Journal of Coatings Technology 1978 Vol.50 No.641

, " V L. -* I." * * a Y *cI.,W .- I.... Y ; * 0 . V.".. "$ *yD

P'5 jhy. :>$Jf+p &*;$$p?; . - - - . 2 * ay 1 re-0 . . .---A

Put Micro-Cel" functional extender to the test. And lower the cost of latex flat paint two ways. Now you can extend Ti01 and control gloss and sheen with just one functional extender. J-M Micro-Cel can replace up to 25% of the Tion in vinyl acetate emulsion or latex flat paint formulation.

Because of its locked-in air voids, it extends Tion particles giving you lower costs and higher opacity. And it disperses quickly and easily in any formulation. But that's only half of the Micro-Cel story.

J-M Micro-Cel efficiently controls gloss and sheen. It acts as a true flatting agent, reducing side and angle gloss and sheen to required levels.

Normally this extra performance would cost you extra money. Not with Micro-Cel. It is competitively priced with those products that just extend Ti02. You get the same efficiency as an extender, with gloss and sheen control at no extra cost.

For information on J-M Micro-Cel, J-M filter cartridges and other J-M flatting agents, write Johns-Manville, P.O. Box 5107-FIM, Denver, CO 80217. Or contact one of the Regional Of- fices below.

Johns-Manville

San Mateo, CA (415) 349-9500 Englewood Cliffs, NJ (201) 854-1511 * .4t!anta, GA (404) 449-3300 Toledo, OH (419) 878-8111 Houston, TX (713) 869-4881 Oak Brook, IL (312) 887-7400 On:ario, Canada (416) 278-7211

As promised, Rohm and Haas is telling things just like they a 1HOPLEX" WL-91 acrylic emulsion was introduced at the Paint Industries' Show In October '^'7.

By April 1978 it was selling in bulk quantities. Here's why it's a success:

Wide formulating latitude. Good lacqmrstability. - 'Yater, salt spray, gasoline, and solvent Wetant?.

Quick dry. Rapid hardness development St.bllity with reactive p~gment& apiuaincarfi+on~nesistantprimerr

High gloss. Excellent iMPbclouItv.

r tlqueous 1 vehicle for c i i ~ d q .

lac~uers scores inst~nt success , I

L A

Start getting ready folr it using our Resinvision;

ricarb" may or may not be the n available ir., .vide line to let you sele concept is coming. We claim no answer to your needs. owever, we have anticipated its e Talk to our people. You'll find we have

your business and ours. And alr

~eing able to see beyond problems to solu ) conceive new types of resins before

ney re required . . . and to be ready with y uture needs. Now.

JUNE 1978

Volume 50 Number 641

27 DEVICE FOR WEATHERING SEALANTS UNDERGOING CYCLIC MOVEMENTS-K.K. Karpati

31 PROGRESSION OF MICROORGANISMS ON PAINTED PANELS IN PUERTO RICO-T.B. O'Neill and R.W. Drisko

33 CONSERVATION THROUGH HIGHER SOLIDS, LOWER ENERGY CURE COATING RESIN SYSTEMS--R.N. Price

41 SURVEY OF THE APPLICATIONS, PROPERTIES, AND TECHNOLOGY OF CROSSLINKING EMULSIONS. PART I-B.G. Bufkin and J.R. Grawe

56 DYNAMICS OF ROLL SPATTER AND TRACKING. PART Ill: IMPORTANCE OF EXTENSIONAL VISCOSITIES--J.E. Glass

72 DYNAMICS OF ROLL SPATTER AND TRACKING. PART IV: IMPORTANCE OF G* RECOVERY AND NI IN TRACKING4.E. Glass

17 1978 ANNUAL MEETINGS NEWS

Departments 7 Comment 85 Elections 92 Obituary

14 Abstracts 86 Technical Articles In 93 Literature Other Publications

22 Government and 94 Letters to the Industry 88 MeetingslEducation Editor

81 Society Meetings 90 People 95 Coming Events

@ 1978 by FEDERATION OF SOCIETIES FOR COATINGS TECHNOLOGY

The non-lead, non-chromah that performs as well 01

Tests prove it!

