino resin. and catalyst level. the choice of alco- The synthesis of amino resins for coatings is a two-step hol (or alcohols. cure temperature. alkyl application since they are not nearly as water sensitive as the ureas. the lower the pH. with properties which depend on such factors as the choice of starting material. a n d 4 take place only under acid conditions.0 to 2. considerable self-con- HOCH2NHCONHCH20R + ROH ) densation takes place during the synthesis.5 to 6. These reactions are all self. ROCH2\ /CH2OH mine./N"'~NI~N'H The kinetics of the methylolation reactions of urea and melamine have been studied extensively [1-7]. With urea. that a variety of amino resins may be SYNTHESIS OF AMINO RESINS prepared. on the other hand.0 for melamine resins. and the degradative effects of sunlight. ROCH2.e. on the amino resin. the parent compound is reacted with polymerization of the resin. etc. find much b r o a d e r R = H. possibly the major. although res- are readily reacted with formaldehyde (Eqs 1 and 2). HOCH2NHCONHCH2OR + H20 (3) Because of these low reaction ratios. Perhaps the largest single use for melamine resins is in >NCH2OH + HOCH2N< ~ >NCH2OCH2N< + H20 (6) automotive OEM (original equipment manufacture). shift the equilibrium. the amino resins for coatings typically offer a product line of 25 methylolated intermediate is reacted with an alcohol (etheri. a number of other reactions may take place N which complicate the kinetics. contributor to high viscosity is reaction strongly pH dependent. the Reactions of Synthesis combining ratios of the various reactants. N reaction. Reactions with mel- amine are analogous. mine resin is shown in Fig. Structure/Property Variations H2NCONH2 + CH2O ) H2NCONHCH2OH (1) The difference between conventional solids and high-solids monomethylolurea a m i n o resins represents not so much a difference in solids HaNCONHCH20H + CH20 ) content as it does a distinction between resin structures. if more than one is used). both types may be formed.. melamine. Typical values for combined formaldehyde are in the range The reactions of melamine are similar to those of urea with 2. i. in the second. leading in the case ROCH2NHCONHCH2OR + H20 (4) of melamine resins to products with degrees of polymeriza- bis(alkoxymethyl)urea tion (DP) ->3 and perhaps somewhat higher for the ureas. on the other hand. the faster the residual imino (>NH) and methylo] (>NCH2OH) groups the reaction. The principal manufacturers of formaldehyde (methylolation reaction).. CHAPTER 8 . Equations 1 through 4 exemplify the pro. Mela- bridges. additional bridges of mine resins are used also in coil coatings. ratios of the various reactants and on whether or n o t the The high-solids amino resins have much higher levels of reactions are driven by removal of by-products in order to combined formaldehyde than the conventional solids resins. 3. all six hydrogen atoms may be reacted with relative ease to give hexa(methylol)melamine. A generalized composition of a typical mela- fication reaction). ether) bridge. In the first step. Wood and paper applications capitalize on the >NCH2N< (methylene) or >NCH2OCH2N< (methylene relatively rapid cure of the urea resin since lower tempera. Reactions shown in Eqs 3 to obtain a manageable viscosity.5 to 3. It can be seen. Although both of these reactions are superficially straightforward. one exception. and etherified with either n. etc.0 tool for urea resins and 2. with urea as the parent compound. these resins Reactions shown in Eqs 1 and 2 proceed quite rapidly when are viscous and must be reduced with solvent to less than 80% catalyzed by either acid or base. or more ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . All four reactions are equilibrium reactions.or iso-butanol. The HOCH2NHCONHCH20H (2) conventional solids (<80%) resins are made from melamine dimethylolurea or urea reacted with relatively low levels of formaldehyde. but there is nothing in the literature on the kinetics of the etherification N. with the rate of Another. coatings applications are predominantly methylene ether humidity. where The bridging groups in amino resins manufactured for the finished paint must stand up to extremes of temperature.

amino chemists now rely very heavily on gel permeation or prisingly.e. i. effectively prevents complete removal of solvent within the ins are sufficiently low in viscosity that no solvent is needed.. >NH. hence will give low tolerance test results. In that case. (1) methods which reflect the solids content in the absence of amino resins of high molecular weight. To the extent that this occurs. The These are discussed below. the measured decahydronaphthalene/toluene mixture described in ASTM solids content will be lower than the "true" value. and (3) solvent tolerance. NMR for determining levels of combined formaldehyde and alcohol.e. The foil is measure potential cure response.or iso-). In some cases. The rack is quickly inverted. the foil solids test may on occasion overestimate size exclusion chromatography (SEC) and on high-perform- the solids content. which reflect of polar functional groups..5 g) is diluted with xylene and placed in a 110~ oven for Christensen [8 ]. where resin condensation/degradation does occur. The size exclusion www. These conditions are known to Chromatography be sufficiently mild that no resin condensation occurs. Thus. the Gardner bubble viscometer method. carries appreciable > N H and >NCH2OH groups. Typical condense when heated. reagents used include xylene. (2) viscosity. >NCH2OH..e. In general. a solids test method can accept before solution clouding occurs. alco. these res. The loss in standard reagent (solvent). and (2) the solvent is not low boiling. and water. a 1-g sample of resin solution is although the tolerance test represents a quick and easy way to weighed onto a piece of preweighed aluminum foil.62 PAINT AND COATING TESTING MANUAL ins made with both methanol and butanol or even butanol polar. amino resins. and (2) other methods. The foil is placed in a 45~ oven for 45 min. does the resin lose formaldehyde via demethylolation. the paint formulator is interested in the "contrib. reported in milliliters of reagent per gram of sample. especially in the absence of acid catalyst. will have varying degrees of self-condensation in addition to loss of limited compatibility with the typical hydrocarbons used and formaldehyde and solvent(s). and Size Exclusion and High-Performance Liquid the solids content calculated. on each foil surface. resin under test is placed in a rack containing reference tubes ized by three test procedures. One stan- dard method is the ASTM Test Methods for Volatile Content Analysis/Analytical Methods of Coatings (ASTM D 2369).iran-mavad. what fraction of the amino resin solution is to determine the amount of reagent which the amino resin remains in the cured film. tion of the resin and hence have a better understanding of For these reasons. Resins are also made which can be retention of solvent. and usually more fully etherified and so less in viscosity as solvent evaporates slows the diffusion rate and polar than the conventional resins. These procedures. analysis of alkoxy groups by Zeisel cleavage. The foil is then opened up to give a thin film both. Solids Content The most common methods used to determine solids con. which tell of known viscosity. or having high levels self-condensation. Sur. however. Methods discussed include 1H NMR and 13C 1 h. the real purpose which approximates the time and temperature of cure might of the test is to gain insight into the structure and composi- be more appropriate. There may also be a hydrogen-bonding Where solvent is required. and the iso-octane/ hol. etc." i. Test Method for Solvent Tolerance of Amine Resins (D 1198). amino resins for coatings have been character. it does not uniquely define folded over on itself and the sample compressed between the the resin structure. These resins are less polymeric. reweighed. solids test methods fall into two groups: how it will perform in a given coating application. nor To obtain more detailed knowledge of resin structure. Essentially. iso-octane. it is usually either isopropanol or effect between solvent and resin which contributes to the butanol (n. One difficulty with this test before the solution turns cloudy/milky. the increase with DP <3. a low tolerance reading can be two foil surfaces to provide a thin film about 3 to 4 in. alone are also widely used. The sample is then reweighed. and regard to formulation and cure ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . reference tubes are letter graded A through Z and Z1 through Z6. A tube containing the Classically. Bubble Time Method (ASTM D 1545). Experience shows The most common of the first methods is the so-called foil that a low tolerance value means a faster curing resin and vice solids test. and the solids sure how much of the reagent the amino resin can accept content is obtained by difference. where a small resin sample (0. Solvent is allowed to evaporate from a There are a number of different solvent tolerance tests.. Chris. This method is simi- destructive methods for removing solvent from amino resin lar to the Test Method for Viscosity of Transparent Liquids by solutions in order to determine nonvolatile content. Apparently. time frame of the test. Other test methods involve much higher temperatures. are measurement the rate of rise of an air bubble in the sample tube is com- of (1) solids content. Results are typically is the tendency of amino resins to deformylate and/or self. There are a number of other.3 Structural analysis of amino resins has been reviewed by to 0. at the end of which time it is removed. and by Viscosity Measurement trans-etherification followed by gas chromatography. which is used almost universally for high-solids versa. Solvent Tolerance tent are gravimetric. reduced with water. with evolution of formaldehyde. i. However. All weighed sample under carefully controlled conditions of time involve titrating a weighed sample of the amino resin with a and temperature. The tubes are equilibrated to 25~ in a the coating formulator most of what he needs to know with constant temperature bath. While the immediate objective of the solvent tolerance test uted solids. similar tests. pared against similar bubbles in the reference tubes. The object of the test is to mea- weight gives a measure of solvent content. particularly when (1) the resin is relatively ance liquid chromatography (HPLC). Amino resin viscosities are most commonly measured by tensen [8] and Kambanis and Rybicky [9] also describe non. Frequently. (7 to 10 caused by either high polarity or high molecular weight or cm) in diameter.

mixtures of products vides information on resin composition. Unlike the resin components primarily by functional groups. the most widely sold commercial high-solids methylated mel- taken together. Because methanol re- rectly obtained or inferred from any of the various solvent acts with an already-reacted formaldehyde molecule. pro. CHAPTER 8--AMINO RESINS 63 chromatograph provides an excellent measure of number acted. Size exclusion and liquid chromatograms for can never have combined methanol greater than the com- a representative commercial high-solids methylated ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . Thus. represents formaldehyde which has not reacted with methanol and which must therefore Combining Ratios be present as methylol (>NCH2OH).6/5. 6). 5-High-performance liquid chromatogram of a typical high-solids methylated melamine resin. Dimer 150 ~ 100- 50 - 20 25 30 35 40 45 Minutes FIG. of course. 0. while HPLC. Penta- methoxy 350- 200 - Tetra- I A I 100- 0 - 20 25 30 35 40 45 50 Minutes FIG. aldehyde/methanol of about 1/5. which are best described by an average composition. which fractionates formaldehyde and methanol per mole of melamine. see hexa(methoxymethyl)melamine and weight-average molecular weight and molecular weight (HMMM) (Fig. are formed when an excess of formaldehyde is used in the 400 - mV Monomer 350 - 300 - I 250"~ 200 . the commercial example. Acetals of the amounts of formaldehyde and alcohol which have re.1.5 tool in mine resin are shown in Figs. and acetals (>NCH2OCH2OCH3). One of cies are eluted first. 4-Size exclusion chromatogram of a typical high-solids methylated mela- mine resin. The excess formaldehyde. The more polar spe. SEC and HPLC provide detailed information amine resins has an average combining ratio melamine/form- on molecular weight and functionality which cannot be di. bridging groups Amino resins may also be characterized by measurement (>NCHzOCH2N<). bined formaldehyde. which has exactly 6 mol each of combined distribution (polydispersity).iran-mavad. www. a resin tolerance tests. most resins are. For example. Hexamethoxy 400 . HMMM. 600"- mV 500. 4 and 5. followed by the less polar fractions.

h/N(CH 20C H 3)2 acute with resins having high methylol functionality. and acrylics.. polyesters. the methyl and butyl content. and because tively by a number of methods.h/N__. The principal but have limited solubility in hydrocarbons. are water solu. Because of their resinous nature. droxyl group on the primary film-former (acrylic. e.. alcohols and glycol ethers. They are therefore present in many high-solids comparison with other coating resins. usually referred to in product specifications as "free" the best. polyester.. There is a marked drop in viscosity when amino resins Free Formaldehyde are diluted with solvent. Sodium hydroxide is liberated Surface Tension quantitatively on a mole-for-mole basis The surface tension of amino resins is quite strongly re- CH20 + Na2SO3 + HaO ~NaOH + CHa(OH)NaSO3 (7) lated to the nature of the etherifying alcohol and is much less The NaOH is either titrated directly with a standard HC1 affected by the level of combined formaldehyde and alcohol. Care must be taken to high-solids. Some resins. Free formaldehyde may be analyzed quantita. at temperatures above about 140~ This tendency to decompose causes difficulties in de. In the author's laboratory. wherein a hy- especially methylol-rich resins with low levels of both com. Good solvents (e. Typically. Formaldehyde reacts rapidly and completely with aqueous sodium sulfite to form a bisulfite addition complex. This can occur ylated resins to about 28 dynes/cm for butylated resins.g.. and When heated. esters. used is the sodium sutfite method [10]. followed by wet-chemical analysis for formaldehyde nificant amounts of >NH and >NCH2OH functionality are and gas chromatographic determination of alcohol (metha- quite viscous. as described result being the same www. resins carrying sig- rials. surface tension measurements on solution. largely due to breaking of hydrogen bonds. involve complete hydrolysis of the resin to the starting mate- Because of strong hydrogen bonding.64 PAINT AND COATING TESTING MANUAL in Analysis/Analytical Methods. aminos have neither a >NCH2OR + HO--A ~ >NCH20--A + ROH (9) well-defined freezing point nor boiling point. bined formaldehyde and combined methanol. The latter may be a more important con- tributor to viscosity than the former. or neutralized with a known excess of standard HC1. The reduction in surface ten- atures. which can be minimized by performing the titration as rapidly as possible at cool temper. PHYSICAL PROPERTIES REACTIONS OF AMINOS IN COATINGS General Amino resins are typically viscous liquids. which are chemically and mechanistically similar to those hols. formaldehyde and alcohol. One of the most commonly it is somewhat higher boiling. Methanol is probably hyde. Additionally. which take place during synthesis of the resin. with an amine- Cure Reactions like odor. e. particularly methylol have given values ranging from about 45 dynes/cm for meth- groups. reducing viscosity than poor ones [11 ]. which is then back-titrated with NaOH. sion vghen butanol is the etherifying alcohol may be one rea- son that high-solids butyl and methyl/butyl resins provide >NCH2OH ) >NH + CHaO (8) improved flow and leveling in high-solids formulations com- pared to their fully methylated counterparts. amino resins. Older methods viscosity significantly. the end termining the solids content of resin solutions. they may also smell of Amino resins in coating formulations cure by reactions formaldehyde and/or solvent. alkyds. High-molecular-weight "tails" increase ily by either IH or 13C NMR techniques [8]. ized. especially in synthesis.g...~N Viscosity The viscosity of an amino resin is a function of (1) polymer N(CH2OCH3)2 content (degree of polymerization) and (2) the nature of its FIG. direct etherification may take place. Isopropanol is almost as effective.. Amino resins are not generally very polymeric. depending on because of the following reaction. even though they may not be highly polymer- nol or butanol). Uncured resins where typically have glass transition temperatures around -40~ R = alkyl. The problem is particularly (C H 30C H2)2N. or alkyd) reacts with an alkoxymethyl group on the amino ble. e. Many more are water reducible in the presence of other resin solvents. boiling point. alcohols) are more effective at Amino resins always contain some unreacted formalde. with release of A = primary film-former. functional groups. 6-Hexa(methoxymethyl)melamine. etc. they undergo decomposition. Depending on composition. although it is not widely used because of its low formaldehyde.g. represents a good compromise.g. average degrees of polymerization are Determination of combining ratios may be done most eas- in the range of I to 5. reaction of cure is one of trans-etherification. ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . hydroxy-functional glycol ethers. II I N. solvent-free resins using a DeNouy tensiometer ensure that reacted formaldehyde. room temperature or lower. is not analyzed as free formaldehyde.iran-mavad. They are readily soluble in alco. Mixed methyl/butyl resins give intermediate values.

Thus. both mono. as dynamic mechanical analysis [19].. (17) >NCH2OH) since these groups help build molecular weight during cure via self-condensation. These catalysts include very strong mechanisms (a) specific acid catalysis acids such as p-toluenesulfonic acid (PTSA). alkoyxmethyl substitution. either natural or accelerated.. and. i.e. Berge proposed two based formulations. as well as those generated during formulation and/or cure.e. Where high cure temperatures are em. by the base of the proton attached to nitrogen A coreactant resin with a low hydroxyl number is best if --NHCH2OR + B ) --I~ICH2OR + BH § (16) formulated with a "polar" amino (i. hydrolysis of an alkoxymethyl 4. ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . both polar and resistant to alkaline hydrolysis. Degradation and Weathering tors. Cure time and temperature.30]. These are Although the individual reactions of cure are reasonably well understood and have been described in numerous pa- >NH + ROCHzN< ) >NCH2N< + ROH (11) pers [13-18]. been described in detail by Berge [22-24]. nuclear magnetic reso- tions.. dinonylnaphthalenedi- sulfonic acid (DNNDSA)..A M I N O R E S I N S 65 >NCH2OH + HO--A ) >NCH20--A + H20 (10) enced by heat. The functionality of the amino resin. These techniques are useful not only for analyzing the >NCH2OCH2OR + H20 ) >NCH20H + CH20 + ROH (14) freshly cured coating. which tends to inhibit catalysis.+ BH + ) ROH + B (19) matched with an alkoxymethyl-rich amino and cured with a strong acid catalyst.N = CH2 + OR. particularly and (b) general acid catalysis those designed for high-bake temperatures. >NCH2OHR + ) >NCH~. etc. >NCH2OHR + (20) benzenesulfonic acid (DDBSA). while reactions of self-condensation are most influ. of course. group on a singly substituted nitrogen is initiated by removal 5. who was the frst to distinguish between mono. Conversely. and these groups are in fact extremely amino resin is less obvious. Two other reactions may also take place. One of the R = H. The amino/coreactant ratio. in practice. CHAPTER 8 . most formulations involving These two reactions both result in chemical bond forma- resins with high alkoxymethyl ether content and designed for tion between the amino and the primary film-former (co- low-temperature cure (250~ or lower) will call for a sulfonic condensation). On the other hand.21]. i. Other methods.17.. dodecyl- >NCH2--OR + H + :. a majority of studies involve analy- sis of the by-products of cure [13. The relative contributions to cure of the co-condensation and self-condensation reactions will depend on a variety of fac. portions of >NCH2OR. difficulties is. >NHCH2OHR + + A. 3. The functionality (hydroxyl number) of the primary film- former (coreactant).N = CH 2 + H20 ) --NHCHEOH (25) reactions which take place during cure are accelerated by either acid or heat. there is still much to be learned about the overall where behavior of amino resins during cure.+ ROH (21) nyl acid phosphate (PAP). >NCH2OH.. >NHCHzOR + HA ) >NCH2OHR + + A. a very low NH content. The trans-etherification reaction takes place very rapidly under strong acid catalysis. even at low tempera- where tures. These include: Amino-based cross-linked coatings exposed to the atmo- 1.. number of workers. FTIR [17]. > N C H f + H20 ) >NCH2OH + H + (22) Amine blocking agents are sometimes used to help minimize resin advancement prior to cure. and weaker acids such as phe. the choice of nitrogen (N(CH2OR)2).. Some coatings. of which involve reaction of the amino resin with itself (self- condensation). alkyl. can or coil coating operations).g. one rich in >NH and/or --NCH2OR ) . www. that the coating becomes intractable >NCH2OH + HOCH2N< ) >NCH2OCHzN< + H20 (12) as cure progresses.e. hydrolysis and deformylation reactions may also occur nance [20. investigate the structure >NCH2OR + H20 ) >NCHzOH + ROH (13) of the cured film. the relative pro- sphere are subject to both hydrolysis and UV-degradation. a high hydroxyl resin is best if OR. need no catalyst.and di-substituted nitrogen with 2. in an alkaline medium. and >NH groups pres- The mechanisms by which melamine resins hydrolyze have ent initially. This is especially true for aminos with a high level of A = primary film-former. it is fair to say that reactions of Berge's work with melamine resins is undoubtedly relevant transetherification are most influenced by catalyst level and to acid hydrolysis of paint films.iran-mavad. particularly if little or no . such Besides the co-condensation and self-condensation reac.. ESCA. both acid catalyst. While all of the various . etc.N = CH2 + H20 ) --NHCH2OH (18) catalyst is present. acid hydrolysis takes place readily for Acid catalysts are usually used as an aid in curing amino. nonpolar aminos are used.and di-substituted nitrogen. This mechanism is clearly not applicable to di-substituted ployed (e. Hence. but also as a means of following the >NCHzOH ~ >NH + CH20 (15) coating through its lifetime. respect to their behavior towards acid or base hydrolysis. ) >N = CH 2 + ROH + HA (24) former to bring about cure [12]. Thus. in particular the rela- tive contributions of each of the various reactions. The level and type of catalyst (weak acid/strong acid). (23) relying instead on the combination of high temperature and perhaps carboxylic acid functionality on the primary film. either blocked or free. which has been studied by a type. butyl acid phosphate (BAP).

"N~ ~'N ~ Melamine resins are much more widely used. are becoming more widely used. They may require a higher cure temperature or a always occurs to relatively new coatings. But it is also the high level of mela- mine resin which provides the excellent gloss and "distinct- ness of image" (DOI). resins FIG. 8) resins have been available for about a interesting aspect of the acid etch problem is that the damage dozen years. Their use is limited by cost and poor cross-linkers. as well as on the nature and top coat. container 28] used IR to analyze acrylic-melamine coatings exposed to coatings (beer and beverage cans). where acid attack is in exposure of workers to hazardous ingredients in the coating any case minimized by the protective clear top coat. www. such as isocyanates and epoxies. It is the formulation when applied. Their technology and use has developed over many years. Automotive paint manufacturers are also actively pursuing ENVIRONMENTAL/TOXICITY waterborne systems. They give H H better chemical resistance. severe. 7-Benzoguanamine. based on urea and melamine dominate the field. tional post-sprayed). degradation of melamine-containing ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . Another factor is the stabil- pounded because modern high-solids automotive coatings ity of the amino towards advancement (molecular weight use very high levels of melamine resins (35 to 45% of total buildup) during storage of the formulated paint. despite some of the recent difficulties highly alkylated melamines underwent extensive hydrolysis described earlier in connection with water spotting and acid of residual methoxy groups during two years exposure in etch of automobiles.iran-mavad. 7) amino resins are used acrylic-melamine bonds and residual alkoxymethyl groups in where film flexibility and hardness are required. They also have good corrosion and humidity automobiles are presently evaluating and using alternative and detergent resistance. amino is especially important in water-borne coatings. and lower levels of melamine The past 20 years have seen increased emphasis on the cross-linker and which are therefore less severely degraded quality of the environment both in the workplace and beyond. but also to possible restrictions on cure conditions light. They cannot be used in automotive topcoats because of their sensi- tivity to hydrolysis. all of which are susceptible to hydrolysis appliance applications (e. by acid rain. Urea resins are traditionally used in clear coatings for wood.. At the present time. giving rise to correspondingly high levels of Benzoguanamine-based (Fig. with its high melamine content. They are also used to some extent in automotive primers. behaving in some ways as a reactive diluent and plasticizer. which is the princi- . but show automobile is protected from the acid environment for the excellent corrosion and humidity resistance and release first six to twelve weeks.66 PAINT AND COATING TESTING MANUAL English et al. as either a partial or complete replacement for melamines.. characteristic of basecoat/clearcoat technology. An obvious conclusion is that the paint is undergoing additional cure (probably melamine self-condensation) as it ages. which are exterior durability due to the pendant phenyl group on the more stable under acid rain conditions and which can serve benzoguanamine molecule. H H and in some appliance and general industrial coatings. e. If a newly painted higher catalyst level than melamine-based resins. etc. The rate of hydrolysis was slowed considerably when a and compatibility of the amino resin with its co-reactant hindered amine light stabilizer was used.g. Suppliers of high-solids coatings for coil stock. The melamine resin also minimizes the amount of solvent required because of its low viscosity at high-for- mulated solids. binder weight). 8-Glycoluril. general metal applications. kitchen cabinets. both residual methoxy groups and acrylic-melamine bonds. Besides automobiles. [25.26] found that coatings prepared from in exterior applications. which ing and spotting due to "acid rain. this has meant strict controls on systems are only used in the base coat.). film.2 pal site for acid attack. An Glycoluril (Fig. damage thereafter is much less lower amounts of formaldehyde during cure [29].2. consideration must be given not only to interior versus exte- with the rate of hydrolysis being faster in the presence of UV rior use. less functional coreactant resins. etc. these waterborne In the coatings industry. both when formulated and as the paint film is formed In recent years. furni- ture.yN. during solvent flash-off and cure. Compatibility of the motive coatings has been particularly severe because of etch. Bauer [27. but there was no evidence of hydrolysis of bonds appliance formulations (both coil appliance and conven- between melamine and the primary film-former. and foil applications. as well as resistance to weathering FIG. which use higher molecular weight. E n d Uses o f A m i n o R e s i n s Amino-based surface coatings protect and decorate the substrate to which they are applied. they are used in Florida." The problem is com. as in some the cured film. refrigerator doors made from under acid conditions. both UV and moisture and found evidence of hydrolysis of In choosing an amino resin for a particular application. however.g. etc.yN. As already mentioned. in paper. resin.