NALZIN" ST-1

dALZINTM SC- I

NALZINTMSC-1 vs. Zinc Chromate (40 PVC Oil Alkyd 1:l Primer)

340 HOURS SALT FOG (ASTM Test B117-64)

Corrosion-Inhibitive Pigments: Equal Cost Comparisons (644) (Formulated to Constant PVC) Substrate: Phosphated Steel Application: Brush Number of Coats: 1 Total Film Thickness: 1.5 mils (dry)

7 MONTHS MARINE EXPOSURE (45O South, Ocean City, N.J.)

Corrosion-Inhibitive Pigments: Equal Cost Comparisons (64t) (Formulated to Constant PVC) Substrate: Hot Rolled Steel, Sandblasted Application: Brush Number of Coats: 1 Total Film Thickness: 2.0 mils (dry)

18 MONTHS ATMOSPHERIC EXPOSURE (45O South, Hightstown, N.J.)

Corrosion-Inhibitive Pigments: Equal Cost Comparisons (64$) (Formulated to Constant PVC) Substrate: Hot Rolled Steel, Sandblasted Application: Brush Number of Coats: 1 coat of primer over all

2nd coat over upper half Total Film Thickness:

Zinc ~nrornare

. . Upper Half-3.0 mils (dr) > I

c-

Lower Half-1.5 mils (dr) -. <- - Zinc Chromz

Journal of Coatings Technology

anti-corrosive pigment

There & an answer to the problem of having to reformulate away from lead and chromate pigments and still come up with an anti-corrosive metal-protective system that will provide the performance benefits that have always been identified with lead and/or chromate-based pigments.

The answer is NALZINTM SC-1, the zinc phospho oxide pigment that is as versatile as it is effective. Lead-free and chromate-free, it works equally well in aqueous and solvent-based coating systems-oi l/al kyds, acrylic latexes, styrene acrylic latexes.

The tests shown at left compare the performance of NALZIN SC-1 with that

It consistently equals or tops Zinc Chromate both at equal weight and at equal cost levels. Low levels perform as well as high loadings, so it takes less to achieve good results.

NALZIN SC-1 has other highly benefi- cial cost and performance features:

Stable in a wide variety of binder systems. White color and low tinting strength allow formulation of virtually any color coating. Minimizes tendency for flash rusting in aqueous coatings.

I Now Available! NL's new Steel Painting Specification I Guide for NALZINTMSC-1 Anti-Corrosive Pigment. I 24 pages of helpful information on reformulating your anti-corrosive I

I paint systems with NALZIN SC-I, including detailed specifications and 1 a color selection guide. I

I Please send me a copy of the new NALZIN SC-1 Specification Guide. I i 1 Please have your representative contact me. I

of Zinc Chromate. They demonstrate

Title

Company

conclusively that: NALZIN SC-1 Pigment performs as N well or better than Zinc Chromate at

Address I

Industrial all levels tested. IIIIIIIIIIIII Chemicals

Vol. 50. No. 641. June 1978 5

I

L l l l l l l l l l l l l l l l l l l l l l l I ~ l l l l l l ~ l l l l l l ~ l l l l l ~ l l ~

City State Zip Mail this coupon to: Industrial Chemicals Division NL Industries. Inc.. P.O. Box 700. Hightstown. N. J. 08520

i I I I

THE JOURNAL OF COATINGS TECHp(0LOGY is wblished monthly by the Federation of Societies for Coatings Technology at

315WeinuI St .Philadelphia. Pa. 19107. R o n e (215)545-1507.

Annual due5 for muinbem of the Federaiion ot Sa-letles for CoatingoTechnology, C15CQ ~ncl&sasubscf~~lcntothispub "xiion, Memtwrshlp In the Federation is obtained thmugh prim

RiliaNan mth, aml payment of durn M, OM, of cts 26Constituwd ~3ewties N o m m k r subw~pt ion rams am

KOLDE 41NT STONE

BOARD OF DIRECTORS

PRESIDENT

JOHN J. OATES Troy Chemical Corp . Newark. N.J.

PRESIDENT-ELECT

JAMES McCORMlCK Inland Leidy. Baltimore. Md.

TREASURER

HARRY POTH Dean 8 Barry Co.. Columbus, Ohio

When ava~lable, s~ngle copier of hack ~ssues of ihe JOURNAI it; OF c0AnN.s r r c H N o L c w at MIOW u m e x

JAMES A. BOHLEN Sherwin-Willtams Co., Greensboro. N.C.