[16] Santer. [5] Okano. Vol. 1986. especially for the a u t o m o t i v e industry. Vol. 1986. as m u c h as 40 to 50% of total [10] Walker. NY. lower. 1987. G. Amino resin suppliers have r e s p o n d e d to these environ. 1.. J. ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . Vol. network. et al.. Chromatography. 23.. R.. L. Halliwell. [17] Lazzara. 1980. 1983. L. Journal of Applied Polymer Science.. 1982. Vol. and Ohe. however. n a n t l y "combined. [18] Nakamichi. and DeJonge. p. London. 3rd ed. Vol.. Progress in Organic Coatings. No. G. Journal of Applied the e n v i r o n m e n t w h e n the f o r m u l a t i o n is cured. p p m (15-min s h o r t . 52. m u m possible extent d u r i n g cure. p. and Wicks. J. T. M. m o s t concern. D. p. ranging from a b o u t 0. 52. European Polymer Jour- OSHA labelling requirements.." American Chemical Society Symposium Series No. 1979. 187ff. DC. R.. p. 63. M. et al. S. Vol. "The Chemistry of Polymerization Processes. O. Journal of High-Resolution Vol. i. [28] Bauer. and Ugelstad. and Rybicki. Journal of Coatings Technology. 1966. No. 56.. 61. Journal of Coatings Technology.A M I N O R E S I N S 67 a m o u n t s of volatile organics (the so-called VOCs) released to [2] Gordon. a n d r e p r e s e n t s 1984. [21] Bauer... p. No. Conference of G o v e r n m e n t a l I n d u s t r i a l Hygienists (ACGIH) [13] Blank. W. V. Journal of Coatings Technology. p r o d u c e r s have i n c r e a s e d the functionality of the c o r e a c t a n t [8] Christensen. 27. 687. p. 1422. [24] Berge. 14.. 74. Vol. T. 1982. Journal of Coatings Technology. and Spinelli. p. a n d the O c c u p a t i o n a l Safety 1982.e. p.. 61. those presenting the least h a z a r d Chemie.. p. 1980. Recueil de Travail Chimie Pay-Bas. 1984. F o r m a l d e h y d e is r e c o g n i z e d b y the I n t e r n a t i o n a l Agency for [12] Yamamoto. molecular-weight aminos. 1966. Vol. European Polymer Journal. 12. Amino resin suppliers have m a d e c o n s i d e r a b l e progress [20] Bauer. [30] McGuire. 51. 6. use with the object of b u i l d i n g m o l e c u l a r weight to the maxi. [6] Braun. A small a m o u n t .. pp. Vol. J. w h e r e possible.. No. O. Huntington. Vol. CHAPTER 8 . some of the c o m b i n e d formal. M. 51. R. to w o r k e r a n d e n v i r o n m e n t are selected. 60." m e n t a l challenges in a n u m b e r of ways. S..... D. Progress in Organic Coatings. J. d e h y d e in their products. In practice. Journal of Coatings Technology. M a n y a m i n o resins are supplied at Society. nal.iran-mavad. 1988. The f o r m a l d e h y d e content of a m i n o resins is p r e d o m i . p. L. Progress in Organic Coatings.. J. o r un. cure a n d m a y r e a c h the environment.. 193. 23. D. I n c i n e r a t i o n of off gases. and Nahm. [19] Hill. J. h i g h e r levels of a m i n o resin. J. p. and Ogata. and Spinelli. 1952. dehyde a n d all of the free f o r m a l d e h y d e is released d u r i n g [25] English. 762. I.. 2347. and Kozlowski.1 to a b o u t 3% is present free. w h i c h are n o w the resins of choice [4] Aldersley. 14. Vol. This has m e a n t using Vol. 658. Nakamichi. Vol. a b o u t 30 to 50% by weight of the resin. No. Washington. A. Angewaudte Makromolekular W h e r e solvents are needed. No. 241. p. J. Vol. G. 1979. 1970. since the a m o u n t released c a n easily be several [27] Bauer. Krieger Publish- b i n d e r weight in s o m e cases. p. 10. J. Kvaeven. A. p. The A m e r i c a n Technology. 243. 14. times t h a t of the free formaldehyde. Journal of Coatings Technology. 309.... Y. "Analysis of Functional Groups in Amino Res- resin while lowering its m o l e c u l a r weight to m i n i m i z e solvent ins.. J. Polymer Science. 711. Vol. K. No. W. one suspected of 1979. 35.. M. 8. p. Progress in Organic Coatings. has been a progressive shift t o w a r d s higher-solids. ods). Vol.. G. 10. 19. A. 171." Progress in Organic Coatings. p. A. J.. Vol. and Ugelstad. B. [14] Blank.. M. "Characterization of Highly Crosslinked Polymers. 51. 486. 667.. 211-239. w o u l d r e m a i n in the coating after cure as p a r t of the p o l y m e r Vol.. 26. 656. 101. and Briggs.. a m i n o resins is the use of f o r m a l d e h y d e in t h e i r m a n u f a c t u r e . and Anderson. 14. 1980. [1] DeJong. F o r their part. a n d Health A d m i n i s t r a t i o n (OSHA) has set w o r k p l a c e expo- [15] Santer. 54. B. chemically reacted. MacromoIecules. O. and Wilson. 55. H. sure limits of 0. D. p.. 643. p. 20. 5728. 1975. w h i c h is i m p o r t a n t b e c a u s e of [22] Berge. REFERENCES [29] Parekh. 1986. 15. Chase. 3651. Chief a m o n g these SCI Monograph No. p. Formaldehyde.. W. W. p. Journal of Coatings Technology. 1984. 71. 981. T. and Legradic.. p. 751. p. A. 5. p. S. 1984. T. Robert E. Perhaps the m o s t i n t r a c t a b l e e n v i r o n m e n t a l p r o b l e m with [11] Hill. Society of Chemical Industry. D. M. Journal of the American Chemical of coatings formulators.. H. J. G... Vol. B. Vol. release of c o m b i n e d f o r m a l d e h y d e d u r i n g cure w h i c h is of Vol. chanics of the coating a n d curing operation.. Vol. 59. 1977. D. 100% nonvolatiles. Progress in Organic Coatings. p. over the p a s t several years in lowering the level of free formal. 45. 9. D. [3] Gordon. J. Polymer. A. 1153. W. p. ing Co. 16. p a i n t [7] Tomita. 1952. Vol. p.t e r m exposure limit). Advances in Organic Coatings Science and Technology. 101. In an ideal situation... r e a c t e d (see the section entitled A n a l y s i s / A n a l y t i c a l Meth. Journal of Polymer Science. d e p e n d i n g on the me- Vol. Vol. Journal of Coatings Technology. Gudmundsen. 33. 1969.e. 1974.... all of the c o m b i n e d f o r m a l d e h y d e [23] Berge. 1991. is the best solution. www. 1968.75 p p m (8-h t i m e w e i g h t e d average) a n d 2 Vol. carcinogenic potential for m a n . 43. 710. M." i. No. lists f o r m a l d e h y d e as an "A2" substance. D. p. [9] Kambanis. F. 345. H. No. Journal of Coatings R e s e a r c h on Cancer (IARC) as a carcinogen. p. It is the p a r t i a l [26] English. Z. R. 667.

8% Electrical porcelain and electronics sensitive electronic ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ .com Copyright9 1995 by ASTMInternational www. stove side panels are outweighs the cost. tion over a substrate for one or more of several reasons [1]. have added to permit the glaze to form at a readily achievable Moh = 9. No organic resins are truly hermetic. Glazes are applied to their limitations in several areas where ceramic coatings are a substrates by one of several powder-processing techniques: more suitable selection.9% Sanitaryware highest standards of cleanability such as ware that comes in 32. When the substrate is a ceramic.9% Wall and floor tile contact with food and drink. Glaze 2 is a sanitary-ware glaze [5]. but one common theme is chemical durability organic media. of which the Even the most thermally stable organic resins depolymer- glaze typically consumed 10 to 15% of the total manufactur- ize at temperatures on the order of 300~ Hence. and surface of the substrate. impervious to liquids and gases. Organic res- ins are soft (Moh 2 to 3). the coatings must be dried and fired at high These coatings may be applied to a substrate surface in pref. and scratching. and paints are not suitable for applications requiring thermal decorative properties provided by the coating usually far stability above 300~ For example. Cheshire. and waterfall. The total market for these products in the United States was reported to be $3459 billion for 1989 [3]. usually a whiteware. 400 Cedar Lane. which readily attacks all silicate glasses. When the substrate is a Glaze 1 is a feldspathic glaze suitable for use on soft paste porcelains or hard stoneware [4]. are formulated to be resistant to a variety of reagents. and some plasma coatings are much Glazes are essentially mixtures of silica with other oxides harder. The raw materials are both crystalline oxides and frits. dipping. as well as to essentially all quirements. It is derived from the 1Consuhant. In a leadless glaze. The only important exception is hydrofluoric and cleanability. are used to provide the fluxing action. functional. A similar argument can be made for abrasion resistance. alumina coatings. coating is called a glaze. combined with a very smooth surface. By contrast. Eppler ~ CERAMIC COATINGS ARE AN ALTERNATIVE t o organic paints for GLAZES surface coating applications. from The major markets for ceramic coatings have different re- acids to hot water to alkalies. However. MNLI7-EB/Jun. After application. Increasing the melting rate by increasing the per- 68 www. abra- sion. together with magnesia (MgO). but stove tops are porcelain enameled. This outstand. it is almost al. zinc oxide (ZnO). painted. the coating is called a glass enamel.9% Tableware for applications requiring true hermeticity. Ceramic glazes find their way into a wide range of applica- stantially exceeds that of organic paints [2]. the Table 1 gives the formulas of a few typical ceramic glazes. temperatures (up to 1300~ typically 1000 to 1100~ to fuse erence to an organic paint to render the surface chemically them onto the substrate.astm. spraying. For example. A ceramic glaze is a vitreous coating applied to a ceramic ways less expensive to paint. Eppler Associates.iran-mavad. coating is called a porcelain enamel. temperature. and more resistant to service temperature. renders uted as follows: many ceramic coatings suitable for applications requiring the 43. quantity. In these wet processes the raw Vitreous (glassy) ceramic coatings are chosen for applica- materials are dispersed in an aqueous slip for application. vitreous coatings are Leadless Glazes harder (Moh 5 to 6). organic ing cost. usually to protect 9. This glaze is typical of that glass.5% Artware 2. When painting with a suitable material will meet all service requirements. more inert. When the substrate is a metal. the boron oxide (B203). acid. used on medieval Chinese porcelains. 1995 Ceramic Coatings by Richard A. Applications for Glazes The chemical durability of ceramic coatings in service sub. CT soft paste porcelain glaze by the addition of ZnO in large 06410. plasma sprayed. These coatings are also suitable 10. the alkali and alkaline earth Vitreous coatings are thin layers of glass fused onto the oxides. organic paints have substrate. more readily cleanable. Hence. the value of the protective. The major products that normally use glazes are distrib- ing durability. Vitreous coatings tions ranging from coffee mugs to automotive spark plugs.

36 62. Whiteware Materials by the Interferometric Method C 372 Test Method for Linear Thermal Expansion of PbO is highly toxic..04 9.T e s t Method for Lead the physical properties of ceramic glazes.00 0..71 0.45 0.72 7 0.44 0. . of appropriate refractive index in the glaze [5]. C 5 3 9 .08 6.07 2. a n d C 5 5 6 .00 3 6.00 4 1. the Ceramic Whitewares by a Thermal Shock Method most i m p o r t a n t of which is the strong fluxing action of PbO.Glazes for electronic substrates. However. Glaze C 738 Test Method for Lead and Cadmium Extracted from 7 is an example of a coating used on integrated circuit pack.00 0.00 28.86 0. tack by Detergents..00 0.00 0.00 0.57 5 3..47 7. Ceramic Whitewares and Related Products C 1034 Test Method for Lead and Cadmium Extracted from nerware glaze [9].00 14.71 9.00 0.17 35. as well as Table 2 [12].00 0. Therefore. [6].00 0.44 69.90 0. Glaze 6 is a n example of a clear glaze Glazed Ceramic Cookware suitable for use o n artware a n d hobbyware bodies [10].00 0. Porcelain Enamel and Glaze Frits and Ceramic a n d some dinnerware.00 6 2.00 0.00 1. dip.36 10. durability. the coefficient of Number Title t h e r m a l expansion m u s t be reduced to m a t c h that of the C 1027 Test Method for Determining Visible Abrasion ware.00 2 2.16 0.24 3.85 1..00 0.00 3.88 0..14 0.T e s t coatings are prepared in a n aqueous system a n d applied to Method for Linear T h e r m a l Expansion of Porcelain E n a m e l the substrate by spray.T e s t Method for Crazing Resistance of Fired Glazed Ceramic Whitewares by a Thermal Shock Method.79 0.00 0. from Glazed Ceramic Cookware. CHAPTER 9--CERAMIC COATINGS 69 TABLE 1--Typical ceramic glazes in weight percent. ASTM Committee C-21 on Ceramic Whitewares a n d Re.. Glazed Ceramic Surfaces ages to seal t h e m [11]. These include: C 6 5 0 .24 9. a n d tiles c o n t a i n lead oxide.00 88. Several other ASTM methods are concerned with chemical minosilicate a n d zinc silicate crystals are c o m m o n l y used. The coating is www.T e s t Method for Linear T h e r m a l E x p a n s i o n of Porcelain e n a m e l coatings are ceramic coatings designed Porcelain E n a m e l a n d Glaze Frits a n d Ceramic Whiteware for application to metals.04 42.16 10. These include: C 5 5 4 .00 0. Glaze 4 is a n example of a glaze for vitreous hotel c h i n a Resistance of Glazed Ceramic Tile [7]. Of particular c o n c e r n are ASTM methods used to control release of lead and c a d m i u m from glazed Testing o f Glazes surfaces.00 16.65 0.99 8.00 35.57 55.05 3. Glaze Na20 KzO CaO MgO ZnO SrO BaO PbO B203 A1203 SiO2 ZrO2 1 2.00 0.54 1.00 0.72 7.81 2.18 0.20 9.08 0.71 0.50 0.15 0. Glaze 8 in Table Test Method for Resistance of Overglaze Decorations to At- 1 is a n example of a matte ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ .00 18.94 3. and C 3 7 2 . artware.87 4.30 8.00 0. velvet appearance.00 0. C 584 Test Method for 60-deg Specular Gloss of Glazed Glaze 5 i n Table 1 is a n example of a lead-containing din. C 650 Test Method for Resistance of Ceramic Tile to Chemical Substance C 609 Test Method for Measurement of Small Color Lead-Containing Glazes Differences Between Ceramic Wall or Floor Tile C 554 Test Method for Crazing Resistance of Fired Glazed Litharge (PbO) is used in glazes for several reasons [8].00 0.00 0. C 4 2 4 .58 59.00 5.09 0.67 0. Calcium alu. To produce a glaze for dinnerware.T e s t Method for Lead a n d C a d m i u m Extracted from lated Products has developed several test methods to evaluate Glazed Ceramic Surfaces.00 5. These are listed in a n d C a d m i u m Extracted from Glazed Ceramic Tile.00 0.37 55. leading to Attack by Detergents greater flexibility in the f o r m u l a t i o n of the glaze to o b t a i n C 539 Test Method for Linear Thermal Expansion of desired properties.iran-mavad.93 7. use of lead-containing glazes Porcelain Enamel and Glaze Frits and Fired Ceramic requires special care in processing a n d in testing the ware Whiteware Products by the Dilatometer Method produced.00 0. C 895 Test Method for Lead and Cadmium Extracted from Glazed Ceramic Tile Satin and Matte Glazes a n d Glaze Frits a n d Fired Ceramic Whiteware Products by Satin a n d matte effects are due to dispersed oxide crystals the Dilatometer Method.91 10. These tests form the basis for most quality C 1035--Specification for Lead and C a d m i u m Extracted control testing programs.T e s t Method for Resist- The crystals m u s t be very small a n d evenly dispersed if the ance of Ceramic Tile to Chemical Substances.62 10.25 0.00 0. Conventional porcelain e n a m e l Materials by the Interferometric Method.00 11. wall-tile glaze such as Glaze 3 TABLE 2--Test methods for ceramic glazes [12].00 0.06 1.00 8 0. a n d C 8 9 5 .00 0~00 0. C 424 Test Method for Crazing Resistance of Fired Glazed Whitewares by Autoclave Treatment which allows the f o r m u l a t i o n of glazes that m a t u r e at tem.92 cent of fluxes yields a fast-fire.46 0. or flow coating.- glaze is to have a smooth. C 7 3 8 .12 11. C 556 Test Method for Resistance of Overglaze Decorations to peratures lower t h a n their leadless counterparts. These include: C 1034--Test Method for Lead a n d C a d m i u m Extracted from Glazed Ceramic Cookware.39 0. There are several m e t h o d s concerned with the fit of the glaze to the substrate.T e s t Method for Crazing PORCELAIN ENAMELS Resistance of Fired Glazed Whitewares by Autoclave Treat- ment.47 7.

00 0.27 0.37 15.s t r e n g t h b o n d to the metal substrate.66 7.20 40.00 0.65 0.T e s t Method for Alkali Resistance of Table 3 is a n alkali borosilicate c o n t a i n i n g small a m o u n t s of Porcelain Enamels. while cover coat enamels do not. Porcelain E n a m e l e d Utensils to Boiling Acid. Cover Coat E n a m e l s tion of powdered porcelain e n a m e l by electrostatic spray. such as ranges.19 0. Again. Newer technology involves dry applica.31 2.01 41.23 K20 2. surface hardness.92 7. is the possibility of defects providing a pathway from the E n a m e l 4 is a c o n t i n u o u s clean coating.04 0. E n a m e l 2 Surface Finishes.33 0.56 0. or opaque.- G r o u n d Coat E n a m e l s Test Method for Acid Resistance of Porcelain E n a m e l s (Citric A general-purpose g r o u n d coat e n a m e l like E n a m e l 1 in Acid Spot Test).05 24.47 0.89 1. G r o u n d coat enamels c o n t a i n ganic Coatings.00 2.18 2.36 11.00 0. a n d cupric oxide (CuO). coating which provides a m e a n s of volatilizing a n d removing Methods in this area include: C 5 3 6 .03 0.00 0. Oxide Enamel1 Enamel2 Enamel3 Enamel4 Enamel5 Enamel6 Enamel7 Li20 0.30 ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . form the basis for most quality control test programs.00 0.00 0.88 0. S e m i o p a q u e A porcelain e n a m e l m u s t be formulated such that it will enamels like E n a m e l 6 are used for most m e d i u m . C 6 1 4 .35 www. nickel oxide (NiO).00 0.99 7.T e s t Method for Color Retention of is a h o m e l a u n d r y enamel that has been formulated for out.00 0. Orange..74 59. can be added to Test m e t h o d s for porcelain e n a m e l coatings are u n d e r the a n e n a m e l f o r m u l a t i o n to improve the adherence between the jurisdiction of ASTM Committee B-8 o n Metallic a n d Inor- metal a n d the substrate.00 13.07 ZrO2 0.55 56.15 12.00 0.00 0. C 7 4 3 .72 Cr20 s 0. About 86% of the ance.00 1.60 13. C 7 5 6 .00 0.00 0. a b r a s i o n resist- ported to be $5486 billion i n 1989 [13].81 1.T e s t Method for Cleanability of adherance oxides to promote the b o n d i n g process.15 3.00 1.30 0.00 0.a n d corrosion-resist.27 0.00 SiO2 44.47 6.00 ZnO 0.00 MoOs 0.00 0. A related issue ance requirements. which for iron a n d steel substrates is ferrous oxide (FeO).20 0.53 7. a n d C 2 8 3 .00 0. a n d resistance to corrosion.T e s t Method for Resistance of E n a m e l 3 have very stringent thermal.73 0.00 0.52 0.81 0.00 0.00 CuO 0.iran-mavad.00 0. Several of these test methods are c o n c e r n e d with the chem- ical durability of porcelain enamels. C 5 3 8 .00 0.86 TiO2 0.00 WOs 0. Hot water t a n k coatings like E n a m e l Surfaces.00 0. developed by saturating the e n a m e l coating a n d the substrate metal with a n oxide of the metal [15]. About 6% are cast-iron sanitary Opaque enamels such as E n a m e l 5 are used for white a n d ware. This structure is lations without the adherance oxides.00 0.00 0. They are similar to g r o u n d coat formu- electronic structure across the interface [14]..00 0.11 A]203 6.97 46..00 0.18 16.02 41.00 0.T e s t Method for Continuity of Porcelain TABLE 3--Typical porcelain enamels in weight percent..00 0.00 Sb203 0.00 MgO 0. a n d miscellaneous pastel coatings [18].00 1. a n d dishwashers.00 0.. The methods are listed in Table 4.47 F 2.00 0. a n d Yellow Porcelain Enamels. Red.50 2.T e s t standing alkali resistance t h r o u g h the addition of large q u a n . a n d products are appliances. C 8 7 2 .56 0.97 13. such as cobalt oxide (COO).25 1. a n d 8% are architectural. semiopaque.00 P205 0.58 MnO2 0.00 7. cookware. This is a porous surface to the substrate.00 0.00 0. Testing. it is necessary to develop a c o n t i n u o u s strong.06 0.80 2.30 9.30 1.00 NiO 0.00 0.58 12.00 0. heat.00 0. They include: C 2 8 2 .00 CoO 0.72 3.00 0.00 0.35 11.31 0.55 0.00 0. h o m e t h e r m a l shock. usually called c o n t i n u i t y of coating.76 Na20 13.18 0.70 0.03 20.20 0.00 0.. titania (TiO2) to provide the opacification.00 0.99 0.34 2.13 16.00 0.00 0.00 0.00 0.00 0.25 3.17 3.71 2.83 CaO 6.66 1.00 0.00 0.00 6. For proper adherance of the colors.04 0.00 B203 15. Method for Lead a n d C a d m i u m Release from Porcelain tities of zirconia (ZrO2) [16].13 9.00 0.24 0.00 0.36 0.05 0. laundry.70 P A I N T A N D COATING T E S T I N G M A N U A L dried before firing.93 2.41 8. Cover coat porcelain enamels are formulated to provide The total market for porcelain-enameled products was re- specific color a n d appearance characteristics..00 0. They c a n be clear.38 2.24 0.03 0. They c o n t a i n high c o n c e n t r a t i o n s of items.T e s t Method for Conti- food soils from the i n t e r n a l surfaces of ovens during n o r m a l nuity of Coatings in Glassed Steel E q u i p m e n t by Electrical operation [17].00 1. Testing o f Porcelain E n a m e l s Certain t r a n s i t i o n metal oxides.00 BaO 7.03 0.29 0.10 1. water heaters.00 Nb205 0.00 0. they adherance oxides. Clear enamels like E n a m e l 7 are used to produce e n a m e l to the metal.26 1. bright colors.00 0.00 0.47 0.45 0.60 1.

lighting. C 385 Test Method for Thermal Shock Resistance of C o m b u s t i o n flame spraying is used for c o a t i n g m a t e r i a l s t h a t Porcelain-Enameled Utensils melt readily. The r e q u i r e m e n t for low ma- turing t e m p e r a t u r e s necessitates the use of very high lead Testing of Glass Enamels oxide c o n t a i n i n g borosilicates for the flux. Three m e t h o d s of h e a t i n g Test Method for Sieve Analysis of Wet-Milled and Dry- Milled Porcelain Enamel a n d propelling the particles in a plastic c o n d i t i o n to the C 703 Test Methods for Spalling Resistance of Porcelain.T e s t M e t h o d for Detergent Resist- C 756 Test Method for Cleanability of Surface Finishes ance of Ceramic Decorations on Glass Tableware. the Lip and Rim Area of Glass Tumblers Externally t h e r m o p l a s t i c s . C 6 7 6 . CHAPTER 9 .T e s t M e t h o d s for Alkali (Citric Acid Spot Test) Resistance of Ceramic Decorations on R e t u r n a b l e Beverage C 614 Test Method for Alkali Resistance of Porcelain Enamels Glass Containers. Glassed Steel Reaction Equipment by High Voltage I n these processes. and Yellow Porcelain Enamels C 9 2 7 . They r e p r e s e n t a spe. oxides.. C 676 Test Method for Detergent Resistance of Ceramic ical d u r a b i l i t y or in cleanability.iran-mavad. b u t have n o t yet achieved c o m m e r c i a l l y of S u b c o m m i t t e e 14. They Decorations on Returnable Beverage Glass Containers provide a m e a n s of decoration.T e s t M e t h o d for L e a d a n d C a d m i u m E x t r a c t e d f r o m C 839 Test Method for Compressive Stress of Porcelain the Lip a n d R i m Area of Glass T u m b l e r s Externally Deco- Enamels by Loaded-Beam Method r a t e d with C e r a m i c Glass Enamels. car- Porcelain Enamel and Glaze Frits and Ceramic Whiteware Materials by the Interferometric Method bides.. a n d C 538 Test Method for Color Retention of Red. a n d automotive. The m a r k e t s for this specialty prod. fluxes. are listed in Table 5. the coating m a t e r i a l is m e l t e d a n d p r o - C 283 Test Method for Resistance of Porcelain Enameled jected as h e a t e d particles onto the suhstrate. s u b s t r a t e surface include: (1) c o m b u s t i o n flame spraying. not an i m p r o v e m e n t in c h e m . These coatings m u s t be ma. The organic s u s p e n d i n g m e d i a are mittee C-14 on Glass a n d Glass Products. Orange. C 7 3 5 .. w h e r e it instan- Utensils to Boiling Acid C 285 t a n e o u s l y solidifies as a coating.T e s t M e t h o d for Acid Resist- C 448 Test Methods for Abrasion Resistance of Porcelain ance of Ceramic Decorations on R e t u r n a b l e Beer a n d Bever- Enamels C 282 Test Method for Acid Resistance of Porcelain Enamels age Glass Containers. Silicates. C 6 7 5 . Method Subject C 724 Test Methods for Acid Resistance of Ceramic Decorations on Architectural-Type Glass C 735 Test Method for Acid Resistance of Ceramic Decorations on Returnable Beer and Beverage Glass GLASS ENAMELS Containers C 675 Test Methods for Alkali Resistance of Ceramic Glass e n a m e l s are vitreous coatings a p p l i e d on glass. a n d (3) d e t o n a t i o n gun spraying. These m e t h o d s [12] similar to m a t e r i a l s u s e d to m a k e organic paints.. As s u p p l i e d to the user. a n d organic s u s p e n d i n g media. Glass Coatings on Glassed Steel R e a c t i o n E q u i p m e n t by H i g h ASTM Voltage. d u r a b i l i t y of glass decorations. glass Decorations on Glass e n a m e l s are m e c h a n i c a l mixtures of pigments.T e s t M e t h o d for Reliability of TABLE 5--Test methods for glass enamels [12]. a n d nitrides have all been d e p o s i t e d by this C 537 Test Method for Reliability of Glass Coatings on process. C 978 Test Method for Photoelastic Determination of Residual Stress in a Transparent Glass Matrix Using cialty p r o d u c t that is m o r e a k i n to organic p a i n t s t h a n to a Polarizing Microscope and Optical Retardation o t h e r c e r a m i c coatings. Decorated with Ceramic Glass Enamels d i u m s ) b y a few select m a n u f a c t u r e r s . Decorations on Glass Tableware t u r e d at t e m p e r a t u r e s b e l o w the d e f o r m a t i o n p o i n t of glass C 824 Practice for Specimen Preparation for Determination of (1000 to 1200~ o r 538 to 649~ Hence.T e s t Number Title Methods for Acid Resistance of Ceramic Decorations on Ar- chitectural-Type Glass.C E R A M I C COATINGS 71 E n a m e l Coatings. They include: C 7 2 4 .. Leadless fluxes are Test m e t h o d s for glass e n a m e l s are u n d e r the j u r i s d i c t i o n u n d e r development. architec. Compensation Procedures uct are c a t e g o r i z e d as tableware. Most of these m e t h o d s are c o n c e r n e d with the c h e m i c a l TABLE 4--Test methods for porcelain enamels [19]. C 777 Test Method for Sulfide Resistance of Ceramic tural. glass containers. C 536 Test Method for Continuity of Coatings in Glassed Steel Equipment by Electrical Testing C 743 Test Method for Continuity of Porcelain Enamel Coatings REFRACTORY COATINGS C 374 Test Methods for Fusion Flow of Porcelain Enamel Frits (Flow-Button Methods) C 346 F l a m e s p r a y techniques can be used to a p p l y c e r a m i c coat- Test Method for 45-degree Specular Gloss of Ceramic Materials ings in the m o l t e n state to heat-sensitive o r massive sub- C 872 Test Method for Lead and Cadmium Release from strates that c a n n o t themselves be h e a t e d to high tem- Porcelain Enamel Surfaces ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . s p r a y m e d i u m s . ultraviolet curable me. Most c e r a m i c coating m a t e r i a l s u s e d currently c a n C 539 Test Method for Linear Thermal Expansion of be a p p l i e d b y flame spraying [20]. P l a s m a arc flame spraying is used for very re- www. they require large Linear Thermal Expansion of Vitreous Glass quantities of fluxing elements so t h a t c h e m i c a l d u r a b i l i t y is Enamels and Glass Color Frits by the Dilatometer Method difficult to achieve.10 on Glass D e c o r a t i o n of ASTM Com- acceptable properties. C 927 Test Method for Lead and Cadmium Extracted from Glass e n a m e l s are p r o d u c e d in ready-to-use form (paste.. silicides. a n d C 5 3 7 .. (2) Enameled Aluminum p l a s m a arc flame spraying.