A. CLARKE BOYCE Nacan Products Lid.. Toronto. Ont.

WlLLY C.P. BUSCH PPG Industries. Inc.. Houston. Tex.

NEIL S. ESTRADA Reichhold Chemicals, Inc.. S. San Francisco. Calif.

JOHN A.J. FILCHAK General Services Administration. Auburn. Wash.

DONALD J. FRITZ Superior Varnish 8 Lacquer Co.. Merchantville, N.J.

PHILIP HEIBERGER E.I. du Pont de Nemours 8 Co., Inc.. Philadelphia, Pa.

HOWARD JEROME Vane-Calvert Paint Co.. St. Louis, Mo.

TERRYL F JOHNSON Cook Paint 8 Varnish Co.. Kansas City, Mo.

ELDER C. LARSON Shell Development Co.. Houston. Tex.

HORACE S. PHlLlPP Sherwin-Williams Co, of Canada Ltd., Montreal. Oue.

HOWARD G. SHOLL Baltimore, Md. I

WILLARD W. VASTERLING Morion-Myers Co. Kansas City. Kan I

EXECUTIVE VICE-PRESIDENT

FRANK J. BORRELLE Philadelphia, Pa


The full-day agenda covered a host of SocietylFederation items and was designed

officers and staff.

To round out the meeting experience, the Society officers were invited to stay over for the Council and Board meetings the next two days, and a goodly number did so to take in the deliberations of those twogroups and get a better insight into the workings of the Federation.

It was a very successful meeting and, while none of those attending returned to his Society with any magic solutions to whatever problems might exis did take back a better understanding of the SocietylFederation re1 how both can work together to their mutual advantage.-TAK

8 Journal of Coatings Technology

Vol. 50, No. 641, June 1978 9

Low cratering is just one reason why Polywet"dispersants

ymP' Whether thev are aml ied

low-foaming, have excellent adhesion, and excellent scrub resistance. It takes less

Polywet than most other dispersants to get these benefits, too.

l! 81/ ufacturers use Polywet. It maintams product performance both on the wall and on the shelf.

Polywet dispersants are low-foaming anionic polyelectro- lytes for dispersing pigments in water in a variety of applica-

tions, including: latex paint, slurry shipment, specialty coatings and water treatment systems. They are resis-

tant to hydrolysis, are effective over a wide pH range, and remain stable over a wide temperature range.

Polywet ND-1 for exterior paints and paints containing reactive pigments and biocides provides excellent stability and imparts thixotropy. Polywet ND-2 is recommended for

slurry shipment and storage and may be used in all types of latex paints.

There are also Polywet Surfactants that provide high surface tension latexes with low foam, excellent stability and

offer other special advantages for both hydrophobic and hydrophilic monomers.

r complete information on Polywet and a comparative study other dispersants call or write Joseph Hochheiser, Uniroyal

Chemical, Naugatuck, CT 06770; (203) 723-3445.

UNIROYAL

High grade coatings with A - excellent

curing - e n t s - --

VEBA-CHEMIE supplies diamines and anhydrides for hot and cold curing.

VEBA diamines IPD and TMD as well as the hardener V214 are colourless, low viscosity liquids. They are of aliphatic or cyclo aliphatic structure.

VEBA anhydrides HHPA, THPA and PMDA are solid pure white products. MHHPA is a low viscosity liquid.

VEBA special hardeners HHPA = Hexahydrophthalic anhydride

B31, 8559 868 and 873 enable THPA - Tetrahydrophthalic anhydride the manufacture of highly reactive or normal curing PMDA -- Pyromellitlc dianhydride

powder coating systems from MHHPA - Methyl hexahydrophthalic anhydride high gloss to matt or dead matt finishes.

Check how the VEBA epoxy curing agents can improve your products. Samples, technical information and advice are available on request.

VEBA-CHEMIE AG Dept. EP103,P. 0. Box 45, D-4660 Gelsenkirchen-Buer, Phone (2 09) 3 66-39 16, Telex 824 647 vebc d.