and space powdered frit melts and adheres as it falls on the hot surface. A.26]. For coating a total several powder-processing techniques. The fluidized powder is siphoned and propelled through Spraying is a process whereby a coating slip is broken powder feed tubes to special electrostatic powder guns for down into a cloud of fine particles that are transferred to the low-pressure application. the molten state to heat-sensitive or massive substrates. R. and Ceramic Superconductors. A. Hence. shape and size of of a vibrating sieve placed over the surfaces to be coated. mechanical. which throw the coating into a fan of droplets. and. REFERENCES Slip can also be applied mechanically with a rotating atom- [1] Eppler. 1. It is then sus- material. 36. Park quality and uniformity of a ceramic coating can be improved Ridge.. face. the silk screen process can be used [20]. the grounded workpiece. available. R. limited to applications grounded substrate following the lines of force. ing material can reach the underside of the ware. They are. a casting is heated in a and flexible [21]. This tech- capital equipment. Its limitations are extreme sensitivity to operator pended in clean compressed air in a fluidized bed container skill and difficulty in automating volume production. In [3] Ceramic Industries. or curtain technique Testing of Refractory Coatings [21]. particle-size reduction. and the one mined on an individual basis. lends itself to high-volume automated systems [24]. E. Corrosion of Glass. There are a few techniques of application that do not re- volves mixing the ingredients. economical. resistant shapes. while still hot. applied readily by any other technique." Chap. Academic Press. sible areas. 1983. They are driven forward to the usually porous.. and the addition of minor amounts of additives dry powder cast iron enameling. All of these factors affect the quality and the cost of This process is also extremely operator sensitive. They include flame spraying. New York. the slip is broken into droplets either by air spraying is used for hard. voltage and then spraying them towards the substrate sur- shaken to remove excess slip.72 PAINT AND COATING TESTING MANUAL fractory materials such as metal carbides. or electrical up to 100 kV. and set down to drain and dry. producing textured coatings on tile. nique involves charging individual coating particles at a high moved around in a controlled way. In dry powder cast-iron enameling. this paste is pressed through the open areas Ceramic coatings are applied to their substrates by one of of a fine mesh screen stretched on a frame. so that the best solution must be deter. Painting and brushing are seldom used the ASTM standards: C 633--Test Method for Adhesion or except for special effects and for applying glaze to inacces- Cohesive Strength of Flame-Sprayed Coatings [19]. p. most recently introduced. coat- such as thermal barrier coatings. www. Charging of particles is accomplished by encapsulating Any bare spots are touched up with a finger wet with coating the coating material with an organic silane. There are other techniques for specific applications. an impelling agency. Detonation gun this system. The ware is immersed in the coating slip. The most important dry application method. a coating process. Slip is passed onto a set of closely spaced rotating disks Technology. but operating costs are reduced through elimina- booth maintained under negative pressure [23]. This suggests the waterfall. ting surface. and electrostatic dry powder to modify the rheological properties of the slip [21-22]. "Glazes and Enamels. Capital costs of this process are anism. "Corrosion of Glazes and Enamels.. The arti- cles are continuously fed under a battery of angled spray guns.iran-mavad. Using a squeegee. Glass Science and izer. These enameling. removed from the slip. 4. Costs are 301-337. a metal). where a continuous feed of tiles is carded under a There is only one test method for flame spray coatings in curtain of fluid slip. The drops acquire a high negative charge and Flame spray coatings generally lack smoothness and are are dispersed as a fine mist. For substrates which require precisely positioned areas of coating. The ware. 12. Noyes Publications. Vol. which causes it to seek out and attach itself to forces. costs are excessive. where the materials cannot be edge coverage is achieved. quire the preparation of a slip. Flame spray coatings generally lack smoothness and are usu- The application process for a ceramic coating must be ally porous. processes are carried out together in a ball mill comprising a Flame spraying can be used to apply ceramic coatings in rotating cylinder partly filled with freely moving. pp." Chap. Selection of the application technique is one furnace to red heat. similar to spraying. The method requires a gun. If the substrate is conductive (that is. disper. August 1990. is dry powder electrostatic applica- Dipping is a simple. Eds. wear-resistant materials such as atomization or by centrifugal force from a sharp-edged rota- tungsten carbide. and full- and wear-resistant coatings. The primary use of this technique is in [2] Eppler. K. rapid technique requiring no tion of all-fritted coatings to conductive substrates. ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . energy and labor costs. by using the electrostatic spray coating technique [25. Slip preparation in. therefore. throughput required. In wet processes the piece. Clark and B. a container or feed mech. straightforward and foolproof. raw materials are dispersed in a slip. dusted with dry powdered frit by means Criteria for this selection are type of ware. reproducible. Coating reclaim is an essential part of automated sys- tems. 1992. Spraying tion of slurry preparation and drying of the ware. where porosity is a virtue. the surface D. The powder carries a potential of substrate by either pneumatic. efficient. It is then withdrawn from the furnace of the most important decisions the coatings engineer makes. Finely pow- COATING APPLICATION dered dry coating material is dispersed as a smooth paste. Equipment and material costs are generally high. but with a very smooth coating. and a properly designed hood or substantial. [27]. sion in water. Ceramics. impact. Zoitos. Tile require only one face to be glazed.

F. Vol.iran-mavad. pp. R. Vol. Vol. Coating. [25] Hebberlein. 51-55. H.. 46." tions.. Proceedings. F. No. 456. 11.. "Performance [6] Orth.05: Metallic and Inor- for Low Lead Release. 53. H. 1984. 1967. 1970. "Glasses in Microelectronics Sanitary Whiteware Shops. No. Vol." Journal of the Amer. Whitewares. "Ching-te-Chen. and Eppler. Painted Post. Vol..Y." Transac- in the Information-ProcessingIndustry. L.A. OH. F. 5... Vol. R. 42. 1982. R. 1t. Part 2.. PEI Technical Forum. OH. New York. OH.. 32. 1983. R. 73. 49. 1959. pp. 532-547. [7] O'Conor.. can Ceramic Society Bulletin. Tripp. No. 5. [17] Monteith. R." "Commercial Glasses.G. PEI Technical Forum. August 1990. J. pp. 504-525. and German." Berichte [14] Pask. New York. L. "Chemical Reaction and Adherance at Glass-Metal der Deutschen Keramischen Gesellschaft. 65-69. Hyde. tion Bulletin. and Bull. O. "Spraying of Earthenware Flatware. "Recent Develop. G. 77. 1976. 1978. W. S. R. pp. 1974. 4. Gill. International ganic Coatings. R. Interfaces. [18] Shannon. Smith and M. ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ .. "Environmental Conditions in [11] Tummala. R. [20] Taylor. Ceramic tions..02: Glass. 4. Vol. 87-102. NY. Part 15.A. Oxford." American Ceramic Society Bulletin. pp. John Wiley & Sons. R. [27J ASM Committee on Porcelain Enameling. Vol. A." N." Proceedings. and Shaw. D. 1-16." Proceedings. 1986... A. 1971. Perga- tions.. W... "Formulation and Processing of Ceramic Glazes [19] ASTM Annual Book of Standards. 107-109. Journal of the British Ceramic Society.. "Ceramic Glazes. B. 22. Vol. 1971. L." Illinois University Engineering Experimental Sta- ing& Vol. 2. mon Press. "Lead in Glazes--Benefits and Safety Precau- [21] Taylor." Metals Handbook. 74-96. 2. II."American Ceramic Society Bulletin. [13] Ceramic Industries. Vol. Introduction to the Principles of Ceramic Processing. 496-499. 18. pp. Vol. W. "Ceramic McLaren.. www." Chap. "Nature of elling to Parts in Sheet Steel and Cooking Equipment. A. No. pp. "Effect of Firing Rate on Physical Properties of Tests for Properties of Low Temperature Thermal Cleaning Wall Tile. and Friedberg.. 1064- [5] Singer. Vol. R. pp. A. P.. M. H. E. D. J. pp. R. 841-844." Ceramic Engineering Society Proceed. R. R. 1067.. and Eppler. Vol. "Porcelain Enamel- [16] Eppler. J. pp. pp. R.. Enameller. M. Linhart." Transac- [12] ASTM Annual Book of Standards... lain Enamels. 1964. 125-129. No. No. E. 10. E.. Views of a Porcelain City. pp.. [10] Eppler. Enamel Resistance and Experimental Results Obtained." Ameri- State Institute for Glaze Research. "Electrostatic Glazing of Tableware. "Formulation of Glazes for Low Pb Release. England. J. C. Glaze Spraying Shops. 11-17. 1988. Ceramics Glaze Technology. 923-932. ASM International. A. 1976. No. 9th ed. "Resistance of ing. and Duckworth.. Lead Industries Association. CHAPTER 9--CERAMIC COATINGS 73 [4] Tichane. [8] Eppler. [9] Marquis. L." Borax Consoli. lumbus. American Ceramic Society Bulletin. A. 1975. Journal of the British Ceramic Society. "Industrial Application of Electrostatic Enam- [15] King. and Slaga. No. V. Advances in Ceramics. [24] Whitmore. 56. 54.. C. 1982. 1960." [22] Reed. F. C." Vitreous Adherance of Porcelain Enamels to Metals. J. Vol. Conference of Ceramic Foodware Safety... P. p. pp. J. 12. Nos. 1977. 921-923. K. Bergeron.. 1986. pp. Co. 50. Porcelain Enamels to Attack by Aqueous Media: I--Tests for Metals Park. dated. A. [23] Bloor. W. pp. American Ceramic Society. 1973. and Smalley. 9th ed. A. ASM International. 73-79. No. W. and Eardley." Metals Handbook. Metals Park. S.. 9. [26] Lambert. ican Ceramic Society. "Titania-Opacified Porce- ments in Leadless Glazes. Eds. Vol.. H. T. Oven Coatings. 5. 24.

Almost since their bisphenol A based epoxy resins. elec- chemical plants. the n value been used in protective coatings. 2 and Michael J. and ketimines. adhesives. the generalized structure of commercial introduction in 1950. been developed over the years for epoxy resins is overwhelm- formance. CURING AGENTS The principal components of any epoxy resin coating sys- tem are the epoxy resin and the curing agent or hardener. Cross-linking agents. ent-cure coatings and the amino. and for chemical-resistant linings of pails and that are commercially available along with their properties drums. Epoxy resins are reactive intermediates composed of mix- Epoxy resins are reactive intermediates that can be liquid or tures of oligomeric materials containing one or more epoxy solid. the epoxy equivalent weight (EEW) in- oxy resin have been growing. cured by reaction of the hydroxyl functionality. curing agents as they are generally called. as does the number of hydroxyl Copyright9 1995 by ASTMInternational www. As n increases. resins with low n values are normally cured by reaction of the Epoxy resin coatings offer a unique combination of adhe. epoxy group. tain one or more epoxy (oxirane) groups per molecule. of the container from corrosion. are normally used in solution and find their great- protect both the inside and outside of pipe. whereas those resins with higher n values are sion. Amine- 77521-1380. Bauer. infusible polymer network. particularly those above 3000 molecu- automotive.O. and marine equipment such as offshore trical castings. it is dependent on the performance requirements of the film and the constraints dictated by the specific method RESIN TYPES of application. or give a three-dimensional. although higher-molecular-weight coatings were the largest single end use for epoxy resins. they ments. aircraft.astm. tomato juice. Watkins 2 EPoxy RESINSHAVEBECOMEtechnologically important materi. epoxy resins most widely used by far in coatings are the ings. Selection of the curing agent is as important as that of the base resin. These coatings are used not only to protect the metal and applications. they must be cross-linked or "cured" into a three- reacting with specific groups in the epoxy resin molecule to dimensional polymer network. epoxy resins can be characterized as a group resin coatings are the amine-functional materials for ambi- of commercially available oligomeric materials which con. To convert epoxy resins into useful with curing agents (hardeners). These applications require liquid resins plications where epoxy resin coatings are used almost exclu. polyamides. Table 1 displays a range of typical epoxy resins products. coatings still represent about creases. forced composites. Westhollow Research Center. having good flow and are cured through the epoxy ring. In these resins the the predominant thermosetting resin used for the interior concentration of epoxy groups is low. and appliance primers as well as to lar weight. Curing agents function by products. cure speed. are used mainly in ambient-temperature cure coatings. ing. and so they are cured linings of beer and beverage cans. Houston. and physical properties that pro. agents used in ambient-cure coatings are aliphatic amine ad- ment Co.iran-mavad. and reinforced plastics. flooring. ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . which can be affected by direct contact with metal. vide outstanding protection against severe corrosive environ. The sively because of the corrosion protection they afford include higher n value resins.. functional materials cure epoxy resins by polyaddition 74 www. Thus epoxy half of the annual epoxy resin usage. and they are converted into the final coating by reaction groups per molecule. and fiber-rein- drilling platforms and merchant ships. 1995 10 Epoxy Resins in Coatings by Ronald S. 1 E d w a r d J. other materials are incorporated to achieve the in the epoxy resin. but also to protect the flavor of the contents. chemical resistance. and film per. thermoplastic resins having n values of 200 or more are avail- Although in recent years the noncoating applications of ep. epoxy resin systems have which is given in Fig. able. TX ducts of epoxy resins. 1. Marx. cans for hard-to-contain with materials that react with the hydroxyl groups along the food products such as sauerkraut. Other important ap. Shell Develop. Epoxy resins are est application in heat-cured coatings. function by reac- though the resin and curing agent are common to all epoxy tion with or cause the reaction of epoxide or hydroxyl groups coatings. The number of curing agents that have desired rheological characteristics. The als that find extensive application in high-performance coat. The most important types of curing agents used in epoxy Generically. P. Box 1380. electrical laminates. In commercial products. MNL17-EB/Jun. Historically. The principal amine-functional curing 1Research adviser and 2senior research chemist.and phenoplast resins for heat-cured systems. They are used extensively in coatings for refineries. Resins having n values less than 1 are viscous liquids. and meat backbone. protective ranges from 0 to about 25.

air dry epoxy and phenoplast cross-linking resins are generally etherified esters. There are a n u m b e r of possible ways to classify epoxy resin coatings. dling advantages. amine-terminated polyamides. In addition to the "two.and phenoplast res.' ~ O ~ CH2CHCH2Jn -. i. solvent-borne coatings for cans.2 140 . ambient cure coatings 900 475 2 Solid 70 1400 900 4 Solid 100 Powder coatings 2900 1850 10 Solid 130 Heat cure. melamine-formaldehyde. grams of resins needed to provide 1 M equivalent of epoxide..iran-mavad. Approximate Average Average Average ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . All three terms are interchangeable. pipe coatings. Alsoreferred to as WPE (weight per epoxide) and EMM (epoxy molar mass). TABLE 1--Typical properties of bisphenol-based epoxy resins. drums. heat-cured coatings are based on the higher-molecular- and other modified polyamines are less hazardous derivatives weight epoxy resins. as well as dicyandiamide and polycarboxlic acids.. Ambient.. motive primers. AMBIENT-CURE epoxy coatings can also be classified similarly. ene triamine (DETA). Since curing agent types have been divided into ambient-cure and heat-cure. t h r o u g h reaction of the amine with the epoxy groups. are generally manufactured from intermediate molecular weight solid resins and are cured t h r o u g h the epoxy group. for convenience the types of TWO-PACKAGE. Amino. bSoftening point by Durran's mercury method [ASTMSpecification for Epoxy Resins (D 1763)]. is a two-part system: www.. The usual curing agents for heat-cured epoxy resin coatings EPOXY RESIN COATINGS are amino. Historically ambient-cure coatings have been applied out of ins cure by condensation with the backbone hydroxyls of the solvent. as well as cured coatings for their high basicity and relatively high vapor pressure. or polyamide. been toward coatings with lower volatile organic content.e. ~ v Applications 350 182 . However. amine adduct.. primers. I-Idealized structure of a bisphenol epoxy resin. and waterborne systems. 25~ Point. O. prepared by esterifying epoxy resins with unsaturated urea-formaldehyde. and triethylene tetramine (TETA) have 100% solids. dry by the same m e c h a n i s m as alkyd resins. which are typically manufac- cure coatings are based on low-molecular-weight epoxy res. however. package" type ambient cure epoxy coatings. ketimines.CHCH2 .and phenoplast resins. ings are the "two-package" type. and they are generally cured t h r o u g h of aliphatic amines and often provide performance and han. package coating. flooring. Conventional solvent-borne and waterborne amine adducts. Epoxy/ pails and drums. diethyl. Solventless and solvent-borne ambient cure coatings.. and phenol. The amino. always been popular curing agents for epoxy resins because Heat-cure coatings are used in industrial finishes. CHAPTER IO--EPOXY RESINS IN COATINGS 75 o F --I CH2. the trend has Aliphatic amines such as ethylene diamine (EDA). reaction of the hydroxyl groups. as the n a m e implies. Powder coatings. etc. typically at about 40% weight solids. the regulation of emissions of volatile organics. 3750 3050 13 Solid 150 aEEW = epoxideequivalent weight. with epoxy resin with elimination of water or an alcohol. 600 310 1 Semisolid 40 Solvent-borne. and coat- aliphatic amines present certain handling hazards because of ings for beer and beverage cans. The bulk of the COATINGS ambient-cure or "air-dry" coatings are cured with polyamines or modified polyamines and generally find application as By far the largest volume of ambient-cure epoxy resin coat- maintenance and marine or architectural coatings.. formaldehyde condensates. Softenin~ Molecular Wt EEW~ Value of n P. tured from liquid or low-molecular-weight solid epoxy resins ins having high epoxy group content and are generally cured cured with a polyamine.CH2CH-CH 2 CH3 n is typically 0 to 1 for liquid resins with solid resins having n values as high as 15 or more FIG. A two- through reaction of the epoxy group. which are used in powder coatings. fatty acids. auto- of their ability to readily cure at r o o m temperature. 80 . appliance primers. However. electrical encapsulation. and filament winding 380 188 0.

Like polyamines. agent. semidrying.iran-mavad. The performance properties of amine-cured coatings are not medium. however. polyamine adducts. coatings for plastic products. transmission lines. Two-package epoxy coat. but they are superior to alkyd paints. of 400 to 450~ (204 to 232~ Initially. resulting in reduced solvent and chemical resistance as well as nonvolatile content of the paint at application EPOXY RESIN ESTER. those based on a high-molecular-weight solid epoxy resin. differ primarily in molecular weight. Resins type are in heavy-duty maintenance and marine coatings. and other highly corrosive to 70% esterification. agent components are mixed. and short oil lengths.76 PAINT AND COATING TESTING MANUAL the epoxy component and the curing agent. one-component systems. made by esterifying the resin with fatty acid at temperatures 9 Lower volatility. Typically. and www. especially where mildly corrosive condi- to moist and poorly prepared surfaces. and they provide a tions are encountered. poly. Subsequently. which in the aged separately and often in volume ratios of 2 to 1 or 4 to 1 of presence of water hydrolyze to produce a ketone and a poly- epoxy component to curing agent. and high- leveling properties. exposure to air. and short indicates 30 to 50% esterifica- chemicals. the flexibility. The compared to the precursor polyamine. between 30 and 90% those based on a low-molecular-weight liquid epoxy resin and esterification is chosen. cross-link density decreases with increasing molecular weight. or short oil esters may be prepared with uses over rigid or semi-rigid substrates. Specific film properties depend on longer pot lives. ene tetramine to give an amine-terminated polyamide. depending on the oil length desired. ings. Thus. Like alkyd resins. amine. flexibility retention. performance architectural coatings. that is. epoxy resin esters may be made in long. Initial flexibility and impact resistance are excel. pigments. ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . ready present in the resin are esterified at higher tempera- 9 Less tendency to corrode metal containers. and ketimines are generally with vegetable oil fatty acids. How. These ketimines react at a practical rate of cure under ings are mixed just prior to application and are characterized ambient conditions. these hydroxyl groups and those al- 9 Greater suitability for application at low temperature. curing agents. tropic removal of water. Among the advantages provided by aliphatic pared from solid epoxy resins having EEWs in the range of amine adducts are: 900. since they cross-link or cure only on phatic polyamines such as diethylene triamine and triethyl. medium. selection among many epoxy resins. internal pipe coatings. long. polyamides are adequate for most R E S I N COATINGS applications where amine cure epoxy coatings are used. acids. By proper selection of acids and adjustment of reaction lent. drying. Typical applications of two-package coatings of the above and modifiers. COATINGS Although aliphatic polyamines are less expensive and have been used extensively as curing agents. Polyamide cured coatings exhibit wearing floor finishes. these coatings are 9 Milder odor. They do not. Atmospheric moisture. amine equivalent weight. outstanding chemical resistance of amine-cured epoxy coat- amides are also mixtures of oligomers. Like epoxy resins. and toughness and durability make them well suited for long- reactivity is available.. Epoxy esters are usually pre- preferred. Although resistance to sol- vents and acids is not quite as good as with other types of HEAT-CURED SOLVENT-BORNE EPOXY amine curing agents. or nondrying characteristics. their amides which vary in viscosity. with typical agent. amine adducts offer maxi. and pot life of the coating increase. tion. somewhat better retention of flexibility and impact resistance on aging than polyamine adducts. resins with EEWs around 1750 or greater. As the molecular weight tank linings. Ketimine curing agents are similar in behavior to the working times of about 8 to 12 h. as well as the ratios of these materials. which are pack. a range of poly. Air-dry epoxy resin ester coatings are "one-package" or densation of dimerized and/or trimerized fatty acids with ali. As in conventional alkyd technology. long indicates 70 to 90% esterification. Polyamides are obtained from the con. aliphatic amine polyamines and amine adducts in rate of cure Two-package epoxy resin coatings include a broad range of and performance of cured films. film. Ketimine curing concentration of epoxy groups is low in these resins. Commercial systems will have serves as the source of water required to activate the curing pot lives of a few hours to a couple of days. agents can be considered blocked polyamines. the fatty acid reacts 9 Less tendency to produce blush when coatings are applied with the epoxy ring at lower temperatures. i. ever. The oil length refers to the significantly different from those of aliphatic polyamine degree of esterification of the epoxy resin with the fatty acid: cured systems. Air-dry epoxy ester coatings are used in maintenance and Polyamide cured epoxy coatings develop superior adhesion marine coatings. for gas of the resin increases. AMBIENT CURE viscosity. Ketones add reversibly to primary amines with the loss of Conventional solvent-borne heat-cured or "baked" epoxy water to give ketimines. In addition. which is ab- by a limited working life or pot life after the resin and curing sorbed during and following application of the coating. possess the high degree of corrosion resistance. The terms More pounds of polyamide curing agents are consumed "drying" or "air dry"are used instead of ambient-cure since annually in the United States than any other type of epoxy cross-linking of epoxy resin esters does not involve a curing resin curing agent. forming hydroxyl under conditions of high humidity. tures with the aid of esterification catalysts and with azeo- Two general types of polyamine adducts are available. The ketimines obtained from the resin coatings are based on high-molecular-weight epoxy res- typical polyamine curing agents have rather low volatility ins. and retention of these properties is adequate for most ratios. medium indicates 50 m u m resistance to solvents. Epoxy resin esters are prepared by esterifying the resin amine-terminated polyamides. aircraft primers.e. but they provide much products and properties.

Electroly- tion coatings account for over 92% of all electrodeposition sis of water occurs. are used only when max. which retain good stability systems. At this point. This epoxy resin is then reacted with a flexi- color and relatively low cure temperature.iran-mavad. At this point. the particular systems used being dependent on the in the CED coating bath. An example of such a curing agent would be the reaction weight epoxy resins onto which are grafted terpolymers of. This methods such as spray. Epoxy-based cathodic electrodeposition (CED) au- tomotive primers dominate this application. plied as "one-component" systems. The remaining epoxy functionality is then re- primers. CHAPTER I O . a uniform uses for epoxy resins in coatings. pounds of epoxy resin are used in the United States in CED regenerating the neutral amine groups and causing the coat- automotive primers. Europe. This diol can be an aliphatic diol or a polyether used in linings for beer and beverage containers and as clear diol. These coating systems are based on high-molecular- ture. Thus. exceptional corrosion protection and because they are depos- tionality. and Japan is primed with bile. product of 3 mol of toluene diisocyanate with 1 tool of tri- for example. and baked to cure CED bath. a CED primer. a tertiary amine) to form ether linkages be- resistant. and phenol-formaldehyde resins which would be inaccessible to other coating application are used as cross-linkers for the coatings of this type.g. Thermosetting resins such as urea-formaldehyde. These primary hydroxyls are re- ances. i. and appliance 1000 to 1500. drum and pail linings. styrene/methacrylic acid/ethyl acrylate. cross-linking requires heat. Phenoplast acted with the epoxy groups in the presence of a suitable (phenol-formaldehyde) cured coatings are more chemically catalyst (e. an epoxy resin with an epoxy equivalent weight in the range hyde) cross-linking resins are used because of their good of 500 to 1000.or phenoplast cured bath. mary hydroxyl functionality. They are typically bilizing diol. The less than 0. ing a bisphenol A based liquid epoxy with bisphenol A to give Aminoplast (urea-formaldehyde or melamine-formalde. Phenoplast resins. tive primers. epoxy-based electrodeposi- cathode) relative to counter electrodes in the bath. catalysts. ited uniformly to all areas of the automobile. is then added to the mixture to make ELECTRODEPOSITION COATINGS a m m o n i u m salts with the amine groups in the resin. resin with pigment paste. rinsed. the CED resin preparation is com- plete. specialized CED resins are used to make The earliest epoxy resin coatings for beer and beverage the pigment grind pastes. The dispersed resin can then be cured with an ami. the resin. and they find application in beer and beverage tween the epoxy and the flexibilizing diol. wire coatings.. This is then reacted with 3 mol of a suitable epoxy/acrylic graft polymers are neutralized with base. The coating is prepared by blending the suitable for beer and beverage containers. forming hydroxide ions in the immediate coatings. resin will have an epoxy equivalent weight in the range of internal coatings for pipe. These hydroxide ions react over 82% of all electrodeposition coatings. In practice. When the automobile is dipped into the part is then removed from the bath. These methylolpropane. and an appropriate electrical charge jected to a vacuum stripping step which can reduce VOC to is applied.7 lb/gal. One favored method to i m u m resistance to solvents and other chemicals is required. In this way. and solvents. These are developed to efficiently containers were solvent-borne amino. In order to reduce the volatile organic resin polymers. These are chosen to be stable and unreactive in the coatings the coatings are still basically amino. Because of their major importance. accounting for vicinity of the automobile surface. to give a resin easily dispersible in blocking agent. and accelerator are packaged together. the ketimine groups decompose to give primary amines. and hospital and laboratory furniture. resulting in stable dispersions at a relatively high bath pH COATINGS (pH > 6). curing agent. These primary amines are fairly ba- HEAT-CURED WATERBORNE EPOXY sic. over the years and is now dominated by waterborne systems.E P O X Y R E S I N S IN COATINGS 77 cross-linking occurs principally through the hydroxyl func. During coating preparation. Pigmented aminoplast cured coatings are used as coatings for industrial equipment. Epoxy resin electrodeposition coatings are also waterborne Solvents may be required in the preparation of the CED resin coatings formulated from either anionic or cationic epoxy or other components. The automobile is then removed from the bath. these systems are sup. www. rinsed. such as lactic or acetic acid.e. the containers (particularly in Europe). appli. making this one of the largest single end ing to be deposited onto the surface. but to unblock and cure the coating at baking tempera- systems. application. such as 2-ethyl-1-hexanol. and usually a strong acid catalyst the remainder of this discussion will deal with CED automo- is used to accelerate the cure. it is usually sub- electrodeposition bath. to minimize further chain extension. such as dimethylethanolamine. Over 40 million with the a m m o n i u m ion groups in the resin near the surface. This mixture is then dispersed in water to make the CED ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . secondary amines are chosen poorer color than arninoplast resins. curing The preparation of CED coatings generally begins by react- agent.. A low-molecular-weight organic acid. Although application technology has changed Curing agents used are generally blocked isocyanates. Virtually every automobile film is applied to the entire conductive surface of the automo- made in the United States. Generally. tin or lead salts are generally used to facilitate unblocking noplast resin to give coatings with properties that make them and coating cure. additives. generally giving coatings of acted with amines. Catalysts such as water. The principal requirement is that the diol contain pri- coatings for brass and jewelry. CED primers are used because they afford and baked. a negative charge is applied to it (making it the the coating.or phenoplast cured make stable pigment dispersions. In the United States. accomplish this is to use a diketimine of diethylene triamine. even in areas melamine-formaldehyde.. The part to be coated is dipped into the compound content of the finished coating. causing the coating to deposit onto the part.

(2) economy in use. [2] May. Powder coatings are broadly divided into either "func- ing coating powders allows nearly 100% powder utilization tional" or "decorative" uses.. K. and ances. (3) energy efficiency. phenolics. through the application of heat. The advantages film thickness of 3 mil or less and are not expected to perform for the use of powder coatings can best be summed up in the significantly better than baked films derived from "wet" coat- "Four E's. furniture.78 PAINT AND COATING TESTING MANUAL E P O X Y R E S I N P O W D E R COATINGS greater than about 650 are nonsintering and extremely ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . and underhood automotive parts.iran-mavad. Powder coatings is the fastest growing REFERENCES area of coatings technology. or carboxylic acid func- pigments. www. tivity via the terminal oxirane functionality. their choice by formulators for use in powder coatings appli. 1973. C. reaction with amines. driving forces for growth. curing agents. applied at film thicknesses greater than about 3 mi] and are The 1970's volatiles regulations and energy concerns raised expected to withstand some rather severe service. manufactur. The unique characteristics of solid epoxy resins account for Marcel Dekker. and various electrical devices. have been improvements rebar. DC. Growth rate for powder coatings [1] Lee. formulations. Some examples of decorative uses are coatings for appli- lence of finish. New York. The real sustaining of functional uses are coatings for exterior and interior pipe. has contributed to even greater interest in the use of powder coatings to meet more stringent volatile organic requirements. Handbook of Epoxy Resins.. as amended in 1990. The Clean Air Act. H. however. (4) environmental acceptability." used by The Powder Coating Institute: (1) excel. and various additives. McGraw-Hill in the 1990 to 1995 time frame is projected to be at 10 to 12% Book Co. New York. powder coatings are functional. S. 1967. The resultant powder powder coatings are yellowing and loss of gloss that occur is normally electrostatically deposited onto grounded sub. Y. Washington. when these coatings are exposed to exterior weathering con- strates and. Bisphenol-A based epoxides with equivalent weights American Chemical Society. The solidified by cooling. versus a conventional "wet" coatings rate of about 2%. Epoxy Resins Chemistry and Technology. They have relatively low melt viscosity and high reac- Powder coatings are produced by melt blending homoge. ground into a finely divided powder primary limitations for bisphenol-A based epoxy resins in form. fillers. Although decorative in powder coating raw materials. and Neville. [3] Bauer. cations. Inc... and Tanaka. ACS Symposium Series 114. very high performance thermoset films. R. Examples interest in powder coating technology. and application equipment. these are normally used at a ing technology. Epoxy Resin Chemistry. converted into ditions. and classified for subsequent use. Functional coatings are normally and evolves almost no volatile organic compounds. The addition nous dispersions of nonvolatile solid resins. The process of apply. 1979. ings. The dispersion is tional curatives allows a wide range of formulations.

These solution resins also initiated the man. motive industries. later. which engendered radio circuit boards Phenol can produce five different methylol-related species. Concurrent with the above developments. CH20 + H20 ) HOCH2OH. The heat-reactive resins. the novolaks could be com. acids. Phenols with substituents in the above positions have lower func- tionalities and are frequently used to modify resin properties. the alcohol solutions of the heat-reactive pends on the catalysts and conditions used. After studying the variables. few years. With the advent of modern analytical tics business. namely the electrical. ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . ufacture of laminates. satisfied the above-mentioned requirements. The type of reaction products and resins formed de- cess in coatings. Baekeland [1]. The expansion of several new technologies of tools. "B" stage--insoluble. is conveniently handled as an aqueous active phenolics or "novolak" resins were prepared as a solution (formalin) or as a solid polymeric form known as hoped-for substitute for shellac. methylol groups to condense with other ring positions (meth- 79 www. but swellable and Phenolic resins. to form excellent films when baked and cross-linked. S. hexamethylene tetramine. while the substituted phenols. and solvents. products such as the methylol phenols shown in Fig. actions. developed by Dr. Somerville. with lower functionality.3]. distributor and reactivity properties of resins.astm. heating to supply reactive formaldehyde for the phenolic re- While the above-mentioned novolaks had to wait for suc. 1. were formulated into blends that were The commercially important phenols used in coatings res- convenient for mass production compression moldings and ins are shown in Copyright9 1995 by ASTM International www. are hard and glass-like and have excellent resistance to B A S E CATALYST chemicals. and. A brief description follows. While phenol is the most common. Formaldehyde in aqueous solutions exists as hy- resilient as shellac and. higher heat resistance. Improved and the substituted phenols are also used to vary the solubility new items such as coil supports. resinous reaction product of a phenol CHEMISTRY with an aldehyde. initially commercialized in 1909. are widely employed while the others have electrical switches all blossomed onto the market within a limited or specialty uses. vacuum tube bases. Phenol has three aldehyde reactive ring positions. The reaction of phenol with aldehydes to produce resinous products was difficult to understand in the early years be- cause many of said products were insoluble or infusible.. combined with the formaldehyde do- nor. water. RAW M A T E R I A L S oils. telephone sets. printed circuit boards. still in wide use to- day. and and bisphenol-A. a gas. and moisture. the chemistry of the reactions has been more fully the time. were not successful drated glycols or low-molecular-weight glycol ethers. These resins were not as paraform. resistant material.HOCH20[CH20]H pounded into another set of thermosetting molding materials Both of the above forms of formaldehyde depolymerize on which found early use in phonograph records. NJ 08876. the 2 and 6 carbon atoms (ortho) and the 4 position (para). and improved resistance to chemicals. Said products may be used alone or in formu- lations with other polymers to produce useful coatings. 2a. and auto. the most reactive of those commercially available. Baekeland at least defined the condi- HISTORY tions to produce three stages of products: "A" stage--soluble and fusible. The cresols. These coatings. FIRST PHENOLIC COATINGS The aldehyde co-reactant of choice for the phenols is form- aldehyde. Fry 1 DEEINmON: a polymeric. the nonheat-re- Formaldehyde. radio parts. MNL17-EB/Jun. Further reaction causes the ~Consuhant. by 1911. resins were found. when used alone. communications. 14 Westbrook Ave. in coatings. all required and depended on new materi- als that had better electrical insulating properties. defined by various workers [2. 1995 ii 11 Phenolics by John S. were the softenable. butyl phenol heads. Early applications in- cluded protective coatings for brass beds as well as other Strong base catalysts (pH above 8) produce initial reaction hardware items.iran-mavad. and "C" stage--cured to an insoluble and heat- first completely synthetic materials for the burgeoning plas. commutators. Leo H. pro- duce fewer methylol derivatives. However.

the pH of the phenol-formaldehyde reaction falls in 3. Under such conditions. the 4 to 7 range.5.80 PAINT AND COATING TESTING MANUAL ~ ~H3~CH3~ OH OH OH OH OH CH3 CH3 CH3 Phenol Orthocresol Metacresol Paracresol Xylenols OH OH OH OH OH 0 () CH3-C-CH3 CH3-C-CH3 CH3-C-CH3 0 I I I cn3 CH 2 CH2 I I CH 3 CH3=C-CH 3 I CH3 OH 2. www. methylene-linked phenolic rings (Fig. or isolated as methylol groups are formed. 3).2 Bis (4. may include the following. Volatile content [ASTM Test Method for Volatile Content When salts of zinc. However. Additional reaction raises the addition to the phenolic ring is highly directed to ortho sub- molecular weight to branched. 2b). hemi-formals and ortho which are dehydrated. catalysts. When phenol is used. With excess formaldehyde. or aluminum are used as in Phenolic Resins (D 4639-86)]. p-Phenyl p-tert-Butyl p-tert p-tert-Octyl Hydroxylphenyl) Phenol Phenol Amylphenol Phenol Propane (Bisphenol-A) FIG. when substituted phenols are used. heat-reactive resin products stitution.5 to 1. the functionality of the system is reduced to two and mostly Typical quality control tests for phenolic resin products linear resins are formed. 1-Phenols used to make phenolic ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . highly branched "novolaks" are TESTING OF PHENOLIC RESIN PRODUCTS obtained. dissolved in solvents. At a pH of 0. With the highly reactive para ring position still open. magnesium. Using lower formaldehyde levels grindable solids for later formulation. 2. leads to the formation of nonheat-reactive ortho-ortho novolaks.iran-mavad. these resins have been employed in relatively rapid ACID CATALYST crosslinking formulations. ylene link) or to etherify with other alcohol groups (meth. the formaldehyde ylene ether links) (Fig. 1. Gel time [ASTM Test Method for Determining Stroke Cure Time of Thermosetting Phenol-Formaldehyde Resins INTERMEDIATE pH CATALYSIS (D 4640-86)] (heat-reactive resins). Viscosity (solution). the acid-catalyzed phenol-formalde- hyde reaction proceeds through an unstable addition inter- mediate to condensed.

2a-Base-catalyzed initial reaction ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . OH OH OH ~ H2OH Base y ~ CH2 ~ CH2OH+H20 METHYLENELINK Or OH OH 0 0 + H20 METHYLENE ETHER FIG.iran-mavad. 2b-Methylol phenol reaction products. CHAPTER ll--PHENOLICS 81 OH OH OH + CH20 Base ~ ~ C ' H2OH + r CH2OH OH OH + < ~ H2OH HOCH2~ H2OH .'H2OH OH HOCH2~ CH2OH CH2OH FIG. www.

spray. pipe. Similar formulations have been used for varying from several minutes to several hours. tank linings. meation chromatography. As a cal coil and armature impregnation varnishes. pH [ASTM Test Method for Measuring Apparent pH or result. Low-molecular-weight resins with a metal is then formed into can bodies and lids. The films are phenolics based on bisphenol-A may be used to minimize then baked at typical temperatures of 135 to 250~ for times critical taste effects. Environmental resistance. while higher mo. but insoluble in aromatic and ali. acids. Such var- www. secondary hydroxyls of the epoxy resin backbone to cross- esters. the resins may be applied by ing the metal and the food. I. brush. Electrical properties.2 mil) are applied to tin plate or tin-free resins are commercially available as solvent solutions. To obtain better toughness and flexibility for applications such as can coatings or coil coatings. baking. ins are blended with blown oils or alkyd resins to form electri- ance and also resist dry heat to 370~ for short periods. When used wire coatings or coil coating primers. then packaged. formulated with said resins as crosslinking agents. In the case of can cases. or roller coating methods. For beer and beverage cans. Tests performed on such 6.2 to 1. Multiple coats may be applied as long as the intermediate coats are given a Heat-Reactive Aromatic Soluble Resins short bake. Since volatiles are released during are used for linings when basic substances are packaged.HO Acid ~ CH 2 ~ O H Q CH2 FIG. 3. 3-Acid-catalyzed reaction products. Molecular weight distribution and free phenols--gel per. P h e n o l i c s as Crosslinking Agents for Other Polymers Coatings based on heat-reactive phenolics alone are not H E A T REACTIVE R E S I N S IN COATINGS very flexible. sion-resistant hardware coatings. such as an epoxy The thermosetting. 4. in ratios of about 15/85 to 50/50 phenolic/epoxy. The linings have to withstand a steam steril- lecular weight resins may be used in dispersion form [4. polyamides. 4). 4. They are not resistant to higher alkyl groups form resins which are soluble in aromatic alkalies unless combined with epoxides as will be discussed solvents and even tolerate some aliphatic diluents. link the system (Fig. ization cycle of about 90 min at 250~ (121~ while protect- Once formulated into vehicles. and poly(vinyl butyral) and are. phenolic resins crosslink with the release of water to are also more resistant to alkalies than phenolics alone and form 0. The coatings. coatings may include: Other tests to characterize resins may be used: 1. Phenolic/epoxy systems alone. I. solids. alcohol-soluble resins are based on resin. Specific gravity. Free formaldehyde-hydroxyl amine method. and tuted phenols such as p-tertiary butyl phenol or those with acidic or neutral inorganic salts. Applications. 2. dip. printed circuit masks. 3. but to a lesser extent epoxies. Baked phenolic coatings are hard and glass-like with excel. some of phatic hydrocarbons. Thermal analysis (curing curves). the phenolic resin may self condense. production pipe. and glycol ethers. printing plate backing. bubbles may develop in thicker films. as drum and pail linings. and as corro- 5.0-mil films. Physical and mechanical.R. boiling water. 4. these products find applications in oil industry drill Water Insoluble Phenol-Formaldehyde Resins (D 4613. Upon muhifunctional monomers such as phenol. xylenols. steel and typically baked for 10 to 12 rain at 200~ The coated or waterborne systems. 86)]. in many than the pictured cross-linking reaction. 2. thin films (0. and foods are high methylol content form water solutions. the phenolic resin's methylol groups react with the and ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ .5]. These resins are also soluble in ketones. Color (Gardner).iran-mavad. These res- later. cure. the pheno- Alcohol-Soluble Resins lic resins are combined with a linear resin.82 P A I N T A N D COATING T E S T I N G M A N U A L OH CH20 H+ ~. Depending on the ratio used. They are compatible with amino resins. These phenolic coatings have excellent electrical resist. Heat-reactive resins or copolymers based mainly on substi- lent resistance to organic solvents. Structure analysis--NMR. cresols.

These resins do not form useful films by Varnish Resins themselves. 4-Crosslink formation. novolak-type resins. www. higher alkyl groups are reacted with formaldehyde under catalyzed reaction of an epoxy group with the phenolic by.CH2_CH_CH2 + \o/ FIG. nishes may be used in both new and reconditioned electrical droxyl group to form ether-type crosslinks which are resist- equipment. Such coatings find application as pipe coatings. ant to chemicals. and electronic encapsulation coatings. the chemistry involves the base. Since this reac- tion does not produce by-products. forcement bar.. acidic conditions to produce "oil soluble" novolak resins. and heat ( ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . 5-Epoxy phenolic reaction. thick films may be Nonheat-Reactive Resins--Unsubstituted obtained via powder coatings or high solids solution coat- ings. CHAPTER l l . B O. but when formulated with polyfunctional epoxy resins they act as co-reactants (hardeners) to produce ther. Substituted phenols containing the ten-butyl group or moset systems. In this case.P H E N O L I C S 83 CH3 OH CI-I3 CH2 I EPOXY A1 PHENOLIC CH 3 OCH2-CH-CH2 I CH3 0 +H20 I I CH2 OH FIG. rein- The acid-catalyzed reaction of formaldehyde with an ex.iran-mavad. 5). cess of phenol and/or cresols produces the nonheat-reactive. moisture.

ning agents. p. L. 1974 (to Union Carbide Corpo- drying clear wood coatings. and Fry. molecular weight allowed the cold blend preparation of var... high solids coatings were mandated by vari.554. Varnishes based the product class is hardly pass6. [1] Baekeland. H. U. 3. Academic. combined with drying oils or alkyds. Newer resins. and anti-skin. high solids and powder coatings. but the advent of the synthetic pheno. 23 to be achieved. air York. R. air drying primers June ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . American Paint and Coatings Journal. 41. duce useful air-dry or baking formulations. 1978 (to Union Carbide Corpora- In the 1980s.84 PAINT AND COATING TESTING MANUAL Additionally. the resin is dissolved in the 1958. 1. nishes were originally prepared via a "cook" method where the phenolic resin was dissolved in the oils at 230 to 310~ while the oil then polymerized to a specified viscosity. the varnish was cooled and then finished with additives such as driers.S. Vol. J.103. Paint and Varnish Production.S. and the before phenolic resins. ous federal and state regulations.." While they are again nonfilm formers. nish vehicles [6]... H. Industrial Engineering Chemistry. mainte- ration). J. [5] Fry. While phenolic resin technology represents a mature field. solvents and the oils and additives are added at mild tempera. substituted phenols may be co-reacted with tall and aluminum-pigmented topcoats have been successfully oil resin and formaldehyde to form modified resins. [3] Martin. N. and as alkyd reinforcements. S. [6] Richardson. In this process. 1956. novel phenolic resins of higher 1909.. New York. Newer phenolic varnish res. which used for maintenance painting of major steel structures such are also "oil soluble. Wiley. Var.. [2] Megson. Patent 4. No. L. www. formulations on natural oil-soluble resins and drying oils were known long for waterborne.823. Applied with airless spray. The Chemistry of Phenolic Resins. J.iran-mavad. the above resins pro. U. In the 1950s. New tures. as bridges and airport light towers [7]. Such vehicles are still used as baked can coatings. S. porch and deck enamels. UV absorbers. August 1955. nance paints. Patent 3. [4] Harding. ins were introduced that allowed vehicle solids of 70 to 80% [7] Yee. S. tion). continued high performance in container and pipe coatings lic resins led to more consistent production quality. J. A. After REFERENCES adding solvents. all indicate a promising future for this class of materials. Phenolic Resin Chemistry.W.124.

MNL17-EB/Jun. present in commercial dimer acids. or cyclic. Reactive polyamides are oligo- mers designed primarily for use in the manufacture of two. Diethylenetriamine is an example of a simple linear ber of double bonds in the feedstock. respectively. CH3[ (~ H2)7 /CH2--C~H2 (~H2)8 ~H H2N--CH2--CH2--N NH \ / CH C CH2--CH 2 I I The reaction between dimerized fatty acids and poly- (~H2)7 (~H2)7 amines yield amide oligomers with amine group termination. or hardener for epoxy resin. The majority of poly.astm. or ene chains. the polyamide reacts with the epoxy CH3 resin and becomes part of the polymer. The solution may be a clear amber liquid or may contain pigments in colored systems. groups. depending on the location and num. The polyamide may function as the curing <~ (CH2)s--COOH CH~CH--(CH2)4--CH 3 agent. The cyclic and branched polyamine isomers contain terti- ary amine groups in addition to the primary and secondary Acyclic CH 3 amine groups. Kight 1 POLYAMIDES ARE POLYCONDENSATIONproducts of dimerized Monocyclic COOH fatty acids and polyamines. ACIDS ~ CH3--(CH2)4~~. as well as components 'Technical Service Representative.~ (CH2)7--COOH The dibasic fatty acids of commercial importance used to (Ctt2)4 manufacture polyamide curing agents are prepared by di. Aminoethylpiperazine is an example of a cy- clic polyamine. Savannah. Some ene polyamines of various chain lengths that are linear. monocyclic. The tall oil fatty acids are a mixture The polyamines commonly used in industry are polyethyl- of Cla isomers with a variable number of double bonds. I CH3 merizing unsaturated C18 fatty acids from Copyright9 1995 by ASTM International www. Examples of three possible isomer types follow. (I ~H2)8 component polyamide/epoxy coatings and adhesives. Many isomers are polyethylene polyamine. of a variety of other useful commercial compositions includ- Box 2668. most of which are HzN--CH2--CH2--NH--CH2--CH2--NH2 difunctional carboxylic acids [I]. P.iran-mavad. Linseed and soya fatty acids are extracted from flax and AMINES soybeans. of the isomers combine via Diels-Alder addition and other branched. with the polyamide usually (though not always) con- tained in Part B. separated by ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . soya. or tall oils.O. Crude tall oil (CTO) is a by-product from the Kraft process for papermaking and is a mixture of The dimer acids are reacted with various polyamines to fatty acids and rosin acids. Polycyclic COOH amides used in coatings are viscous liquids that are usually I supplied by the coatings manufacturer as a solution in or- ganic solvents. These amide oligomers are used as coreactants with epoxy COOH COOH resins in high-performance coatings. coreactant. terminated on either end by primary amine polycyclic in structure. The two-component coatings are generally labeled Part A and Part B. Polyamides (CH2)4 should not be considered as catalysts although they may I initiate the reaction. 1995 Polyamides by Robert W. The characterized as secondary amine groups separated by ethyl- dimer acids produced may be acyclic. The linear polyethylene polyamines are mechanisms to form C36 dibasic acids or dimer acids. from which the fatty acids are form polyamides and a variety of other useful products. 85 www. GA 31402. ing two-component adhesives. Union Camp Corporation.

that is also specified in trolled to yield a product with specific useful properties.. such as 1:1 or 2:1. grams of potassium hydroxide required to neutralize 1 g of Similar reactions occur at the other carboxylic acid group of sample.N. Such as industrial maintenance coatings.05/~m. The proce- of reaction is evolved. and marine applications. with very low Commercial products range from about 35% to more than toxicity. The result is reported as either a ratio of H H imidazoline:amide (I/A) or as a percentage. a total of 3 tool of water Value of Fatty Quaternary Ammonium Chlorides. and terti- a nitrogen bonded carbonyl. 2 mol potentiometric titration using ASTM Test Method D 2073: of water are evolved. however.N .C H 2 . the ethylene chain ary amine values are not applicable to polyamides. an interesting Test Methods for Total. ab- I I sorbs at 6. eliminates an active hydrogen to yield a terti. pri- --C N . which is methods specified therein for primary.N . C~2/N hesives and high-performance coatings. The acid value may be determined using ASTM Test the dimer [2]. and the nitrogen-bonded carbonyl..C H 2 . dure specified for determining the amine value in Method lowing structures: D 2076 is not applicable to polyamides. and the viscosity level of much better flexibility as well as better wetting and adhesion the polyamide in solvents. The ratio of these values.. however.C H 2 .05/~m. One of the primary amine groups by Referee Potentiometric Method.. By varying the mix ratio of tage is that epoxy/polyamide coatings are prone to severe the polyamide to the epoxy resin. The advantage of having a long usable required to react with a given amount of an epoxy resin of pot life comes with a much slower cure rate. The total next to the amide function and the secondary amine nitrogen amine value is commonly listed in the specification proper- are incorporated into a five-membered ring.C H 2 . 1 mol of dimer acid is reacted with 2 mol of The total amine value of the polyamide is determined by diethylenetriamine. In a typical commer- CHEMICAL PROPERTIES cial example.C . Amidoamines. 80% imidazoline to allow the coatings formulators latitude in Epoxy/polyamide coatings find utility in a wide variety of customizing the properties of their products.C H 2 .com ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . is most often only a cure and three to four days for a full cure. about 550 to 140. Imidazoline level can best be H H measured by scanning the polyamide with an infrared spec- trophotometer and comparing the absorption at 6. Note. In the example www. ary amine group.. such as requiring critical mix ratios and toxicity. which is related to The presence of the long fatty chains gives coatings with active hydrogen equivalent weight. starting point for the formulator.. As the reaction proceeds. certain properties of the chalking during exterior weathering. cured coating are enhanced (and others are sacrificed) to obtain specific application properties. The N CH 2 \/ introduction of polyamides allowed the coatings manufac- CH2 turer to produce high-performance coatings characterized by convenient mix ratios. thus epoxy/ known epoxide equivalent weight. known as an ties of commercial polyamides and is defined as the number imidazoline ring.N .C H 2 . which also of milligrams of potassium hydroxide equivalent to the basic- evolves water.. Other properties of the polyamide that are important to the chinery and equipment enamels. . The early commer- CH2 cial epoxy/amine coatings contained aliphatic amines.. which had several negative fea- II r tures. For the polyamide The imidazoline content is not specified in commercial polyamides except in special cases where the level is deemed O critical.C H 2 . respectively. The acid value. C2A compatibility and/or solubility. coatings formulator are the amine value.N H2 marily diethylenetriamine. Another disadvan. The degree of cyclization obtained is con. such commercial polyamides is defined as the number of milli- as improved solubility and compatibility and longer pot life. This condensation reaction. or amide. The level of imidazoline is usually controlled by the II polyamide manufacturer to provide products with specific H2N--CH2--CH2-. Amine values range from about than was obtained with the earlier aliphatic amine cured 100 to about 400. secondary. that the reacts with the dimer acid to form an amide linkage.iran-mavad.C . with active hydrogen equivalent weights of systems. The active hydrogen equiva- The epoxy/polyamide coatings are not. and Diamines from a secondary reaction.86 PAINT AND COATING TESTING MANUAL EARLY H I S T O R Y and for the imidazoline Polyamides were commercialized in the late 1950s for use H2N--CH2--CH2--NI ~-C34 with epoxy resins in the manufacture of two-component ad. ity in 1 g of sample.. If 50% of the diethylenetriamine present in the Method D 2076: Test Methods for Acid Value and Amine polyamide is cyclized to imidazoline. without lent weight is used to calculate the amount of polyamide some disadvantages. applications. These products are shown in the fol. During this condensation reaction. and Tertiary side reaction occurs: an additional mol or so of water evolves Amine Values of Fatty Amines. In addition. Secondary. S Y N T H E S I S OF P O L Y A M I D E S Polyamides are polycondensation products of difunctional fatty acids and polyfunctional amines. polyamide coatings generally take 8 to 10 h to reach an early known as the stoichiometric mix ratio. ma.N H2 6.25 /zm.C H 2 . Primary..25/zm to O the absorption at 6. generally less than 5.. The imidazoline ring absorbs at .