Cut Your Energy Costs With Pfizer's New Fast Dispersing

Pure Yellow Iron Oxides Also make significant labor and time savings,

and improve equipment utilization for increased profits.

Pfizer's unmatched range of yellow synthetic iron oxide pigments is now available in both standard and new easy dispersing grades.

Unsurpassed in the market place to improve paint manufacturers' profitability, our new "D" grade yellows are produced by a sophisticated method that's the latest achievement of Pfizer's engineering' expertise.

These new yellow iron oxides disperse with great ease, speed, and economy. They also achieve al-

most instantaneous full color development, and high, clean Hegmans.

Pfizer's new "D" grade yellows are offered in shades ranging from light lemon to dark orange. The more popular shades are available in both regular and low oil absorption versions for maximum utility in different formulations.

Their acicular shaped particles are controlled in size to an average of less than one micron, and the uniformity of their color from lot to lot is verified by a sophisticated color computer system.

Pfizer's compurer-con~ro~~ed color measuring system incorporates a Hardy spectrophotometer and Chromascan abridged spectrophotometer, interfaced with a disc-based PDP-11 computer.

MINERALS, PIGMENTS& METALS DIVISION Dept. 6C-6 235 E. 42nd Street New York, N.Y. 10017

* DEVICE FQR WEATHERING SEALANTS UNDERGOIN( SURVEY OF THE APPLICATIONS, PROPERTIES. AND CYCLIC MOVEMENTS--K.I<, Karpati TECHNOLOGY OF CROSSLINKING EMULSI0NGB.G.

Bufkin and J.R. Grawe i Journal of Coatings Technology, 50, No. 641.41 (June 1978)

ENERGY CURE COATING RESIN SYSTEMS-R.N. Price

Journal of Coatings Technology, 50, No. 641,33 (June 1978)

Higher solids polyester and alkyd resins have been developed which, when crosslinked with amino resins, provide coatings which have performance comparable to currently used lower solids syetems. Paint formulating, preparation, and application werefound to bevery similar to that of conventional coatings. When crosslinked with an aliphatic polyisocyangte resin, low temperature cure systems are obtained. Two-package polyester-epoxy systems which offer a combination of higher solids along with low temperature cure are also described.

vry color ro~u~a~ne rea, II . , >UP-R-CONC" L toluidine reo, Jry color toluidine red, It., 3 minutes in a high-speed It., 3 minutes mixing time to 45 minutes in a high-speed

disperser. achieve uniform mixture. disperser.

Stir-B- colorants for deeptones and tin&

the same type. The result - high Help cut labor costs production using far less energy in Have low environmental impact the shortest possible time. SUP-R- CONC L captures the discrete pig- energy consumption

ment particle in its unagglomerated r Eliminate need for expensive

form to achieve stir-in ca~abdi ty dispersing equipment with optimum results.

Now - energy saving colorants for SUP-R-CONC Pigments: Are standardized to achieve

water based coatings that help you uniform results

increase production and profits, Stir-in for deeptones and tints Sick of the same old dry grind? SUP-R-CONC@ L Pigments stir-in Help reduce inventory require- ~ o o k to Hilton-Davis for the innova- uniformly in a fraction of the time tive response to the coatings indus- required for ordinary dry color of Help increase production capacity try's needs - SUP-R-CONC L NEW

Gentlemen: So I can compare for myself the amazing mixing speed of new SUP-R-CONC L please send me a sample in the following color:

Toluidine Red, Lt. r X-48 Yellow Please have a sales representative contact me. --- JAWS Toluidine Red, Dark Phthalo Blue, R.S. NAME: Division of Sterling Drug Inc.

2235 Langdon Farm Road TITLE: Cincinnati, OH 45237 r Dinitraniline Orange r Phthalo Green, B.S. Telephone (513) 841-4000 PRODUCTS

Complete coupon and mail COLOR DESIRED PIGMENTS NOW USE@ with your company letterhead.

DYNAMICS OF ROLLSPATTER ANDTRACKING. PARTIII: : IMPORTANCE OF EXTENSIONAL VISCOSITIES--J.E.