glycol ethers. and the respiratory system must be avoided.iran-mavad. an indication of cure. Commercial polyamides are generally supplied in a resistance of the coating is not achieved before three to four single organic solvent at between 60 and 80% solids. of the tube most closely matching the sample. and cal resistance but will tend to be less flexible. the surface to be coated should be polyamide or polyamide solution is determined in accord. 1. A secondary reaction occurs between pendant hydroxyl groups PHYSICAL PROPERTIES in the epoxy resin molecule and other oxirane rings present.5]. polyamide and the oxirane ring of the epoxy resin. or at a minimum tonian Materials by Rotational (Brookfield) Viscometer. to form one component of roller. if possible. as well as guidelines for hazardous waste /\ I ~ J disposal. and ultimate cure is achieved after about three weeks. A plus ( + ) or a amidoamines are used. and aromatic hy. Thus the coatings manufacturer has consider. Polyamide R E A C T I O N OF P O L Y A M I D E S IN C O A T I N G S solutions must also be handled with care to avoid exposure to ignition sources as they contain flammable or combustible Polyamides react with epoxy resins in several stages to solvents and the vapor level from polyamide solutions must form a complex insoluble cross-linked matrix. These products do not contain polyamides. when applied appear to dry because of solvent evaporation. CONSIDERATIONS sured in accordance with ASTM Test Method D 1545: Test Method for Viscosity of Transparent Liquids by Bubble Time In response to environmental concerns over the emission Method. is one mechanism for the cross-linking that occurs. The percent nonvolatile content of polyamide solutions Cure results from a chemcial reaction between the polyamide may be determined in accordance with ASTM Test Method and epoxy resins that generally requires about 8 to 10 h D 1259: Test Method for Nonvolatile Content of Resin Solu. Though polyamides are less toxic than aliphatic amines and amine adducts. or steel. greater than the stoichiometric ratio is recommended. The should be wire brushed and chemically cleaned [4. which should be consulted for hazard infor- This initial reaction can be represented by the following mation and guidance on the safe use of the products. The initial re- be monitored in the workplace to avoid overexposure to the action is between the terminal primary amine groups of the organic solvents present. and the observation is reported as the alphabetic letter (VOCs). ketones. products formulated from m o n o m e r minus ( . the of Transparent Liquids (Gardner Color Scale). For ease of han. A significant volume of or less than the designated letter. drocarbons. which is another mechanism for the cross-linking reaction Polyamides are supplied commercially in solution or as [3]. wood surfaces should be first cleaned thoroughly and any old The viscosity of the polyamide may be measured at ele. This early dry time is not.. thoroughly cleaned and degreased.+ H--N-. however. Polyamide/epoxy coat- ance with ASTM Test Method D 1544: Test Method for Color ings are not normally applied to wood: when so used. they may be supplied in various solvents. which days. the use of close to or including alcohols. hazardous waste due to the presence of organic solvents must www. provide coatings with m a x i m u m cross-link density. Chemical tions.C H E M I C A L DESCRIPTIONS 87 reaction described previously. The color of the adhesion to the substrate. viscosity of commercial polyamides is typically specified at 75 or 150~ The viscosity of polyamide solutions that may also be measured by this method is generally specified at 25 or ENVIRONMENTAL/TOXICITY 40~ The viscosity of polyamide solutions may also be mea. To provide more these polyamides are soluble in a variety of organic solvents flexible coatings with greater elongation. sheets (MSDS). many coatings which the polyamide solution is placed in a sample tube. faces should be sandblasted. Such dling. polyamide/epoxy coatings continues to be used. Polyamide/epoxy coatings contain organic solvents.0 and the percentage would be 50%. or with a solvent blend. The coatings formulator may design the solvent system the two-component system. instead. including spray. A modification of this Method is usually used in of organic compounds into the atmosphere. MSDS also contains information regarding procedures to fol- O OH low if a spill occurs. before the film will resist mechanical deformation. loosely adhering paint removed. Polyamide/epoxy coatings may be applied by any conven- ther dilutes the polyamide solution with more of the same tional commercial applicator. Concrete surfaces may be vated temperature in accordance with ASTM Test Method chemically acid etched or mechanically brushed. which able latitude in selecting specific solvents for optimum ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . or solvent. direct contact exposure with the skin. Steel sur- D 2196: Test Method for Rheological Properties of Non-New. the imidazoline ratio would be The reaction of the oxirane ring and active hydrogen. eyes. The active Polyamide manufacturers supply material safety data hydrogen opens the ring and the oligomers join end to end. CHAPTER 1 2 . ~--N--CH2--CH-. cations properties. Those polyamide solutions that are classified as H2C--CH-. the manufacturers have begun to produce high solids coatings viscosity is compared to Gardner-Holdt Letter standard that contain much lower levels of volatile organic compounds tubes. brush. provides a handleable viscosity. Because of this latter reaction it is desirable to mix the 100% reactive liquids depending on the handling and storage polyamide and epoxy in less than a stoichiometric ratio to requirements of the coatings manufacturer. for a particular type of applicator. The coatings formulator fur. coatings will be characterized by excellent impact and chemi- ides suitable for coatings applications are quite viscous. which also occurs at the secondary amine sites in the polyam- ide. concrete. For optimum pigments in colored coatings formulations.) is then used to indicate that the viscosity is greater fatty acid rather than dimer acid [6]. Most polyam. Polyamide/epoxy coatings The polyamide component may be clear or may contain may be applied to wood. The simplified structure.

John Wiley & Sons. such as a g r o u n d clay a b s o r b e n t [2] Lee. Unit 20.. 1974. ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . ings Technology. 2-12. a n d p l a c e d in a s a n i t a r y landfill. E. Chapter 10. Compounds as Epoxy-Resin Curing Agents. www. "Characterization of Products from Clay Catalyzed Polymerization of Tall Oil Fatty Acids. K. resin. "Epoxy Resins in High Solids Coatings.iran-mavad. P o l y a m i d e s m a y b e stored in d r u m s o r tanks con." The Epoxy Resin Formulators Training Manual. p. New York. and Crowell. [6] Bozzi. E. s h o u l d be avoided b e c a u s e of d a r k e n i n g of the p r o d u c t from [5] Allen.. 2nd ed. Vol.. pp. Ed. James Kaszyk. H. 348-354. 1984.. s t r u c t e d of stainless steel or a l u m i n u m . John Wiley & Sons. [1] McMahon. The So- ciety of the Plastics Industry. and Neville. Chapter XIII.. 1972. 1988. pp." Encyclopedia of PolymerScience and Engineering. New York. and Engineering. Liquid (100%) p o l y a m i d e s are not generally REFERENCES classified as h a z a r d o u s waste t h o u g h their disposal m a y be r e g u l a t e d as an oil b e c a u s e of their liquid nature. C a r b o n steel tanks Vol. 476-489. pp. solid a b s o r b e n t m e d i u m ." Encyclopedia of Polymer Science o r more. d r y environment." ucts m u s t be either i n c i n e r a t e d o r a b s o r b e d b y a suitable Journal of the American Oil Chemists Society. Vol. New York. [3] "Epoxy Resins. R. 2nd ed." Handbook of Epoxy T h o u g h p o l y a m i d e s are reactive in the presence of epoxy Resins. "Epoxy Resins in Coatings.88 PAINT AND COATING TESTING MANUAL be incinerated.. 6. pp. 149-162. New York. 11.. they are quite stable c o m p o u n d s w h e n kept in a cool. 522. McGraw-Hill. these p r o d ." Federation Series of Coat- iron c o n t a m i n a t i o n . 1988. a n d they m a y r e m a i n u n c h a n g e d for a y e a r [4] "Polyamides from Fatty Acids. "Amides and Miscellaneous Nitrogen product. 51. D.. Inc.

or combination. ide and dibutyltin dilaurate are used to promote ure- sumption of polyurethanes was about 2750 million lb (1. factor is a major reason for use of polyurethanes on plastic Type III. active isocyanate groups. it is removed by addition of a forms. million lb (1. The coatings are also called million metric tons) with the forecast for 1993 about 3150 uralkyds. and coatings. floor finishes. water. G. 1995 13 Polyurethane Coatings by Joseph V.2] in the Leverkusen laboratories of I.astm. that had been introducedby duPont. Consolidated Research. ASTM [8] defines polyurethane coatings as vehicles contain. elastomers. and/or crosslinking agent. tional alkyds.or amine-functional compounds. example. toughness. quantity of free isocyanate groups. Koleske 1 INTRODUC~ON Excess isocyanate groups capable of reacting at the time of application may be contained in the reaction products. good light stability when aliphatic isocyanates are used as sealers for concrete and wood. They are often resistance. (95 000 metric tons) [7]. polyester or poly- million lb (137 000 and 46 000 metric tons). it is readily apparent that wood and floor finishes because they provide improved scuff. these as water. "One-package. urethane alkyds. or multifunctional isocya. Catalysts such as dibutyltin ox- ucts. ether prepolymers that are capable of reacting with ad- Reasons for the use of polyurethane coatings include: high. They are usually the cation to prepare elastomeric polyurethane products from reaction product of a multifunctional isocyanate and a Bayer's products that were like nylon or other engineering polyhydric ester of vegetable oil acids and are hardened plastics in physical characteristics. thenates or tertiary amines. For rigid foams. and composites. flexible foams prepared in both slab and molded isocyanate is present. now known Type I. and stain polyurethanes are used as clear coatings. and benindustrie AG in 1937 [3. WV 25314-2307. and similar compounds. "Two-package catalyzed" polyurethanes are ing a minimum of 10% by weight on a nonvolatile vehicle made up of one package that contains a prepolymer basis of a multifunctional isocyanate monomer reacted in having free isocyanate groups and a second package that such a manner as to yield polymeric systems with urethane is a catalyst. Varnish. ventitious moisture to form mainly urea linkages be- performance characteristics such as flexibility. In 1991. The coatings are often used in coil coatings and electrical wire coatings. These coatings are not Road. widely used. For the most part. accelerator. respectively [7]. Initiators or crosslinking hate monomers in any ratio. moisture cured" polyurethane coatings are isocyanate-terminated.. including reaction-injection-molded prod. ASTM THERMOPLASTIC POLYURETHANES WERE FIRST developed by has classified such polyurethanes into six general types Otto Bayer [1. "One-package. They are often used as automobile refinish coatings and thane coatings is large and growing. and used. Type IV. In an overall sense. detergent. Far. urethane-modified alkyds. with the aid of metallic dryers such as cobalt napthenate. "One-package prereacted" polyurethane coat- as nylons. Although the market for polyure. In 1991 consumption of polyurethanes for coatings in Western Europe and Japan was 301 and 100 Type ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . Cure is achieved by the oxi- market for polyurethane coatings was about 209 million lb dative crosslinking of unsaturated fatty acid molecules. and stain resistance over those of conven- it represents only about 5 to 10% of the total domestic poly. chemical resistance such polyurethane/polyurea coating.25 thane-linkage formation. 89 www.iran-mavad. Catalysts are compounds such as metal nap- linkages. [ASTM Terminology Relating to Paint. linseed oil and glycerol may be first reacted and then modified with a diisocyanate that reacts with a part the polyurethane business is huge and is concerned with rigid or all of the available hydroxyl groups. Lacquer. Polyurethanes are widely used in coatings. the national and oil-modified urethanes. and abrasion resistance. proportion.4] as they searched for a product Related Products (D 16)] [8]: that would be competitive with the Copyright9 1995 by ASTM International www. agents are glycols or other monomeric. elastomers. flexible and manganese neodecanoate. con. cure or crosslink by thermal release of blocking agents which results in regeneration of active isocyanate groups that will subsequently react with active hydrogen groups DEFINITIONS contained in the formulation. tween the molecules and the final coating is a strength. initiator. the 1988 U.S. monofunctional alcohol. Charleston. heat cured" polyurethanes substrates. Excluding coatings. multihydroxyl. The latter deck finishes. MNL17-EB/Jun. ings are characterized by the absence of any significant after. and low temperature-cure characteristics. If any residual foams. Shortly there. many industrial chemicals. Schollenberger and coworkers [5] used formula modifi. Pot life is limited after the JSenior consultant. 1513 Brentwood two packages are combined. Inc.43 million metric tons) [6]. urethane market.

4-cyclohexane diisocyanate (CHDI).and 2.4'dicyclohexylmethane diisocyanate. CHEMISTRY 1. ASTM classifications are polyurethane and polyester. thus related to the ASTM Type III coatings. aliphatic isocyanates are widely used for from about 40. phenol. original automotive equipment always manifests itself as yellowing. The main aliphatic isocyanates are hydrogenated MDI (4. there are many ramifications of this blocked by reacting the free isocyanate groups with phenol: reaction that will lead to the polyurethane products currently in use.and Aliphatic isocyanates are more costly. and similar outdoor end-use products. Other linking groups that may be found in polyurethane ISOCYANATE-TERMINATED ADDUCT PHENOL coatings are allophanate.N H C O .000). ketoximes. These coatings. Yellowing in itself is a clear coats over pigmented decorative coatings. and they are converted into a solid film by solvent diphenylmethane diisocyanate (MDI) and toluene diisocya- evaporation. the molecules disso- nate group and that can be represented with monofunctional ciate and the blocking group leaves. For example.2. biuret.. including powder coatings. the systems matic isocyanates are used in products where weathering have limited pot life. They are used mainly in Japan. Two types of isocyanates are used in coatings--aliphatic tains active hydrogen groups.90 PAINT AND COATING TESTING MANUAL Type ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . At elevated temperatures. In actual practice. are used in high performance areas such ance. urethane coatings that require excellent sunlight resistance able urethanes. resistance. Blocking groups are proton donors such as O H E-caprolactam.6-isomers. malonic. . After mixing the two packages. is not important because of discoloration. hexamethylene diisocyanate (HDI). which almost as automobile refinishes. anate have excellent chemical and physical properties.4'- groups. The following information is meant to give C2HsC(CH2OCONH--C6H3(CH~)--NCO)3 ISOCYANATE-TERMINATED ADDUCT the reader a brief excursion into the raw materials and some of the reactions that are important to polyurethane chemis. Aro- or acrylics. in nature because of the high molecular nate (TDI). functionalities of two or greater are usually trimethylolpropane (TMP) can be reacted with TDI and then involved.5-trimethylcyclohexyl iso- As with many phases of chemistry. truck and bus coatings. which is a mixture of the 2. TMP TDI ucts are formed. They are characterized by both interior and exterior applications. aircraft loss of an aesthetic property. though MDI has some use due to its low vapor pressure. freeing the isocyanate materials as follows functionality that then readily reacts due to its nature and the ROH + R'NCO ~RO--C--NR' kinetic effect of elevated temperature with available active II I hydrogen groups. and aromatic.000 to 100. and industrial-struc. The second package may or may not contain a catalyst. Type III polyurethane coatings. Recently tetramethylxylylene diisocyanate today for the popular cast or transfer-process fabric coat. These relatively low molec. It is interesting to note that urethane formation takes C2HsC(CH2OH)3 + C6Ha(CHa)(NCO)2 place through a rearrangement reaction and that no by-prod. ture.4-4-trimethyl hexamethylene diisocyanate (TMHDI). Simplistically. and waterborne urethanes [7]. Naph- Three other types of polyurethanes not included in the thalene diisocyanate has also been used. The lacquers are low solids. (TMXDI) and isopropenyl dimethyholuene diisocyanate i~ngs as well as other fabric coatings. The first two and no discoloration. and acetoacetic esters as well as other enolizable esters. "Two-package polyol" polyurethanes coatings Raw Materials have one package that contains an isocyanate-termi- nated prepolymer or a multifunctional isocyanate and a Isocyanates second package that is made up of a polymer that con.. IPDI and HI2MDI are the isocyanates chemistry of urethane coatings in a simple or a complex most widely used in coating preparation. while these factors can be weight polyurethane (weight-average molecular weight cost considerations. polyethers. C2HsC(CH2OCONH--C6Ha(CH3)--NCO) 3 + 3 C6Hs--OH try. particularly sunlight or ultraviolet light resist- solids in nature. (TMI) have been introduced by American Cyanamid. Polyurethanes prepared from either type isocy- ular weight polymers are usually polyesters. one-package systems that are activated at elevated ment reaction when an hydroxyl group reacts with an isocya- temperatures. ultraviolet light-cur. weight involved and concomitant high viscosity of such Moisture-cure urethanes and urethane alkyds usually employ molecules in solution. types have been considered as energy-activated materials and automobiles. one can consider the cyanate or IPDI) [9]. manner.. attacks the labile hydrogen atoms on the aromatic ring struc- Type VI.4.4- and 2. Aliphatic isocyanates are less reactive and more costly tem that basically is a solution of a high molecular than aromatic isocyanates and. These films have very high gloss TDI. mixtures of 2. and isophorone diiso- cyanate (3-isocyanatomethyl-3. PHENOL-BLOCKED TRIISOCYANATE www. These linkages will be discussed later. about 10-15% by weight. urea. or H12MDI). and are used in the textile industry to achieve the "wet Xytylene diisocyanate (XDI) is used to some extent.iran-mavad. which are high. the absence of any significant quantity of free isocyanate The two main aliphatic isocyanates currently used are 4. but look" that was popular in the late 1970s. urethane coatings contain urethane employ blocked isocyanates that provide room-temperature linkages.5. Ultraviolet light ture maintenance coatings. and isocyanurate C2HsC(CH2OCONH--C6Ha(CH3)--NHOCOC6Hs)3 groups. HMDI. etc. "One-package nonreactive lacquer" is a sys. These coatings are used on plastics. that are formed through a rearrange- stable. but its cause and result do not coatings. particularly in a biuret or trimer form for improved vapor pressure. In addition. deleteriously affect mechanical properties. and they are used for polyacrylic-urethane powder coatings. signs.

hydroxyl groups react with isocyanates mary hydroxyl groups reacted about 3. for example. package coatings as would be used in Type IV and Type V cantly affect isocyanate reactivity. and V coatings. Popular catalysts include dibutyltin dilaurate. Glycols ISOCYANATE-TERMINATED PREPOLYMER and low-molecular-weight triols require relatively large amounts of isocyanates. usually the most costly ingredient. anate end groups. For example: links [13]. vinyl esters. and the like. which form urea linkages with iso- ings. primary hydroxyl groups react much more rapidly than secondary hydroxyl groups. triols. and zinc octoate. and polylactone polyols. It should be apparent that this method of glycol. Hydroxyl groups are available [14-16]. lecular chain length increase in either a prereaction to form nate group in the para. diethylene glycol. coatings. and glycols. This demonstrated that neighboring groups can signifi. which is polyester are hydroxyl groups. Polyols function as soft segments and impart flexibility to polyurethanes [10]. about 200 to 3000. It was also link molecules as in Type I urethane alkyd [17] to cause mo- found that n-butanol reacted five times faster with the isocya. diol. An chain extension cannot be carried too far since viscosity will excess of glycol is used to ensure that most end groups in the increase very rapidly as chain extension takes place. other Moisture-cure polyurethanes are molecules with free isocy- acrylates and methacrylates. As would be ex- pected. cyanates. The epoxide. Acrylic polyols are prepared not a desirable result if materials for high-solids or other from hydroxy functional compounds.5 faster with phenyl to form polyurethanes. OLIGOMER(OH) 3 + 3 R'(NCO) 2 cone-based materials have good thermal resistance. Sufficient quantities of isocyanate are re- rated. butyl acrylate. and phenolic- based materials have good chemical resistance. Low-molecular- weight compounds such as ethylenediamine are used as Active Hydrogen Sources chain extenders to make polymers for Type VI lacquers. acted with polyols such that there are more equivalents of mers are ethyl acrylate.4-toluene diisocya. stan- where in the manual. ethyl and 2-hydroxypropyl acrylate and methacrylate. These polyols. and tertiary hydroxyl Reactions groups react slower than either other type. trimethylolpropane. Polyether polyols are Catalysts are often used to promote the reaction between usually poly(propylene oxide) polyols that may or may not be isocyanates and hydroxyl-containing compounds. Other prepolymers can be prepared by reacting. diethylene glycol. and 1. Diaza(2. usually supplied by polyfunctional compounds such as gly- cols. of an end-capping manner to provide primary hydroxyl end catalyst are needed to cause marked increases in reaction groups. copolymerizable monomers. Multifunctional reactants are used to isocyanate than secondary hydroxyl groups and about 200 times faster than tertiary hydroxyl groups [11].or trihydroxyl functional nous octoate. triols. that have number-average molecular weights of from nium octoate have been used. phenolic. Epoxide. In other instances. Both hydroxyl-functional and isocyanate are termed "hard segments" that function as pseudocross. pri- As indicated above. particularly ethylene the prepolymer. polyester polyols. and the sili. are usually di. an hydroxyl-terminated prepolymer with two molecules of ten used for polylactone polyols. 2 HO--R--OH + OCN--R'--NCO and impart hardness and rigidity to the final coating. which are described in detail else- rate. diisocyanate to produce an isocyanate-terminated prepoly- lactones are prepared from difunctional carboxylic acids. coating or to form prepolymers that are later reacted in two- nate. DIOL DIISOCYANATE sent only a few percent of the total polymer molecular weight OCN--R'NHCOO--R--OOCNHR'--NCO yet play a significant role in final physical properties.2)bicyclooctane compounds. particularly 2-hydroxyl energy-conserving formulations are produced. Catalysts acrylic polyols. and oligomers that ple. these chain extenders in combination with the isocyanates IV. and tetraols with isocyanate functionality as is needed for Type II. such as HO--R--OH + 20CN--R'--NCO those used for Type VI products. vinyl. polyether polyols. of. For example. ment in specialty finishes. Isocyanates readily react with active hydrogen sources Amine-terminated oligomers based on the alkylene oxides are such as hydroxyl groups and amines. styrene. on the order of 10 to 100 parts per million. tetraols. Examples of such ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . silicone. Polyfunctional amines. and as chain extenders when preparing polyurethanes [12]. and other ethylenically unsatu. these chain extenders repre.2. bismuth stearate. CHAPTER 13--POLYURETHANE COATINGS 91 Technology such as this is used in polyurethane powder coat. a trifunctional oligomer or polyol can be reacted with an contain hydroxyl groups are also reacted with isocyanates to isocyanate under moisture-free conditions and then pack- form urethane linkages and accompany property enhance- aged under moisture-free conditions. These DIOL DIISOCYANATE compounds are also used as initiators for preparation of the HO--R--OOCNH--R'NHCOO--R--OH various polyols with glycerol often used for poly(propylene HYDROXYL-TERMINATED PREPOLYMER oxide) polyols and with glycols and triols such as 1. though higher functionalities are used in special (DABCO). butanediols.6-hexanediol. mer that contains urethane linkages in the central portion of particularly adipic acid. dibutyltin diacetate.4-butane. and zirco- cases. multifunctional (usually di- Low-molecular-weight or monomeric compounds are used functional) isocyanates are used to end cap diols.or 4-position group than with the the final polyurethane that could be used in a Type VI lacquer isocyanate next to the methyl group in 2. are also used as chain extenders.iran-mavad. functional prepolymers are used. Polyesters other than poly. Only small copolymerized with ethylene oxide in a random manner or in amounts. For exam- etc. OLIGOMER(O--CONHR'NCO)3 www. vinyl. isocyanate groups compared to hydroxyl groups. In high-molecular-weight polyurethanes.

particularly at IO0~ or Thermoplastic Polyurethanes higher. nature of the urethane linkages in the hard segment results in ages. the types and functionalities of polyols. Moisture-free conditions are achieved by blan- keting the system during preparation and storage with dry O nitrogen. When the wide range of values of X. they are usually referred to as polyurethanes. poly. and creases which often are undesirable in various polyurethane final free isocyanate content usually ranges between about 3 formulations. the solvent used for the reaction and for any dilution to final product must be carefully dried to exclude moisture. and 16% [7]. number-average molecular weight of about 300 to 3000. mers. are urethane/urea poly. and they contribute to cross-linking (note that biurets can be equivalent to trifunctional isocyanates). ages.iran-mavad. which allows time for the evolved carbon dioxide to leave before it is undesirably entrapped in the solidifying film. polymers of the ABn type. elastomeric macromolecules ble mixed anhydrides that decompose into an amide and are formed. they may be described as linear block co- --R'NCO + --R'NHCOOR'-. Isocyanates are less reactive with urethanes than with ureas. hard segment aggregation and domain segregation from the meric network. cross-linking. these polymers can be viewed as polyol/ R'NCO + RCOOH > R'NHCOOCOR2 > R'NHCOR + CO2 T diisocyanate/short-chain extender polymers that are formed MIXEDANHYDRIDE AMIDE in an equivalents ratio of 1/X/(X . Their chemistry is similar to that of prepolymers except Isocyanates will also react with urethanes to produce al. When \/ applied to a substrate and contacted with ambient moisture. The end product of this reaction to keep final free isocyanate content and storage reactivity at results in stoppage of chain growth and a lower than expected a nil level. A small excess of hydroxyl groups is used lactone. C these products cure by reaction with water to form an unsta. The hard segments act as pseudo cross-links. range of polyol molecular weight available is considered. pared and that a broad range of mechanical and chemical nurates. short-chain extenders are used to connect the prepolymer lophanate linkages. and unexpected molecular weight in. though more This reaction is important to keep in mind when polyesters typically in coatings X has a value of one or less to about 3 or 4 prepared from glycols and dicarboxylic acids are used or [10. Even though Thermoplastic polyurethanes are used in Type VI lacquers these cured films. Biuret linkages are formed in thermally accelerated systems. and in many industrial end uses that require solid products. and the will react with isocyanates to form acyl ureas. soft segment.13].1). the types of molecular weight. 1/2/1 is often used. In most cases this is undesirable. ~ --R'N(CONHR'--)COOR'-. nates reacting with hydroxyl groups to form urethane link- ing. The n u m b e r X c a n vary from 1 or less to as much as 20 or more. strong.92 PAINT AND COATING TESTING MANUAL Exact ratios of hydroxyl to isocyanate are seldom used. In a structural sense. I I UREA LINKAGE O~-~C C~-~O \/ --R'NCO + --R'NHCONHR'-. Carboxylic acids will react with isocyanates to form unsta. ISOCYANURATE These systems cure relatively slowly. The polar significant reaction rate for the formation of allophanate link. www. This can be de- scribed by the following reaction scheme: --R'NCO + H20 ~ [--R'NHCOOH] > --R'NH2 + CO2 T O CARBAMICACID. 2 --R'NCO --R'N NR'-- Solvent drying can be done with molecular sieves. and will lead to branch. One of the blocks is a relatively AN ALLOPHANATELINKAGE long. polyether or polyester that forms the soft or flexible segment. molecules and build them into long polymeric materials. The other block is formed by the reaction of a diisocyanate and temperatures of about 120 to 140~ are required to give a and a low-molecular-weight diol chain extender. strictly speaking. or other ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . a ratio of about when acid numbers are unexpectedly high in polyether. O ble carbamic acid intermediate that dissociates into an amine and carbon dioxide. Since these products are almost always prepared in II solution. readily apparent that a myriad of polyurethanes can be pre- ones and trirnerize (aromatic and aliphatic) to form isocya. it is Isocyanates will dimerize (aromatic) to form uretidine di. Because of solubility characteristics. AN II UNSTABLE INTERMEDIATE /% 3 --R'NCO --R'N NR'-- --R'NCO + --R'NH2 ~ --R'NHCONHR'-. carbon dioxide. In a mole sense. N BIURET LINKAGE I R-- The first reactions leading to urea linkages predominate. a cost factor. The amine in turn rapidly reacts with URETIDINE DIONE isocyanate to form a urea linking group. Amides isocyanates. Allophanate formation results in branching in the poly. and as a result tough. These reactions decrease the expected equivalent properties can be achieved. ~ --R'NHCON(CONHR--)R'-. The chemistry is basically isocya- weight of isocyanates.

dryer drums. and the www. methyl diethanolamine. a cross-linking mechanism that is stable under storage condi- photoinitiator (for example. nificant amount of reaction between the ingredients so that chain extension occurs and molecular weight increases. These adhesives The reactions as depicted above have been idealized. The polymer then is dispersed into water. N. N-hydroxyethylpiperi. "no wax" vinyl flooring. COOH 20CN--R'--NCO + HO--POLYOL--OH > [ + (n + 1 ) H O . High temperatures are needed for the powdered poly- that will cure when exposed to actinic radiation. and tile.--POLYOL--OH CH2~CHCOOCH2CH2--O--OCNH--R'--NHCO--O--POLYOL-. Many of these were mentioned solvent by first preparing an ionomer prepolymer that is above.. mer to flow and level to the extent needed for a particular end tions. Two features of polyurethane coatings that have been neutralized and then chain extended to a desired molecular often looked on as disadvantages are high cost and special weight. the vari- Cationic systems employ an amine-containing diol such ous industry segments have been able to develop safe han- as diethanolamine. lysine. 2 0 C N .com ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . However. Both handing of the potentially hazardous isocyanates that are cationic [21.. etc. the urethane acrylate is considered as the main ingredi.24] systems are known. tronic circuit boards.22] and anionic [23. This causes the final product to have a markedly higher-than- expected viscosity.P O L Y U R E T H A N E COATINGS 93 Radiation-Curable Urethanes [18-20] boxylic acid-containing diol such as dimethylolpropionic acid (2. range cabi- tures such as clear overprint lacquers on vinyl decals. area such as for snack food and similar packaged products. or other compounds for viscosity reduc. because of difficulty with light pen- etration or absorption. CHAPTER 1 3 . elec.. droxyethyl)-a-aminopyridine. and similar compounds. terminated prepolymer from a polyol and then end capping CH3 the prepolymer with an hydroxy acrylate such as 2-hydroxy. The key to successful powder coatings is related to a ent contributing to mechanical properties of the cured film. Another require- is added as a free radical source. In all are expected to be for the low-to-medium demand product commercial and most laboratory preparations there is a sig. nets. used in manufacture or as curing agents. Oligomeric compounds such as these are Powder Coatings formulated with triacrylates such as trimethylolpropane triacrylate to provide cross-linking.2-bis(hydroxymethyt) propionic acid).high performance characteristics of polyurethanes. dihydroxyben- Acrylate-terminated polyurethanes are used in a number of zoic acid. etc. Anionic systems use a car.. The propanesulfonic acid." They are prepared by first forming an isocyanate. For example: products are termed "urethane acrylates" or "acrylated ure- thanes. balance between molecular weight and related viscosity and a When the actinic radiation source is ultraviolet light. In formula.P O L Y O L . and similar compounds.2-diethoxyacetophenone or tions and not effected to any significant degree until flow and benzophenone in combination with an amine synergist. fled polyesters and polyacrylics that cure at high tempera- tion to provide low-viscosity. monomeric acrylates.--coatings. The very.) leveling takes place at the cure temperature. use. ciently high that the powder does not block during storage.iran-mavad.N C O + CH3--C(CH2OH)2--COOH .N-bis(hy. dling and use methods that overcome one of the objections. their ability to cure at lower baking temperatures. dine. sulfonic acids as 2-hydroxymethyl-3-hydroxy- ultraviolet light and electron beam curable formulations. Polyurethane powder coatings are usually urethane-modi- N-vinyl pyrrolidone. Radiation-cured polyurethanes are often used on plastic The main end use for powdered polyurethanes is in the major substrates that require only low or moderate curing tempera. MARKETS Water-Borne Polyurethanes Polyurethanes of the various types are used in a number of Water-borne polyurethanes are prepared in bulk or in a market areas and end uses. essentially 100% solids systems tures. WATER DISPERSIBLE POLYURETHANE O--OCNH--R'--NHCO--OCH2CH2OOCHC=CH2 Water-borne polyurethane laminating adhesives that are A URETHANE ACRYLATE completely free of volatile organic compounds are expected to be the next developments in this area [25].R ' . appliance market--refrigerators. the skill needed in preparing such products. ! ethyl acrylate.O H OCN--W--NHCO--O--POLYOL--O--OCNH--R'--NCO ISOCYANATE-TERMINATEDPREPOLYMER CH3 I OCN--R'--NHCO--O--POLYOL--O--OCNH--R'--NCO+ HO--(POLYOL--OOCHN--R'--NHCOOCH2CCH2OOCHN-- CH2~-CHCOOCH2CH2--OH / COOH 2-HYDROXYETHYL ACRYLATy R'--NHCOO). is readily apparent. 2. The reactions leading to urethane acrylates are OCN--R'--NHCOOCH2~CHzOOCHN--R'--NCO almost always carried out in an inert solvent. Electron beam curable ment is that the glass transition temperature should be suffi- formulations do not require a photoinitiator.. Al- though radiation-cured colored and pigmented inks and coatings are used in the marketplace.

thin coatings t h a t do not m a r k e d l y increase fabric weight o r [19] Martin. J.. 1948. Wire coatings Railroad cars 2493. 65. p. C. M.. Noren. p e c t e d that the two-package (ASTM Type IV a n d V) systems [26] Wojcik. J. Table 1 is a s u m m a r y of m a n y end [22] Scriven. 819. and Koleske.. 1947. and Chang. 42. P.066. Jr. I. I n [18] Salim. U. REFERENCES HOME FURNISHINGS PLASTIC SUBSTRATES Drum dryers Fascia [I] Bayer.. Vol. Piscataway. CA. L. Colour Journal. R. g r o w t h a r e a for t h e r m o p l a s t i c p o l y u r e t h a n e lacquers with [15] Yeakey. C. Varnish. p o w d e r e d p o l y u r e t h a n e s are also i m p o r t a n t growth areas.. 24. Patent 4. and Barush. Leather Tarpaulins [8] ASTM D 16: Terminology Relating to Paint. and Erikson. 275.S. Vol. 1969. 19. These include g o o d elasticity at low t e m p e r a - and Fisher.. tures.098.. T. [23] Scriven. No. 4.. p...S.." Adhesive Age. p. Adhesives. A. and Critchfield. new low-viscosity.412. "Super-Low-ViscosityAliphatic Isocyanate Cross- will have a l m o s t d o u b l e the c o m p o u n d e d a n n u a l g r o w t h rate linkers for Polyurethane Coatings. 22. Public utility works [7] Linak." Journal ofElastoplastics. I n the five-year p e r i o d b e t w e e n 1991 a n d 1996. Patent 4. H." Journal of Applied Polymer Science. 549. V.e." Journal of Coatings Technology... No. R.. C. C.S. L. The textile a r e a is a m o d e r a t e [14] Lee. M. Marine coatings Plant equipment Toys SRI International... 3. Vol. Siefken.. the excellent c o m b i n a t i o n of p r o p e r t i e s as the m a i n driving [16] Bishop. Mast and spar finishes Aircraft and Elastomers. 2503.e. Lacquer. of the overall u r e t h a n e coating market. E.729 (1977). Menlo Park. To decrease volatile [20] Hodakowski.981 (1942).. and Carder. Patent No. 8..743 (1978). E. a b o u t 10%. "Ther- ket. C. L. SRI International. G.641 (1987). E." Supplement C.895 (1966).. i m p r o v e d total coating solids. L. N. E. Vol. U. the high p e r f o r m a n c e can be achieved with very 4203. p a r e d in a b r o a d variety of tensile/elongation properties.762 (1987). NJ. W. [24] Milligan. 06. Patent 4. P. p. R. J.. E. V. Scott. No. V. Vol. d e c r e a s e d volatile o r g a n i c [12] Critchfield.S. E. Range cabinets Optical fibers Printed circuit boards [3] Bayer. a n d p o l y u r e t h a n e polyols [27] are being developed. p... U.. Furniture Electronic parts and [2] Wright. Magnetic tape coatings TRANSPORTATION [9] "Chemical Products for Resins. Koleske. Coatings. 1972.J.. 1975. "Urethane Surface Coatings..S. No. B. F.222. C. F. Elsevier Publishing Company. L... p. Windows Apparel CA. Vol. Effects of Hard Segment p e r f o r m a n c e m a k e the a p p l i e d cost of the p o l y u r e t h a n e c o m . a n d a n ability to be pre- (1980). L. Koleske. c o n s u m p t i o n rising from 84 million lb in 1991 to 133 million [27] Gardon. R. and Cumming. July 1993. Inc. Vol. New York. II. p o l y u r e t h a n e s are replac= Based Polyurethanes. Amsterdam.S.. 1975. m a c h i n e washability.. F..01. U. G. Marcel Dekker. A.911 cleanability. Rubber Bridges Golf balls World.370 (1972). U. L. INDUSTRIAL MAINTENANCE RECREATIONAL PRODUCTS [5] Schollenberger..R. 218. F. p. [13] Seefried.94 PAINT AND COATING TESTING MANUAL T A B L E 1--Polyurethane end uses. J. 1947. 36. O. S.. D. Vol. W. 10C. with Vol. G. 1992.236. a b r a s i o n resistance. G. ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ .046. uses for p o l y u r e t h a n e coatings. "Polyurethane Polyols: Ester-Bond Free Resins lb in 1996 (38 200 to 60 500 m e t r i c tons).H. "VOC-Free Adhesive Use Grows Due to a c o m p o u n d e d a n n u a l rate of 5% o r f r o m 209 million lb to Increased Performance. Vol. J.. H. p. Polymer. Effects of Soft Segment Vari- Vinyl decal overprints Motorcycles ations. and Chang. p.131. and Winfrey. Patent 3. c o m p o u n d content.S.054 (1968). 0. 83. E. Patent 4. Industrial buildings Golf clubs Gym floors [6] Smith. aliphatic isocyanates [26] (1978).. Vol.. C.. www. i.8000. Lower coating thickness a n d equivalent o r i m p r o v e d moplastic Urethane Elastomers. Luggage 1992.654.. [4] Bayer. Vol. W. 4. "Polyurethanes. Medical equipment Automotive OEM Automotive refinish [10] Seefried. Paint. p o l y u r e t h a n e coating m a r k e t will g r o w at [25] Long.602 organic content. R. Variations. 592.S. Trucks and buses [11] Bailey. p. M. 19...iran-mavad. p. Alkylene Oxides and Their Poly- Vans mers. and Takei. i. J. 1991. and Chang." Journal of Applied Polymer Science. O. It is ex. J. and Critchfield. M. it is n o t a c o m p l e t e listing. Report No.E. January ing poly(vinyl chloride) plastisols as u n d e r c o a t i n g s a n d seal. Zimmerman.591 (1978). Koleske. Coady. J. H. A59. ber 1993. F. Jr. 7. Rinke. H." Roof coatings TEXTILES Chemical Economics Handbook. and Dodd. Refrigerators Wood floors Sheet molding compound German Patent 728. Magnus. 39... C. No.. 4. J.. change styling factors such as drape. Septem- 265 million lb (95 000 to 123 400 metric tons) [7]. and Schild. Solid Polyurethane Elasto- "No wax" flooring and tile equipment mers.. 3. that can be o b t a i n e d are factors that "Effect of Short Chain Diol on Properties of Polycaprolactone offset their high cost.S. U. Sealants. K. petitive with the plastisol. May 1991. C. L. V. Angewandt Chemie." Modern Paint and Coatings. No. W a t e r b o r n e a n d for High Solids Coatings. Modern Plastics. solvent a n d w a t e r resistance.. MISCELLANEOUS Aerospace coatings Upholstery and Related Products. J. 177. d r y [17] Christenson. U. Menlo Park. ASTM Book of Standards. Radiation Curing. F o r example. August 1986. U. E. 10. European Patent Publication 209. Kalt.S. 13. ants in the a u t o m o t i v e a n d o t h e r t r a n s p o r t a t i o n coating m a r . W.. it is esti. August 1992. H. addition.. p. 137. and Moore. Orthner. April 1993. G.. 25. Patent 4. m a t e d t h a t the U. force for use. 149. "Ther- Safety glass Shoes Golf carts moplastic Urethane Elastomers. Patent No. J." Hill America Inc. R. Although [21] Scriven. T. H..

some silicone resinous coatings and erty makes silicone coatings ideal for conformal coating of fluorosilicone based coatings. controlled-release drug delivery. the chemical plications for biocompatible silicone coatings include drug processes usually associated with aging of coated surfaces are delivery devices for both transdermal and long-term im- often much slower and in many situations virtually elimi. almost gel-like character. coatings can be ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . solvents. such as that from a cobalt-60 source for doses furnace parts. Properly designed and which are used to provide coatings for medical devices. Such resinous coatings can provide physical Silicone coatings are available in various forms ranging scratch resistance as well as chemical resistance. ments. which require approximately 1 h at case of silicone elastomeric coatings. the ganic substrates in varied spacecraft applications. Also. incinerators. Petraitis ~ UNIQUE PROPERTIES OF SILICONES THAT implants such as heart pacemakers. elastomeric coatings. can cause depolymeriza. provide soft tissue replacements by forming an envelope to als for a wide variety of applications. Highly porary basis. the silicone coatings can and Silicone coatings based on trifluoropropyl methyl poly. as condensation between silanol groups alone. dissolution of the coat. Technology to Carpinteria. In addition. thin silicone elastomer coatings are used to Silicone based coatings are among the most useful materi. because the Si--O and A final characteristic which makes silicone coatings useful Si--C bonds are not present in the natural organic world. viding higher performance under moderate heat environ- cellent weatherability characteristics. as well as the ultraviolet and infrared and missile coatings. nated for silicone coatings. in excess of 20 Mrd. silicone biocompatibility and resistance to degradation via biochemi. 1995 Silicone Coatings by D. Typically. Among the most common curing agents tion of the siloxane backbone. strophic thermal degradation. They have also been used M A K E T H E M U S E F U L AS C O A T I N G S to coat temporary implants such as catheters and surgical drains. condensed resins can be fornmlated to provide hard silica- cone coatings are used to encapsulate and seal permanent like abrasion-resistant coatings. the hardness of the final low earth orbit. NuSil Technology. Because the basic bond encapsulate gels and/or normal saline solutions. minimize shrink and maximize adhesion during the cure 95 www. This prop- In a similar manner. variation of the R group itself can result in somewhat differ- cal and biochemical characteristics of silicones are those ent flexibility and other properties.astm. and when these prop. Operations. in particular. For complaint coatings. CA 93013. Sili. MNL17-EB/Jun. branched resinous silicone coatings chemically begin to ap- proach the properties of silica surfaces as the organic pen- dant content is reduced. plantable. in plied in a solvent solution and are mixed with curing agents particular at elevated temperatures. or in the are lead and zinc octoate. do provide an SiO2 ash coating which may permit the emer- siloxanes have resistance to swelling from such agents as gency operation of the electrical device on a short-term tem- gasoline. resulting in failure. involves the condensation of silanol groups In a similar manner. is their inherently low or nonflammability. When combined with their hydrophobicity and been designed to mix with organic coatings and paints. As the R: Si ratio is decreased. Silicone from a hard. Strong acids or bases.iran-mavad. cross-link density of the resin effectively increases. high-temperature appliances. do not provide good resist. silicones provide ex. rigid resin to a compliant elastomer to a soft. Recent ap- energies of Si--C and Si--O bonds are so high. Underwriters' Laboratories Flame Test (UL-94). silicones are unsurpassed in resistance to Specific coating applications include jet engine components. As the organic pendant groups are F O R M S OF S I L I C O N E C O A T I N G S reduced. pro- oxygen and ozone resistant properties. Such coatings often involve the condensation of alkoxy groups with silanol groups as well 1Vice president. and various other reagents. Another family of applications which combine the chemi. 1040 Cindy Lane. Similarly. The cross-linking mechanism ing itself. however. In the event of cata- solvent resistance. Also. silicone coatings provide protection for or. elastomer coatings have been rated SE-I when tested via cal and biophysical processes are also significantly reduced. hard radiation. the SiO4/2 content increases and the chemical resist- ance Copyright9 1995 by ASTMInternational www. The rigid resins are typically sup- ance to strong acids and/or bases. silicone coatings are resistant to virtu- ~-~SiOH + H O S i ~ ~ ~ S i O S i F + H20 ally all frequencies of the electromagnetic spectrum. have excellent various electrical circuits and devices. erties are combined with the resistance to atomic oxygen in By varying the R group:Si ratio. specific silicone resins have frequencies. 250~ to attain complete cure. prior to application. J. jet fuel.

This ultraviolet mechanism is often combined with a high-strength elastomers to soft gel-like coatings. Applications include solar reinforced. 2) is used where one-part insoluble components such as high surface area fumed silica convenience is desired. The addition cure system (No. despite www. but they find limited use as coating materials and were these elastomeric coatings depend. however. and coating of are 1. ~--~SiOH + ROSin--.1-trichloroethane for thin layer ap- radiation from various rocket motors and jet engines.~ + ROH characteristic of many peroxides. kets for fire resistance. tough physical proper. Another novel silicone elastomer coating which has been 4.88 to 43. molecular-weight alcohols such as ethanol and isopropanol ity characteristics for certain thermal protection surfaces on and ketones such as acetone are not suitable because sili- the space shuttle. true solutions can be ties. Other cure systems have been developed for silicone elasto- The properties and the cure systems which are chosen for mers." Among the most common inhibitors are sulfur. Because of envi- per-million levels of platinum catalyst. compliant. for reinforcement and often other solid components such as able. which have not involved the use of solvents. Low- quartz blankets to provide adequate emissivity and reflectiv. Because the system contains parts. Various methyl isobutyl ketone for adequate dispersing. selectivity of the specific peroxide is 1. VM&P naphthas. 2. ~ S i O H + CH3COOSi~ ~ ~ S i O S i ~ + CH3COOH 3. Fluorosilicones re- ~ ~ O S i . negative characteristic of the addition cure system is its sus. and where acetic acid given off during the cure is not a titanium dioxide pigments for coloration or reflectivity prop- problem. and application ease.8 kN/m place. flexible coatings. and various fibers. SiOH + HSi (No. Spark protection welding blankets are meric siloxanes with appropriate cross-linkers to provide a common application for peroxide-cured silicone coatings. In particular. These coatings have limited use. most commonly described as a dispersion because it contains The acetoxy cure system (No. Among also often include blends of solvents to provide the proper the applications for the oxime cure systems are coatings for combinations of flow. Pro- Type A = 70 cesses using the combination cure can be used to minimize Tensile Strength: 0.8 MPa the time and space required to hold the coated parts until Elongation: 50 to 1500% cure is completed before downstream assemblies can take Tear Strength: 0.1. Typically. chlorinated hydrocarbons. ~ S i O H + HSi-~. 1) mechanism is often used to provide The most common form for silicone coatings is a disper- release coatings for backing paper for pressure sensitive ad- sion of the silicone in solvent. The dispersions leaving group instead of an acetic acid leaving group. Also. made for unfilled silicones or for silicones that are resin the best overall flame resistance. Among the cure mechanisms Since peroxide-cured silicones require higher temperature which result in elastomers are the following cures. The actual coating itself has poor strength but attains tough elastomeric silicone.34 to 13. the uncured elastomer base is its properties by simply impregnating the substrate. particularly for satellites. ~SiCH~---CH2 + HSi I~ Pt ~ ~SiCH2CH2Si~ Sn developed is a combination cure involving the ultraviolet 5. containing organic rubbers and organo-tin compounds fluorochlorocarbons and chlorinated hydrocarbons. and xylene.1. when cones are generally incompatible with these lower-molecu- combined with certain thermal enhancing fillers such as iron lar-weight oxygen-containing solvents. and erties of the acetoxy cure system. The carrier solvent for these dispersions may include The oxime (No. the sealants or glazing compounds.iran-mavad. standard cure mechanism to provide a combination cure. 3) cure system. on the generally developed for specific applications such as building end use and the method of application. If the coating is based on a hesives. and. and one simultaneously optimize cure rate and adhesion. and burn-through cause the final cured elastomeric coating lacks the overall protection for the liners of solid rocket motors. the elastomer could have properties within the following This system provides quick surface cure followed by the ranges: slower room temperature cure of unexposed. be- cell protection.96 PAINT AND COATING TESTING MANUAL needs to be incorporated to prevent cracking and subsequent which are often used as plasticizers in plastics and also as flaking of the coating from the substrate. alkoxy silanes are often incorporated into the formulation to There are other silicone elastomeric cure systems. 5) cure system provides many of the prop. glass microballoons. plication. where relatively slow cure is accept. to a large extent. shadowed areas Durometer: Type 00 = 10 to ultimately provide a fully cured conformal ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . The only toughness of the filled materials. Aminofunctional catalysts for other silicone coatings. For instance. is often used to quire the use of such solvents as methyl ethyl ketone and provide ablative and thermally insulating coatings. Fluo- products incorporating the alkoxy two-part cure system are rosilicone-dimethyl copolymer-based silicones can be dis- used to protect surfaces and components exposed to plume persed adequately in 1. Recent developments have resulted in silicone coatings ceptibility to inhibition. sions and solutions has become less desirable. it can be readily ronmental concerns. The alkoxy 2-part (No. fluorochlorohydrocarbons. erties. of the most significant applications is to coat fiberglass blan- Silicone elastomeric coatings incorporate the use of poly. electronic components and protection for organic compos. evaporation. ~ S i O H + R2NOSi~-s--~2 ~ S i O S i ~ + R2NOH photoinitiation via free radical formation to provide cross- These elastomeric coatings can range from extremely tough. For example. their usefulness is constrained by the substrate upper temperature limits. 4) has characteristics which True solutions can also be made if the silicone contains no permit rapid heat-accelerated cure. but results in an oxime both aromatic and aliphatic hydrocarbons. the use of solvent carriers for disper- "poisoned. insoluble components. Among the most common solvents for silicone dispersions ites to prevent atomic oxygen degradation.1-trichloroethane. due to the platinum catalyst. virtually nil shrinkage. ~ ~SiOSiw~ + H2 critical to prevent poor cures due to the oxygen inhibition.

bath life. Additionally.2 torr. ongoing to develop water-based dispersions. the demonstrated physical properties. thin layer applications are difficult unless solvent bubble formation. nonvolatile content. elongation. a steam autoclave may be used. variables including solvent. tion and by acceleration with heat. normal air circulating oven. If accelerated cure is required for therefore. several variables need to be considered. Among Dielectric Withstanding Voltage the variables to consider are the following: viscosity. Needless to say. Durom- apply. the physical properties usually not applicable for either large areas or mass produc. the use of levels of purity to prevent the contamination of solar cells. Flammability vent to maintain optimal bath viscosity. Similarly. are significantly less than the current TESTING CONDITIONS solvent-based silicone coatings. Dipping. but only provide coatings that are resistant to handling. respectively.S I L I C O N E COATINGS 97 their low toxicity and nonflammability. inclusion. pot life. the evapora. but to date. The current products. although higher than the 100% solids coatings. of the cured elastomer are critical parameters. and ASTM even after removal from the vacuum. The tensile tion coatings. The thinnest coatings result Coating Thickness from spraying of two solvent dispersion utilizing standard Fungus Resistance aerosol spray guns. Q Resonance The most securely sealed surface layer is accomplished by Q Resonance after Immersion dip coating. however. to apply a uniform silicone coating. For often used to ensure uniform coating with minimal drip re. low-viscosity. controlled immersion and withdrawal rates. ASTM Test Method for of the reactive volatile components which would prevent cure Weight Loss of Plasticizers on Heating (D 2288). Again. the cure parame. the vacuum removal of solvent is unwarranted and sity of Plastics by Displacement (D 792). Test Method for Specific Gravity (Relative Density) and Den- monly. Vacuum Environment (E 595). Test Method for Rubber Property--Durometer Hardness ters demand significant considerations. MIL-I-46058C includes the following tests: on the device being coated and the specific type of silicone Curing Time and Temperature being used. and Thermal Shock cure systems must be optimized. the maximum CVCM value for coatings intended for space Low viscosity. Unfortu. If a one-part Materials which are used in applications for spacecraft are humidity-actuated cure system is used. and Vacuum treatment may also be used to enhance removal of specific gravity tests are defined in ASTM Test Method for the solvents. most com. is For silicone elastomeric coatings. because of Montreal Protocol Agreements. are being phased out therefore solvent is merely evaporated at ambient pressures.0%. virtually all of the strength. and other sensitive instrumentation. the application ity. which are cured via moisture activation. Leakage Current Testing percent solids. www. The and vibration of the bath and/or object to be coated can be coatings intended for satellite applications require these high used to minimize bubble entrapment. for one-part silicone coatings the viscosity is low enough to permit proper coating. consideration must tested via ASTM Test Method for Total Mass Loss and Col- be given to provide a dry blanket over the bath to prevent a lected Volatile Condensable Materials from Outgassing in a partially cross-linked elastomeric skin from forming. Flexibility tion of solvent during the dip processing needs to be compen. Similarly. Another consider. (D 624) respectively. eter and tear strength measurements are defined in ASTM Regardless of the methods of application. Silicone-based con. hydro. and environmental effects. The solvent evaporation can also be enhanced by air circula- carbon solvents are undesirable because of their flammabil.iran-mavad. silicone coating does not exist. Basically.. two distinct solvents with different rates of evaporation are optical surfaces. Dry ar. CHAPTER 1 4 . are very low strength and do not one-part coatings. For painting application. spraying. Thermal Humidity Aging sated for by periodically or continuously adding make-up sol. However. solvent. it is ineffective to use nately. and painting are the most Appearance common types of application. the technology for high-strength. experience involving Insulation Resistance aerosol spraying is critical for acceptable coatings. of heat should be limited or applied in a stepwise manner to formal coatings have been developed without solvent prevent solvent entrapment below the surface resulting in carriers. ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . most silicone materials. and modulus are defined in ASTM Test variables discussed in the above dipping and spraying also Methods for Rubber Properties in Tension (D 412). Also. but care should be taken to prevent evaporation Viscosity of Adhesives (D 1084). This test is used to determine gon is often utilized to prevent moisture in the air from the amount of collected volatile condensable material and reacting with the silicone base coating. Research is after all of the carrier solvent is removed. Again. for the polymeric components prior to compounding into the Painting or brush coating substrates is yet another method finished product. Vacuum exposure (D 2240) and ASTM Test Method for Tear Strength of a may be used to remove air bubbles and to ensure flow under Convential Vulcanized Rubber and Thermoplastic Elastomer surface irregularities or impregnation of porous substrates. toxicity. and cure system choices. Of course.1% and the m a x i m u m TML is 1. The viscosity. 100% heat acceleration because humidity is obviously reduced in a solids. total mass loss that eludes from a material when exposed to ation for the dip coatings is the possibility of air bubble 125~ for 24 h at vacuum less than 5 • 10 . when cured. The test requirements for silicone coatings include MIL-I- 46058C for qualifying silicone coatings as insulating com- Methods of Applications pounds for electrical coating applications of printed circuit The methods of applications for silicone coatings depend board assemblies. extended devolatilization is required gions and minimal bubble formation. However. applications is 0.

Coating perma- nent implants as well as temporary implants with silicones provides improved safety and efficacy. Combinations of silicone coat- conformal coating of electronic circuit boards. Electrical coatings with semiconducting prop- posite materials would be unusable due to their atomic oxy. Silicone coatings typically have nated with drugs can be used for transdermal drug delivery. sity of silicone coatings to cause "sticking" to contacted sur. silicone elastomeric coatings are produced by meet the requirements of specific applications. cal properties are also being developed. Specifically. erties for electronic applications and elastomeric coatings gen degradation. stiffening points of -65~ and can be formulated with When combined with a silicone pressure sensitive adhesive. a number of tests which are oriented toward the spe. Foley catheters coated SPECIFIC APPLICATIONS FOR SILICONE with silicone elastomers result in less patient discomfort and COATINGS reduced infection rates. Because of ings are being investigated for use in various drug delivery their previously described stability properties. Included the addition of iron oxide. silicones make devices. NEW REQUIREMENTS FOR SILICONE dation is significant enough to rapidly erode and degrade COATINGS organic substrates including epoxies. the biocompatibility of silicones cific application have been developed and ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . As discussed previously. cone coatings with even more stringent requirements and tages of high strength and low weight associated with com. makes them ideal for medical applications. philic silicone coatings are being developed for reduced ide. hydro- bined with specific fillers including zinc oxide. Similarly. glass or ceramic microballoons. Silicone coatings with variable properties of silicone resins make them ideal impregnant electric properties are also being researched. The incorporation of phenyl siloxanes into the basic tested by subjecting the interface to an applied pressure for a silicone polymeric species provides increased ablative prop~ fixed time followed by measurement of the force needed to erties. Coating protection permits the use of Research and development efforts continue to provide sili- composite materials in space applications where the advan.115~ This makes them ideal for complete system of controlled drug delivery devices can be extreme environment electronic device protection. The inherent stability of silicone coatings when com. with volume resistivities in the 10-4 to 10-5 ohm-centimetre The high-temperature stability and excellent dielectric range are being investigated. and various copolymers--including silicone-boranes reseparate the surfaces. coatings for high-energy capacitors used in jet engine ig. Again. urethanes.iran-mavad. fabricated. temporary pres- sure-sensitive silicone adhesive coatings are used to provide Among the varied applications for silicone coatings is the adhesion directly to the skin. among these are the "blocking" test to determine the propen. protection from impingement of high-energy lasers. www. launch equipment. Atomic oxygen degra. Specifically layered coatings of silicones impreg- ideal conformal coatings. silicone coatings which provide specific biologi- nitions. Similarly. which provide ablation protection. and zinc orthotitanate are often used to provide specific thrombogenicity. a stiffening points as low as . and microporous coatings are under devel- emissivity and reflectance required for thermal control coat. and polyes- ter-based thermosets. and thrust reversers are faces after application and cure. For similar reasons. Launch vehicles. opment for controlled tissue in-growth response. and graphite fibers. This test involves contact often coated with specially formulated silicone ablative coat- between the silicone-coated surface and the surface to be ings. Silicone coatings are used almost exclusively to provide protection from atomic oxygen degradation in low earth orbit (approximately 100 to 500 miles high). A variety of tests have been developed and silphenylenes--have and are being evaluated to provide to measure the adhesive force of the coating on the substrate.98 PAINT AND COATING TESTING MANUAL Other tests have been developed for silicone coatings to ings. titanium diox. specifications.

Water-based in autoclaves under moderate to high pressure. a n d poly(vinyl chloride).13. and Vinyl resins for coatings are made by several processes. dilute acids. Organosol and plastisol coatings technology that permitted ate modifiers. tate) resins was begun in 1936.b a s e d c o a t i n g s . is typically initiated by free radical generating compounds ular-weight polymer latexes that require heat to fuse. of vinyl resins used for plastisol and organosol coat- lent resistance to water. air-dry or baking finishes can be produced the use of very-high-molecular-weight resins were developed having thermoset-like properties. The use of high pressure and low temperature generally favors the formation of high-molecular-weight resins. vent-soluble grades are also made by the emulsion process. while emulsion or disper- while proper pigmentation helps to protect vinyl coatings sion polymerization is used to make the much higher molecu- from attack by UV light. vegetable oils. achieve special properties. Special techniques have been developed that enable the use of high-molecular-weight vinyl chloride homopolymers as dispersions in organic media called plastisols or organosols that require a heat fusion step to form films or coatings. though by formulating with appropri. compatibility with other resins mers were introduced in 1939 and hydroxyl-modified resins and polymers. and McClure described applications of vinyl resins including mers to improve solubility. red.9~ Polymerization is carried out electrostatic spray or fluidized bed techniques. Post-polymerization processes are applied to some resins to ~Union Carbide Corporation. In 1933. These modi. The M. are: (1) relatively high glass transition temperature. eventually black. alcohols. The reaction vinyl chloride polymers and copolymers include high-molec. aliphatic hydrocarbons. Some stabilizer systems can provide lar weight polymers for plastisols and organosols. or other mono. or adhesion to specific surfaces. and chain transfer agents are commonly used to control molecular growth.iran-mavad. Vinyl chloride monomer is a gas at standard conditions pounded for use as powder coatings for application by either with a boiling point of . NJ 08805. and (3) inertness in contact with foods (FDA-listed resins only). i n k s . W. (2) excel. and alkali. about 1943 [2. to make the solvent-sofuble resins. growth (molecular weight) of the polymer. 1995 15 Vinyl Resins for Coatings by Richard J. Functional monomers contribute their use as swimming pool coatings [1]. The polymerization is exothermic.astm. Commercial production of poly(vinyl chloride-vinyl ace- mers provide adhesion. Suitable heat stabilizers are employed that Polymerization by solution and suspension processes is used allow the processing of vinyl coatings at high temperature.and vinyl chloride and vinyl acetate in 1928. Some sol- limited protection to clear vinyl films. The first commercial use of these vinyl resins was in fied vinyl resins are most often used as thermoplastic. vinyl acetate. B o u n d Brook. 1936 as a coating for the inside of beer cans. ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . Burns 1 VINYL RESINS FOR COATINGS History Definition About 1912 Ostromislenski pioneered the industrial inves- tigation of vinyl polymers and made and fractionated THE VINYL RESINS USED IN s o l v e n t . ings ranges between about 60 to 110 000 [4]. Reid invented the copolymers of adhesives are low-to-medium molecular weight co. 99 www. Vinyl Polymerization chloride homopolymers and copolymers are also com. and aqueous dispersions of low-molecular-weight polymers that reaction temperature regulation is necessary to control the utilize coalescents to form films at room temperature. The num- General ber average molecular weight (M. Davidson tercopolymers of vinyl chloride. carboxylic acid-containing mono.) of commercially available solvent-soluble vinyl chloride homopolymers and copoly- Important characteristic features of vinyl resins/coatings mers ranges from a low of a few thousand to about 45 000. while hydroxyl-containing mono. MNL17-EB/Jun. E. Manufacture with a resultant change in color from clear to amber. Copyright91995 by ASTM International www. vent-soluble lacquers. specific properties. in 1945.3]. and also such as peroxides. Vinyl resin films can be degraded by exposure to high temperatures or by long-term exposure to ultraviolet light. Carboxyl-modified copoly- mers contribute to reactivity.

several U. b. qualitative characterization of separated paint vehicle solids lyze the pendant acetoxy groups to yield a vinyl alcohol moi.100 PAINT AND COATING TESTING MANUAL Solution Process Vinyl Chloride Copolymer Coating Resins Polymerization is carried out in a solvent in a batch or Four types of solvent-soluble coating resins offered by continuous process. The first step consists of the preparation of a sion resins for plastisols and organosols [10]. and ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . Other suppliers of solvent-soluble vinyl resins and their product lines are listed in Tables 2 through 5 for Denka Kagaku. shear viscosity measurements to characterize vinyl disper- step process. www. Epoxy-modified vinyl chloride copolymers. The viscosity of the reaction medium Union Carbide are shown in Table 1. by infrared spectroscopy. Vinyl chloride-acetate copoly- acterized as spherical with a size between 100 to 300/~m. poly(vinyl chloride-acetate) copolymer by either a solution or ASTM Test Method for Infrared Identification of Vehicle suspension process. 2. 176. These polymers are increases as m o n o m e r is converted to polymer. which accounts ASTM D 2124-70 (Reapproved 1988). the copolymer resin is dissolved in Solids from Solvent-Reducible Paints (D 2621-87) covers the a suitable solvent and a catalyst is added to partially hydro. the auto. Test Method for for its unique solubility/compatibility properties. surfactants are normally used to stabilize the smaller fying and characterizing vinyl resins [5.S. and 177. of polymerization can be monitored and controlled via vis. mers. Next. Each component can then be analyzed by infrared cross-linkers. Carboxyl-modified vinyl chloride-vinyl acetate copoly- clave varnish is stripped of unreacted vinyl chloride mono. Emulsion Polymerization Vinyl Resins--Analysis Like the suspension process. Hydroxyl-modified copolymers of two types: or water/alcohol mixtures.6]. several ASTM documents deal with the identification used in plastisol and organosol coatings. the slurry is centrifuged to remove a. vinyl chloride-acetate modified vehicle is presented dried as described for the solution process. ranges from about 75 to about 200 ~m.and copolymer vi- nyl resins to determine important characteristics such as Post-Polymerization Process total chlorine content for composition. Wacker Chemie.170. Vinyl copolymer resins are listed by chemical identity in dal polymers are used in small amounts to stabilize the drop.300. transporting food. heating. mer. ASTM Guide for Testing Poly(Vinyl Chloride) Resins (D 4368-89) describes methods for homo. hydroxyl-modified vinyl chloride-acetate copolymer. Particles of suspension vinyl resins are char. cometry. most of the liquid. Normally the preparation of food contact surfaces of articles used in processing.iran-mavad. When the appropriate viscosity is attained. plasticizers. The resin thus [11]. and characterization of vinyl resins used in coatings materi- als. Food and Drug Administration regulations such lets of suspended monomer(s) to control particle size. A spectrum for an ortho-phthalic ety. holding. stabilizers. technique [12]. The as 21CFR 175. or produces resin of particles size ranging from about 0. and the polymer is precipitated by the addition of water 3. but in place of water-soluble poly. Vinyl chloride-vinyl acetate copolymers.180. The modified resin is then precipitated from solution and alkyd.1210 as compo- stabilizer used remains with the resin during and after poly. There are many references to chemical methods for identi- mers. nents of coatings on metal and paper substrates for use as merization and resin recovery. However. packaging. is irregular. and with coreactants such as isocyanate or amino-formaldehyde fillers.2 to 2 specific papers dealing with the subject [7-9]. Suspension Polymerization Suspension polymerization is generally carried out in a FDA Status water medium. or as components of closures with sealing m u m viscosity. Vinyl-alcohol-modified polymer derived from poly(vinyl The particle size of the dried resins produced by this process chloride-vinyl acetate) in a post-polymerization process. manufac- solutions of suspension resins requires that mild heating be turing packing. Hydroxyalkyl acrylate modified directly polymerized. producing. BASF. high and low Some vinyl-alcohol modified resins are prepared in a two. High-molecular-weight water-soluble colloi. mers. /~m. and the extent produced by the solution polymerization process. dilute solution vis- cometry to assess polymer molecular weight. then the resin is dried in fluid-bed dryers. Spectra of neat vinyl resins can be uses an oil-soluble rather than water-soluble initiator and found in sources such as atlases. gaskets for food containers. presents prepared directly using other hydroxy-containing monomers methods whereby vinyl compounds can be separated into in their compatibility with alkyds and in the rate of reactivity components including resins. 1. These high-molecular-weight powdered products are Also. or employed to achieve m a x i m u m clarity of solutions at mini. formed has only secondary hydroxyl groups. encyclopedia of plastics. 176. Analysis of Components in Poly(Vinyl Chloride) Compounds These vinyl-alcohol-containing resins differ from those Using an Infrared Spectrophotometric Technique. emulsion polymerization is also carried out in water. and several other vinyl chloride copolymers made with monomers having acid or ester functionality are described. the in- m o n o m e r droplets during polymerization. and the particle shape 4. A special form of frared spectra of vinyl resins are very useful for qualitative emulsion polymerization called dispersion polymerization and quantitative purposes.

Vinyl Vinyl Isobutyl Approximate Solution T a b l e 6 lists t h e r e l a t i v e a d h e s i o n o f s e v e r a l v i n y l r e s i n s t o Grade Chloride Ether Viscosity.4 1000GKT 91 3 . 0. s t r o n g a d h e s i o n is d e s i r e d . /Oxirane oxygen. . . TABLE 2 w S o l u t i o n vinyls from Denki Kagaku. . stain resistance. 0. wt% Vinyl Vinyl Carboxylic Acrylic Inherent Grade Chloride Acetate Acid Ester Viscosity 1000A 86 14 . .50 74 27 000 650 VMCC 83 16 1a Acid 1. ~ Wt. .44 77 22 000 400 VAGF 81 4 15e Hydroxyl 1.15 54 5 5O0 2O *Referenced to polystyrene standard.56 70 33 000 930 VAGC 81 4 15e Hydroxyl 1. 67 15 000 --. . .0 0. 0. 6 0. i n m o s t cases. ~Hydroxy alkyl acrylate. .8g~ --. . .V I N Y L R E S I N S FOR COATINGS 101 TABLE 1--Typical properties of UCAR | solution vinyl resins.. .0 0. VAGH 90 4 6d Hydroxyl 2. .. and d e g r e e o f p o l y m e r i z a t i o n p r o d u c e a w i d e r a n g e o f v i n y l poly- o p t i o n a l i n g r e d i e n t s s u c h as s t a b i l i z e r s . . . Highest solubil- and cross-linker(s).74 79 44 000 1300 i VYHH 86 14 .S u s p e n s i o n vinyls for solution coatings--BASF.0 0. J20% resin in MEK. t i o n s is c o m p a r e d i n T a b l e 1. . . .5 1000CS 86 13 1 -.0 0. t h e r e a r e s p e c i a l c o a t i n g s s u c h as Composition. .30 65 15 000 70 VYES-4 67 11 22 e Hydroxyl 3.38 72 19 000 100 VMCA 81 17 2a Acid 2. . . Variation in the ratio of vinyl chloride to vinyl ester and the plasticizer.40 72 22 000 200 VMCH 86 13 1a Acid 1. CSolution--40% resin in MEK/toluene 3 • 2. ity is f a v o r e d b y l o w v i n y l c h l o r i d e c o n t e n t a n d l o w m o l e c u l a r T h e r e s i n is n o r m a l l y s e l e c t e d o n t h e b a s i s of its a b i l i t y t o w e i g h t . 0.9 0.iran-mavad.53 79 27 000 1000 VAGD 90 4 6d Hydroxyl 2. ~Maleic acid. 0. . The resin selection may be made on the need for reactive MP-25 75 25 35 MP-35 75 25 35 functionality to produce cross-linked coatings that change MP-45 75 25 45 the nature of the coating from thermoplastic to thermoset- MP-60 75 25 60 like properties that are characterized by improved solvent or a20% resin solutions in toluene.3 0.44 65 24 000 275 VROH 81 4 152 Hydroxyl 2. aPoly(vinylalcohol)..0 0. VEpoxy-containing monomer. www.32 70 15 000 55 VERR-40 82 9 9 b'c Epoxy 1. wt% s t r i p p a b l e o r p e e l a b l e c o a t i n g s w h e r e a d h e s i o n is n o t w a n t e d . .com ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ .~ ~ 0. Formulation of Solution Coatings Solubility A typical vinyl coating usually consists of resin. .5 TABLE 3 . . 0. CHAPTER 1 5 . Composition. mers with different solubility characteristics.3 0.. M.. . T h i s r e l a t i o n s h i p i n t e r m s of v i s c o s i t y o f r e s i n s o l u - p r o v i d e a d h e s i o n to t h e s u h s t r a t e .5 1000AS 86 14 . pigments (required for exterior exposure). . gOn solids. m o d i f y i n g r e s i n ( s ) . Polymer Composition.4 IO00C 86 13 1 --. . 0. ." MPa.50 72 27 000 600 VYHD 86 14 . . wt% Reactive Inherent Glass Solution UCAR| Functionality Viscosity. .s various polymers and substrates. solvent(s). .* cP VYNS-3 90 10 . . h30%resin in MEK. W h i l e . Transition Average Viscosity ~' Solution Po/y(vinyl Poly(vinyl ASTM Temperature Molecular at 25~ Vinyl chloride) acetate) Other Type Wt% D 1243 (Tg). . .

Aromatic hy. Typical solvent blends used for spray application a n d the reformulated c o m p l i a n t MPR-TA 91 3 6 . a n d desired solids.56 E 15/40A 85 . Plasticizers are often used with vinyl resin coatings to im- I n response to regulations restricting the type a n d a m o u n t prove flexibility.4 E 20/55A 80 .. up s h o w n in Table 8. The extent of the aliphatic h y d r o c a r b o n s c a n be usd as diluents.7 H 40/60 60 40 . Higher levels can lead to Vinyl chloride copolymer solutions also exhibit what is viscosity instability. A graphical p r e s e n t a t i o n of the m e m o r y blend. Careful attention m u s t be paid in vinyl coating formu. solution will r e t u r n to the same value as that of a solution that ily formulated with other resins that are carried in alcohol.88 E 15/45M 84 15 1 9. This behavior is higher solids at lower solution viscosity. The viscosity increase m a y be small or so can be used at high levels. in the range of 50 to 65% of the large that the solution sets to a gel. a n d only low boiling aliphatic hydrocar. aromatic h y d r o c a r b o n s a n d m a k i n g up the difference with Composition. effect is presented in Fig. are read. (b) solids c o n t e n t of the solution. the viscosity will n o t immediately r e t u r n to its original Alcohols are strong precipitants for vinyls a n d are n o t value because of the time lag needed for the effect of the generally used in unmodified vinyl lacquers. lations that c o n t a i n alcohols to be sure that problems do n o t develop d u r i n g application a n d drying of the coatings. the viscosity of tain chlorinated solvents. formability.. Properly formulated vinyl solvent b l e n d depending on the resin composition. Guidelines for the p r e p a r a t i o n of viscosity usually used only in baking finishes. The Aromatic 100 a n d 150 are a b o u t 3 to 5 weeks. to a b o u t 30% of the solvent blend. are preferred as they of the solvent blend... stable solutions for resins of varying molecular weight are Aliphatic h y d r o c a r b o n s can be used in limited a m o u n t s .iran-mavad. The heated to a b o u t 60~ the effect of microcrystallinity is elimi- use of higher boiling aliphatic h y d r o c a r b o n s can cause pre. W h e n a vinyl resin solution is bons..6 H 40/43 60 40 9.102 PAINT AND COATING TESTING MANUAL TABLE 4--Suspension vinyls for solution coatings--Wacker Chemie. . 1. usually hydroxyl-modified vinyls. ture. was not heated. Aromatic a n d between polymer molecules in solution.. MPR-TS 87 13 . F r o m the time a vinyl resin is dissolved... k n o w n as the m e m o r y effect. chiefly toluene a n d xylene a n d higher boiling weight. 0.. 0. The converse relationship hold w h e n vinyl With ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . www. (c) a n d the strength fractions such as Aromatic 100 or 150. 0.56 TABLE 5--Suspension vinyls for solution coatings--Nissan. 0.5 H 15/45 85 15 9. MPR-TM 86 13 .68 E 22/48A 78 7 15 0.. . If the solution is then cooled to its original tempera- cipitation of the resin d u r i n g drying. those with boiling points up to 117~ are suitable. a n d some nitroparaffins. molecular resin solutions usually reach a n e q u i l i b r i u m viscosity i n weight.. However. Hydrocarbons are believed due to the f o r m a t i o n of regions of microcrystallinity chiefly used as diluents primarily to lower cost. esters. M o n o m e r i c as well as polymeric plasticizers or com- later versions. the viscosity of the some cases vinyls. vinyl coatings were reformulated as c o m p l i a n t patible polymers with low glass t r a n s i t i o n t e m p e r a t u r e (Tg) systems by reducing the a m o u n t of b r a n c h e d ketones a n d m a y be used to plasticize a vinyl coating. 0..6 H 40/55 60 40 . Composition.5 H 15/45M 82 17 1 9. .. in microcrystallinity to redevelop. nated. 0. 0. 15 0. With time. viscosity increase is d e p e n d e n t on: (a) resin molecular drocarbons. . solutions increases with time until a n e q u i l i b r i u m is reached ketones are the best solvents i n terms of the ability to dissolve after which the viscosity r e m a i n s constant. . 20 0.. 9-. Though it was neces- Vinyl Vinyl Vinyl sary to use more oxygenated solvents. cer..5 H 15/50 85 15 9. a n d impact resistance of the of solvents used in coatings. the p e r f o r m a n c e of Grade Chloride Acetate Alcohol Acid c o m p l i a n t coatings stayed the same. Glycol ethers a n d glycol ether esters are sometimes used in vinyl Plasticizers coatings to improve flowout of baked coatings...46 H 40/50 60 40 9.. up to 15 to 20% alcohol m a y be used in the solvent solutions are cooled. 0.wt% esters a n d aliphatic h y d r o c a r b o n s [13]. 1 S o l u t i o n Characteristics Vinyl solution resins are dissolved by ketones. systems are shown i n Table 7.. such as Los Angeles Rule 66 a n d coating. As a class.wt% Vinyl Vinyl Acrylic Inherent Grade Chloride Acetate Acid Ester Viscosity E 15/45 85 15 9. 0.

iran-mavad. For a m o u n t s tend to make the film soft a n d p r o n e to dirt reten. treated 0 0 0 0 Polypropylene. ing o n a n equal volume basis. Other resin) of plasticizer is considered a b o u t m a x i m u m for use inorganic pigments can be used to replace TiO2 by substitut- with coating resins. 50/50 VMCC.3 Resin Solids Blend. not recommended. phosphate. Product Type Hydroxy Carboxy Modified WB Copolymer Modified VAGH Vinyl Substrate VYHH VMCH VAGF AW-875 Steel 0 10 5 0 Galvanized 0 10 5 0 Paper (glassine) 10 10 10 10 Aluminum foil 0 10 7 10 Polyethylene. 0 = No adhesion.M e m o r y effect. 10/90 Vinyl coatings are p i g m e n t e d (1) to achieve the desired color. to humidity.5 VYES-4 60 MEK/toluene. 50/50 Weeks VMCH. Ambient Heated TABLE 8--Guidelines for viscosity stable solution. a n d glycol ester plasticizers are typi. VYHD 15 VERR. VYHH FIG. VMCA. treated 0 0 0 0 Polysulfone 7 10 10 10 Acrylic 10 10 10 10 PVC plastic I0 10 10 10 ABS plastic 10 I0 10 10 Polycarbonate 10 10 10 10 Polyphenylene oxide 4 I0 0 0 Polyethylene terephtalate 0 0 5 0 Impact polystryene 0 0 0 0 Inked surface 0 5 8-10 5 Rating: 10 = Pass Scotch Tape ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . 67/33 0 1 2 3 4 5 27-34 VAGF. Ordinarily. be used at a level sufficient to protect the vinyl resin. 33/67 Pigmentation VROH 5. TABLE 7--Typical solvent mix for spray-applied coatings. carboxyl-modified resins. VAGD. which are EPA 33/50 listed solvents.g 100% Cyclohexanone 9 MIAK 15 Toluene 12 Butyl acetate 40 Xylene 7 Cyclohexanone 9 VM&P naphtha 1___22Toluene 100 VM&P naphtha 20 6 g Cooled ~50% reduction of MEK and toluene. as these pigments can react to form resistance to extraction by solvents. Resin Molecular Maximum Typical Solvent Weight • 10. t i t a n i u m dioxide (TiO2) pigments. basic pigments m u s t be avoided with of the coating that m a y include low-temperature flexibility. Most organic a n d inorganic pigments can cally used.. VAGH. 19-22 VAGC. irreversible gel. Blends of plasticizers m a y be required to P r i m e or color pigments which absorb UV r a d i a t i o n m u s t meet specific requirements. wt%. 180 Compliant with Rule 66/EPA Non-Regulated Rule 66 Compliant 33/50 Initiative ~ MIBK 50 MEK 14 MEK 7 Toluene or Xylene _ 50 _ Butyl acetate 46 Acetone 3 . Plasticizers are selected to meet the r e q u i r e m e n t s be used. Table 9 presents a listing of plas. a m i n i m u m level of a b o u t tion. However. Care m u s t pigments or fillers do n o t absorb UV r a d i a t i o n a n d can only be exercised in choosing the level of plasticizer as excessive he used in c o m b i n a t i o n with a UV absorbing pigment. 5 = Some loss of adhesion. wt% I / I I I 44 VYNS-3 15 MEK/toluene. 33 MIBK/toluene. 25 MIBK/toluene. resistance to migration. Memory Effect composition. a level of 25 p h r (parts per h u n d r e d parts 75 p h r is needed to provide resistance to UV light. Extender ticizers that are c o m m o n l y used with vinyl resins. 1 . use outdoors [14]. Organic p i g m e n t s that are www. etc. no loss of adhesion. 28 MIBK/toluene. CHAPTER 1 5 .V I N Y L R E S I N S FOR COATINGS 103 TABLE 6RAdhesion of vinyl resins. a n d (2) to prevent degradation of the vinyl resin from the effect of ultraviolet light for coatings that are i n t e n d e d for Phthalate.

An organosol coating may also require a hyde resins to achieve a degree of thermoset properties. At elevated A plastisol is a dispersion of discreet particles of high. Heat stabilizers are usually combinations of Plastisol coatings are usually formulated with the addition of metal salts of organic acids in combination with epoxidized coarser particle-size PVC resins called extenders from sus. the volume of ture for a long time period. The modifier resin may Primers for Plastisols and Organosols contain carboxyl groups to make self-adherent coatings. control viscosity. elongation. the metallic salts must be (up to about 10 wt%) to reduce viscosity and provide better avoided as these will usually cause gellation. The type of pigment and level of pigment used in pig- An organosol differs from a plastisol in that much lower mented organosols follow the guidelines given for solution levels of plasticizer are used. such as amino-formaldehyde or phenolic resins to provide www. Undercuring or baking at temper- dispersed resin relative to the volume of liquid plasticizer. Excessive high coupled with good viscosity stability. other polymers such as acrylic polymers may ified vinyl resins and may require the use of thermoset resins be used. Plastisol coatings do capto tin or tin ester compounds are used in combination not adhere well to most substrates and most often require the with an epoxy stabilizer. Because lower levels of plasticizer are used. Commercial organosols are usually modified with a sol- vent-soluble resin to prevent mud cracking or film splitting during the bake to fuse the film. ing effect of the plasticizer on the resin particles. to avoid excessively high viscosity. the atures lower than that required for fusion will yield films size and shape of the suspended particles. deficient in tensile strength. of 50 to 55% nonvolatile by weight are typical. or it may be a hydroxyl containing resin to provide functionality to Plastisol coatings need a primer to develop good adhesion react with cross-linkers such as amino or phenol/formalde. more difficult to prepare pigmented called diluents are used to provide sufficient fluid to make a plastisols because there is generally little solvent used to fluid dispersion. are used polymers are used. called dispersants in combination with hydrocarbon solvents It is. mer- flow and leveling of the plastisol ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . and the and all other properties. At fusion. Additionally. minimum amount of about 55 to 60 parts plasticizer per Films of plastisols or organosols need only to reach fusion hundred parts of resin to form a fluid mix. temperature. especially when carboxyl-modified amounts of thinner. The relatively high levels of Plastisols and organosols also require the use of heat stabi- plasticizer needed to produce a flowable liquid mix results in lizers to protect the vinyl resin against degradation during the the formation of fused films too soft for use as coatings. Special attention must be given to pension or bulk (mass) polymerization that allow the use of the selection of heat stabilizers for organosols modified with less plasticizer and thus harder films. homogeneous film. use of a suitable primer. fusion bake. the resin no longer exists as discreet dation during baking (fusing). however. abrasion resistance. Commercial organosols loading of pigments can lead to early chalking. usually aliphatic hydrocarbon. Phthalates Linear Dibasic Acid Esters Butyl benzyl phthalzate (BBP) Di-n-butyl sebacate (DBS) Di-2-ethylhexyl phthalate (DOP) Di-2-ethylhexyl adipate (DOA) Diisooctyl phthalate (DIOP) Diisononyl adipate (DINA) Diisononyl phthalate (DINP) Di-2-ethylhexyl azelate (DOZ) Diisodecyl phthalate (DIDP) Phosphates Citrates Tri-2-ethylhexyl phosphate (TOP) Acetyl trim-butyl citrate Isodecyl diphenyl phosphate Epoxies Polymerics Epoxidized soybean oil (ESO) Adipic acid polyesters 2-Ethylhexyl epoxytallate Azelaic acid polyesters manufactured to smaller particle size are used at a lower Careful consideration must be given to the selection of the concentration. small solvent-soluble resin. Suitable primers can be formulated from carboxyl-mod- for organosols. particles. viscosity of the liquid plasticizer. In such cases. Low oil absorption pigments must be used films with much greater hardness can be obtained. solvating or swell. oils or liquid epoxy resins.iran-mavad. to metal substrates. typically. the plasticizer or plasticizer diluent mix exerts a molecular-weight vinyl homopolymer resin in plasticizer. The viscosity of the temperature and do not have to be held at the fusion tempera- dispersion is dependent on packing effects. and blends of inorganic and organic pigments solvent/diluent mix for organosols to attain the highest solids are often used to achieve the desired color. but rather as a continuous. strong solvating or swelling effect on the dispersed PVC resin with a low level of heat stabilizers sufficient to prevent degra. A combination of weak solvents vinyl resins. Plastisols and organosols require a high baking tempera- Organosols and Plastisols ture of about 350~ (177~ to fuse the films.104 PAINT AND COATING TESTING MANUAL TABLE 9--Typical plasticizers compatible with solution vinyls. primer if it is not modified with an adhesion-promoting mod- Though vinyl copolymers are usually the modifier of choice ifier. Plastisols normally require a particles.

Other applications include decorative coatings for the alu. This system has become polymers to formulate heat-sealable coatings for applications the subject of numerous specifications. and coatings for aluminum foil for the vapor barrier insulation for construction applications are also coated with vinyl resin coatings. substrate failure when the package is opened. highly plasticized vinyl surfaces are usually formulated with ing. ment agencies and agencies of other governments have writ- tainer. and puckering of the films. ease of heat sealing. the ink is firmly bonded to the substrate and the carrier is peeled away cleanly. and tight but readily peelable bond is required. resistance. the vinyl coat. food plied by air atomizing spray guns at low two-piece construction. soups. and the like where the need is for a very water tanks. Inks for cal properties to withstand the forming steps without crack. These systems consisted of a poly(vinyl butyral) wash nate. When ready for use. In this application. plastisol or organosol coatings. marga. As beverage cans needed to achieve hiding in the thin films typical of inks. usually carboxyl-type for adhesion. appurte- for packaging materials such as pharmaceutical prepara. have also been used on precoated stock for can ends. vinyl upholstery. polypropyl- contents [15]. MAJOR MARKET AREAS FOR VINYL COATINGS Inks R i g i d Packaging The major markets for vinyl inks are on vinyl surface prod- ucts such as floor and wall coverings. vinyls quickly became established as maintenance fin- Vinyl coatings are also used to coat collapsible metal tubes ishes. nant structures for waterways. Liners for Interior Surface Coatings. Dry Film Printing (Hot Stamp Transfer) grade chemical resistance and permit the use of such coat. ing also changed from lacquer to hydroxy vinyl/amino-form. paper and Heavy duty marine finishes were developed in the mid- plastic films such as polyethylene terephthalate. flexibility. CHAPTER 15--VINYL RESINS FOR COATINGS 105 resistance to excessive softening from highly plasticized rine. cause the plates are susceptible to solvent attack. fast dry and ease of application.17]. or other suitable surfaces to which the ink will not Vinyl lacquer and vinyl thermoset coatings are used as size adhere strongly. so that when the die is removed. Vinyl inks are often reverse printed on a clear vinyl film. This type of resin is used for its primer. flexographic printing is not suitable for vinyls be- tab can ends. ene. polycarbo. equipment in chemical plants. as maintenance paints [16. dams. The vinyl resin may be sion to wash primer]. interior linings for potable tions. and the printed film is then laminated to substrates such as aldehyde thermosets to meet the need for higher corrosion wood or metal to make articles having simulated wood finish. decorative labels. Decorative foil for floral wrappings. Govern- requiring varying degrees of force needed to open the con. with the surface. Many contents of the package even though high stresses from col. The early vinyl maintenance and marine finishes were ap- minum foil paper laminates for cigarette packaging. Ink formulation is Closure~Caps and Crowns quite similar to that used with coatings except solvent choices The first commercial use for vinyl coatings was as the are somewhat narrowed and higher pigment loadings are topcoat lacquer for the inside of beer cans. 1940s. swimming pool liners. evolved from three. repair. good weathering as jellies or cream containers found in restaurants where a qualities. vinyl inks are printed on a carrier sheet ings for packaging food that will be autoclaved to sterilize the such as polyethylene terephthalate. ester solvents to avoid excessive softening of calendered films Organosol coatings containing a solution resin component. an application that requires excellent mechani. PVC.S. Flexible Packaging Solvent-soluble carboxyl-modified vinyl chloride copoly- Maintenance and Marine Finishes mers have good adhesion to most materials used in flexible or semi-rigid packaging including aluminum foil. and cellophane. the printed carrier film is or as crowns for beverage bottles.iran-mavad. and garment fabrics. Can Ends. and the like. and so on. to items such Because of their good water resistance. Vinyl organosols are further modified with amino-formaldehyde or phenolic resins to up. These systems serve as the placed with the inked side on the surface to be decorated. steel structures such as bridges. Thermoset coatings of epoxy-modified vinyl resin Vinyl inks are printed by gravure or screen process because with carboxyl-modified vinyl resin are used to coat on coil these presses are compatible with the strong solvents needed stock. A primer coat for gasketing compounds made with plastisol or heated die presses the composite to make intimate contact vinyl resin dry blends. vinyl-red lead anticorrosive intermediate coatings adhesion characteristic. This area includes coatings for locks. many U. and vinyl copolymer/wood rosin/ used alone or modified with plasticizers or other resins and cuprous oxide anti-foul top coats. and resistance [based on poly(vinyl alcohol)-modified resin needed for adhe- to attack by the packaged product. specifications have been written that require the use of vinyls lapsing and rolling up the tube are encountered. This could range from applications such as blister ten specifications with this coating system specified for use packaging where the bond needs to be strong enough to cause below the waterline of ships. The coated coil stock is then formed into the stay-on for vinyls. The inks are applied and dried usually in coats for metals that are formed in caps and closures for jars web ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . were needed to attain coverage sufficient for good corrosion www. for butter. Cans. toothpastes. polyethylene. electrical flexible coating that will not crack nor be attacked by the towers. Several coats wrappers for fast food restaurant items.

. at the low molec- will adhere to the part and begin to flow to form a film. Cryogenically ground powder coatings are applied by elec. may be used alone for less demanding applications. it is tionality to allow for reaction with added coreactant materi- not necessary to preheat the parts.. but a bake is necessary als to build molecular weight.iran-mavad. However. These finishes also have excel- products are available that can use lower temperature bakes lent resistance to a variety of household chemicals. about 80~ Coalescents are needed used because of their good adhesion. TABLE 10--A line of waterborne vinyl resins dispersions. pipe. lower Tg humidity or water splashing. they are cle size allows the deposition of smoother and thinner films than is attainable from fluidized bed or powder spray pro. The metal pared at two to three times the level of solids content that was parts are heated for fluid bed application so that the powder possible with earlier vinyl resins. developments in vinyl coatings have Henschel mixer. polyurethane resins are used as the plasticizer as the the latter. For high solids vinyl coatings. glycol-ether ester. coatings made from such resins was greatly reduced in terms forming process by fusion or melting. High-build airless spray-applied vinyl coatings PVC Latex were developed in the 1970s to fill the need for coatings Emulsion polymerized vinyl chloride homopolymers and systems that could be applied in fewer coats at less expense copolymers are used in the latex form not so much to make [18]. pigments. the performance of after the powder application is needed to complete the film. and linked with amino/formaldehyde resins. technology of tapes advanced and placed more stringent re- glycol-ether.106 PAINT AND COATING TESTING MANUAL protection. With the electrostatic method. By varying the type and amount of comonomer used to particularly when the coated wood becomes wet from high make emulsion polymerized copolymer latexes. As a result. then polyesters. the high costs of cryogenic grinding made Composition. A line of and video [20]. fencing. the cryogenic ground powders Grade Solids Water~ Cosolventb pH account for only a small share of the PVC powder-coating AW-850 38 50 12 7. This lat. A bake ular weights needed for high solubility. However. and stains and have been used as fine furniture finishes [19]. so that viscosity stable solutions could be pre- applied by fluidized bed or by spray techniques. high solids vinyl resins are modified to contain hydroxyl func- trostatic powder spray. In a sense.0 PVC powder coatings are used to coat products such as aContains less than 2% amines. Some powder coatings are prepared by a centered on high solids and waterborne systems. and a co-solvent free variety is also available. Magnetic Recording Media Waterborne Vinyl Dispersions Waterborne vinyl dispersions made from solution-poly- Vinyls. Alkyd resins were some grades are sold as preplasticized latexes. and the like. Some dispersions are good pigment wetting properties. The vinyl chloride homopolymers need veloped consisting of a hydroxyl-modified vinyl resin cross- to be modified with a substantial loading of plasticizer. and additives in ribbon blenders followed by To meet the VOC requirements that are either in place or attrition or dispersion to powder in mixers such as the proposed for the future. bEthylene glycolmonobutylether. such use could be considered analogous to a waterborne version of Reactive heavy duty vinyl finishes for wood have been de- an organosol coating. and metal furniture. solvents. of chemical resistance and physical properties. their retention of excellent adhesion and water resistance. finished coatings but rather as material coated on a base or support to provide the substrate for items such as wall cov- Wood Finishes erings. melt mix technique followed by cryogenic grinding. Such finishes became based materials require a high temperature bake to fuse the established as the standard for kitchen cabinets because of resin plasticizer mix into a continuous film. The finer parti. coat- Powder Coatings ing. plasticizer. powder spray. solubility was achieved by reduction in the polymer molecu- Powder coatings prepared by dry compounding are usually lar weight. waterborne vinyl dispersions is shown in Table 10. substantially increased resin ter technique produces powders of smaller particle size [21]. www. These water- often added to improve film build. to form films. abrasion resistance. and heat-sealable coating applications where solvent- based vinyl coatings had been used. the formulator can choose whichever coalescent. as binders for magnetic iron oxide tapes since the beginning These waterborne vinyl dispersions are of medium molecular of the development of tape recording. Vinyl powder coatings are formulated with vinyl chloride homopolymers and copolymers for application by fluidized bed. have been used merized vinyl copolymers became available in the 1980s. especially hydroxy-modified vinyls.0 market. or electrostatic powder spray. With rently. and with these products to form a film. cess. The early binder formula- available with a glycol ether coalescent already present in the tions used alkyd resin as ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . 7. AW-875 39 61 . The vinyl resins are weight and have high Tg. or blend of co- quirements on the performance of magnetic tape for audio alescents that best meets performance requirements. plasti- cizer. wt% these materials substantially more expensive than dry grind- ing and as a consequence. backing for carpeting. Though the high solids resins after application to fuse the powder to a film. cur- product. Waterborne vinyl dispersions are used in many ink. Powder Trends i n V i n y l Coatings coatings are prepared by dry compounding resins.

CHAPTER 1 5 . 14. with a m i n o . K. o r e p o x y ." Applied Spectroscopy. J." Official Digest. Vol. 1993. [15] Good. 1984.W.H. 25. or to improve r e c o a t a b i l i t y [10]ASTM Guide for Testing Poly(Vinyl Chloride) Resins [21].. New York.. J. Journal of the Oil and Colour Chemists Associa- York. www. Linings. VOC content such as acrylics. R. Eds. Italy.. April 1990. "Vinyl-Modified Epoxy Coatings. A. "Pigmentation of Magnetic Tapes." Proceedings of X1 Congress [17] Steel Structures Painting Council. "Pigmented Vinyl Copoly- [2] Myers. o r as modifiers for alkyds. The waterborne vinyls are compat- dards.01. 1972. initial drying o r set-to-touch rate. Journal of Protective Coatings and ASTM. Pergamon Press. Dekker.. pp. I and II. ASTM Book of Stan- mulate low VOC coatings. urethanes. Philadel- phia. DC. 6. Ed. [21] Ginsberg. J.. [16] Corps of Engineers CW-099040. R. R.iran-mavad. and McKenna. "Spectroscopic Analysis Ed. Federation of Societies for polyester-isocyanate. Vols. Vol. S. Society for Testing and Materials... and Potter. (D 4368-89). No. Philadelphia.03. of Poly(Vinyl Chloride) Compounds. Department of the Army. R. 1973. [8] Burley. [14] Hardman. R. ASTM Book of Standards. T. H. 13th ed. G. 5. [7] Infrared Spectra Atlas of Monomers and ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . C. [9] An Infrared Spectroscopy Atlas for the Coatings Industry. American The waterborne vinyl dispersions previously described rep. 36. September 1988. J..f o r m a l d e . Federation Series on Coatings Technology." Modern Paint APSPA. John Wiley & Sons. 4th ed. [1] Industrial and Engineering Chemistry.01. and Bennett. [12] ASTM Test Method for Analysis of Components in Poly(Vinyl formaldehyde cross-linkers. American Chemical April 1972. [5] Paint Testing Manual. J. 476. pp. G.. Vol. Vol. [11] ASTM Test Method for Infrared Identification of Vehicle Solids resent an alternative to high solids vinyls as a way to for- from Solvent-Reducible Paints (D 2621-87). 08. American Society for Testing and Materials. Patton. J. D. 1988. and Coatings. M. Vol. R. Dilute and Concentrated Solutions.. and amino.. T. mer Coatings: A Discussion of Factors Influencing Exterior [3] Powell. J. Florence. L.. New York. November 1988... Part II. Paint No. Vol." Pig- search Labs. E. FATIPEC. 1993. Paint and Varnish Production. W.. ment Handbook. ACS Symposium Series 365. and Long. tion. 06. Pittsburgh. February 1972. 73. 4. ASTM STP 500. 32. 1960. Philadelphia. ible with a wide variety of other waterborne resins with low Philadelphia. [18] Martell. P. Treatise on Coatings. U. Ill: Applications and Markets. 1972. namic Properties of Vinyl Chloride-Vinyl Acetate Copolymers in August 1981.. and Yee. 06. Vol. alkyds. Chloride) Compounds Using an Infrared Spectrophotometric Technique [D 2124-70 (1988)]. 9. Society. REFERENCES [13] Burns.. Vol.J. No. Federation of Societies for Paint Technology.. Ed. Koleske. G.a m i n e coatings to i m p r o v e Coating Technology. [4] Breziuski. 1993. American Society for Testing and Materials. 963-984. T. 1. 203-216.V. Durability. Philadelphia. Philadelphia. J.. Sward. ASTM Book of Standards. Film Form- ing Compositions. A. 1991. Unit 19. [6] Crompton. Philadelphia.. [20] Kreiselmaier. R. h y d e o r isocyanate cross-linker. W. Brezinski. New [19] Mayer. and Brezinski. No. Sadtler Re. Vol. G. Washington.V I N Y L R E S I N S FOR COATINGS 107 b e s t used either as a reactive system. Vol. D. 1980. No. June 1933. 1968. p. "Hydrody. Analysis of Plastics. PA. 1964.S.. A. SSPC-9.

C H ( C H 3 ) ] b . which are tions. which are typified by the poly(propylene needed [13]. v. for use in the manufacture of polyurethane ~Senior consultant. Higher functional free hydroxyl groups. trimethylol low-molecular-weight polycarbonates [8-10]. pounds since they are dealt with elsewhere in the manual. poly(butylene oxide) and polybutadiene polyols. veloped. propagating 1. including polyols based on lactose that have flame- lactone polyols (PCP).2-propylene glycol and glycerol.O H are not discussed elsewhere in the manual.. 1513 Brentwood foams and elastomers. of intermediates used in polyols usually used in coatings. as well as gid substrates [11] and flexible substrates [12] are available. urethane coatings based on polycaprolactone polyols for ri- ents in high solids and cationic photocure systems.and . MNL17-EB/ Copyright9 1995 by ASTM International www.. and so on.O . 7]. they can be and are used in coating Road. low-molecular-weight polyesters pre. There are propane.O . ethylene glycol.R . However.. and pharmaceutical prepara.4-butanediol adipate) Polyester Polyol H--[O(CH2)5CO]s--O--R'--O--[CO(CH2)sO]t--H POLYOLS Poly+caprolactone Polyol Polyols. respectively. A variety of other specialty polyols also exist such as dentistry. Details about preparation of radiation curable formulations. there is no need for an initiator. so polyhydric alcohols.R . good hydrophobic character. 108 www. s. but usually two or more. 1995 Miscellaneous Materials and 16 Coatings by Joseph V. Koleske 1 THIS CHAPTER IS CONCERNED WITH A VARIETY of products that HO--[CH(CH3)--CH2~L . most end groups are hydroxylic rather than carboxylic in pared from the above mentioned as well as other polyhy. trimethylolpropane. R and R' may be the same or or glycerin. neopentyl glycol. The subscripts a. etc.and trifunctional products.O . in a number of other end uses including elastomeric fibers. Both classes of polyols are available as retardant characteristics as well as polyols with different end difunctional and capping.R ' . list typical polyols as compounds such as mon than that of the di. and they can take on a wide variety of values with the number Polyols are important compounds used in the manufacture average molecular weight ranging from about 150 to 3000 for of alkyds and polyurethane coatings. In the ethylene glycol.. Poly(1. Inc.iran-mavad.. Caprolactone acid) [3-5]. Since these polyols are prepared by a condensation droxyl compounds and dicarboxylic acids (particularly adipic reaction. hydroxyl-containing glyc. but they are that the hydroxyl groups are both secondary. u. [14].. Most definitions. vinyl alcohol copolymers. Charleston. Although new polyols such as these are often designed.. or polyalcohols as they are sometimes known. group will be found due to an unexpected opening of the idyl ether compounds. Poly(tetramethylene oxide) polyols also have oxide) polyols (PPO).4-butanediol. propylene glycol. Some topics are Poly(propylene oxide) Polyol mentioned only briefly to indicate that the area has not been H--[O(CH2)40--CO(CH2)4CO]. and particularly those polyols are known and available. Today the word "polyols" is far more encompassing and more Difunctional and trifunctional PPOs are usually initiated often than not refers to alkylene oxide [1 ] and E-caprolactone with 1. dues of the polyhydric alcohol initiators. and diethylene glycol.O . glycerol. nature. WV 25314-2307. which in.O .O . The two main classes of polyols used in coatings are the useful when very high levels of barrier hydrophobicity are polyether polyols. and t in This chapter will not be concerned with these latter com. polytetrahydrofurans prepared by a cationic polyols are initiated with a variety of diols and triols such as ring-opening polymerization of tetrahydrofuran [6. Compounds such as these are usual case. pentaerythritol. formulations. 1. which is the not usually termed polyols. The above structure for PPO indicates other compounds that meet the above definition. b. etc. artifact preservation. the above structural formulas can be the same or different.. Consolidated Research. The adi- [2] adducts of the above-mentioned and other monohydric or pate polyols are usually prepared with an excess of diol.are the resi- that were used in the preparation of alkyds and polyesters. as copolymerizable ingredi.2-epoxide. but their usage is less com- over ten years old. are trifunctional hydroxyl compounds though the adipates are compounds containing one or more. glycerol above structural ‫ﻣﺮﺟﻊ ﻋﻠﻤﻰ ﻣﻬﻨﺪﺳﻰ ﻣﻮاد‬ . from time to time a primary hydroxyl certain vinyl chloride copolymers. and sorbitol different and . and the polyester polyols. New polyols are also being de- clude both poly(glycol adipates) (PEA) and poly+capro.--O(CH2)40-- forgotten and that the topic is not within the scope of the [CO(CH2)4CO--O(CH2)40]v--H manual..astm.[ C H 2 . almost always difunctional in nature.

In using the O /c\ II /c\ / polyols. the industry. carboxyl. oxycyclohexylmethyl 3. which has obvious including even very weak bases can result in neutralization of implications. and do ture that imparts a high degree of weatherability and excel- not sublime with even a few molecules of ethylene oxide lent electrical properties such as dielectric constant. Also described in the liter. and the main products in this class are the diglycidyl cyano. ERL-4221. For example. The hydroxyl group that is determining it. These compounds react well [17]. if functionality is known. described in ASTM Test Method for Polyurethane Raw Mate. dielectric breakdown voltage. These grafted polyols retain their original for their use in coating formulations. Since the protic acids www. termed "cycloaliphatic epoxides. Such epoxides are the largest volume products of all epoxides ature [1. formed on the ring is quite acidic in character andwill readily Another important reactivity parameter is the acid number open other cycloaliphatic epoxide groups. Ways to apply nuclear mag.. allyl. 7] are polyols modified to have amine. as evidenced by their time-honored use had carboxyl groups grafted to their backbone with acrylic or as acid scavengers. H H H H and can be cross linked with cycloaliphatic epoxides when \/ k/ H terminated with carboxylic acid end groups. epoxides. made into mois. Manufacturers provide information about hy. The equivalent weight or other cycloaliphatic epoxides that are commonly known in combining weight of a polyol is determined from the hy. poly(propylene oxide) polyols which APHA Color of Polyols (D 4890).4-ep- [18]. respectively.2'-dimethyl. when potassium hydroxide is used as the titrating agent. the hydroxyl number [19] is their most important physical characteristic to be measured and used.M I S C E L L A N E O U S 109 End capping polyols can provide adducts with different Polyurethane Raw Materials: Determination of Gardner and properties.2-epoxides that are not attached to a ring structure. epoxides as well as their copolymerization with active hydro- terification used to produce polyester polyols. color. tion factor. Manufacturers can also be helpful in supplying information about methods of analysis for specific products. Epoxide equivalent weight can be determined droxyl number by the following relationship with ASTM Test Methods for Epoxy Content of Epoxy Resins Equivalent Weight = 56 100/Hydroxyl Number (D 1652). Acidity and alkalinity in polyols can affect formulations [22]. Of Usually these epoxides are reacted with polyols that function course. can be cross linked with aminoplasts. used. poly(propylene oxide) polyols have with carboxylic acids.iran-mavad. shelf life. However. photocurable Polyols (D 4662). can be determined with ASTM Test Method for the protic acids formed by photolysis. philic attack on the epoxide ring to form an ether linkage and droxyl number and usually about methods for analytically a hydroxyl group on the ring. contain terminal secondary hydroxyl groups can be end cap- ped with ethylene oxide to provide polyols with more reactive primary hydroxyl groups [1. In the coatings industry. and vinyl ether end groups. have low viscosity. CHAPTER 1 6 . This epoxide is well known by the familiar name designation als: Determination of Primary Hydroxyl Contents of Poly. separate chapter in this manual. modified with a few ethylene or propylene oxide groups to These epoxides are characterized by a saturated ring struc- yield new polyols that are liquid. However. and other ingredients. can be specialty coatings and in cationic radiation-cure coatings. Five wet chemical methods and two nuclear magnetic resonance methods for determining the hydroxyl number are given in H/ \/c\ / \/c\ / \ H ASTM Method for Testing Polyurethane Polyol Raw Materi- als: Determination of Hydroxyl Numbers of Polyols (D 4274) H H H H and in ASTM Method for Testing Polyurethane Raw Materi. idyl or 1. to coatings and Polyols can be end capped with an anhydride to form adducts other products made from them. cycloaliphatic epoxides are used rials: Determination of Acid and Alkalinity Numbers of as a major formulating ingredient in cationic. 7]. there is a special class of and/or that have subliming characteristics.4-epoxycyclohexane carboxylate that Polyols can be incorporated into alkyds. as 2. hydroxyl end groups and are used in coating formulations The main commercial cycloaliphatic epoxide is 3. and this reactivity o