Glass

Journal of Coat~ngs Technology, 50. No. 641, 56 (June 1978)

L rl

@ Interior paints thickened with different molecular weights i: of either acwlamide/acrylic acid copolymers (PAMC) or

ethylene oxide homopolymers (PEO) were formulated for roll application studies. Both water-soluble polymer types

k have been reported to exhibit high extensional viscosities *-

at low solution concentrations. Paints formulated to Stormer viscosities of 120 and 90 KU gave filaments with high apparent extensional viscosities. Differences between the shear deformational responses of these paints and formulations thickened with other water-soluble polymers prepared from the same grind were not evident. On rollout, the paints with high apparent uniaxial extensional viscosities (q) exhibited extremely large ribs and associated tracking patterns and either extremely stable

f roll fibers or a high degree of spatter. Ribbing is the precursor of tracking, i.e., surface irregu-

L. larities in roll-applied coatings. The sizes of the rib . structures leading to tracking patterns are related to the

formulation's extensional viscosity, and the ribs are capa- I ble of growing, with increasing roller velocities, to mag- r

nitudes comparable with the roll's diameter. In addition to ' },

the striations generated by such ribs, tracking patterns r are complicated by partial substrate-connected filaments

which fall back upon the coated surface, with the dissipation of extended roll fibers.

Newtonian fluids exhibit ribbing and fiber stability. However, as noted in investigations of paints with comparable q and in formulations containing mixed thickener

jt combinations, elastic~ty can be important in roll applica-

I/ tion performance. The contribution of a ourelv elastic 1 effeciappears to be dependent upon the magnitube of the t paint's n and the roll's application velocity. Elasticity con-

tributes.directly20 a broad distribution-of spatte; drop sizes when high q filaments dissipate via a ductile failure mechanism and indirectly through stabilization of droplet-thread networks as the filament's q decreases. Spatter, i.e., roll fiber dissipation, is observed to occur via capillary force, ductile failure, and hybrid combinations of these two primary mechanisms.

Using differential techniques, equationsfor the rates of extension are derived for roll application conditions. The rates of extension (i) at a constant roll velocity are in- ersely related to the filament's length. At typical trade

plication rates, i.e., 1-3 ftlsec, is predicted to vary from 0 to 20 sec-l for filament lengths of 0.2 to 2 in. (observed flow visualizafion studies). In the paint filaments exam-

ined apparent uniaxial extensional viscosities were not obtainable over the total predicted application i. Some of the complexities associated with measurement of non-steady state, "very apparent uniaxial extensional viscosities" are discussed. The data are presented on a comparative basistoimpress upon theoaint chemistoren- gineer that extensional deformationsand flows are important in understanding coating performance in roll applications.

DYNAMICS OF ROLL SPATTER AND TRACKING. PART IV: IMPORTANCE OF G* RECOVERY AND Ni IN TRACKING-J.E. Glass

i e - 'I ,?'

' 4 ' Journal of Coat~ngs Technology. 50. No 641:?$r.u'~uiie 1978)

The interrelationships amona rheoloaical ~arameters. formulation components andioll trackkg are di?ussed: Formulations with high extensional viscosities (n >I000 poise over 20-150 sec-' extension rates) and moderate to high complex modulus responses (G' Recovery >I50 dyn cm-2 at 0.08 sec-' shear rates) after high shear exposure give3ignificant tracking patterns. However, paints with high q but low G' Recoveries (< 50 dyn cm2) rapidly flow out to provide smooth roll coated surfaces. Rapid relaxation from the high q reached during applicatioj apparently occurs. Formulations with low to moderate q (<50 poiseland moderate G* Recoveries (5 200 dyn ~ m - ~ ) or very low q (<I0 poise) and high G' Recoveries (7 800 dyn ~ m - ~ ) provide rollouts of intermediate roughness. Specific examples for each formulation type are discussed.

Chemical composition of the thickener and latex me- , dian particle size, particularly important at high total volume solids, are the formulation components of impor- j tance in roll tracking. Increasing hydrophilicity in the i thickener's structure, with molecular weights <500,000, and increasing biomodal particle size latices are desirable I for good flowout. With small monodispersed latices, di- ! rectional surface irregularities are observed and are be- lieved to be related to yield stress characteristics.

First normal stress differences (N,) are proposed to represent both elastic responses at low shear rates (G' Re- covery) and yield stresses in highly pigmented paints. The merits of G' Recovery and-N, as rheological tools for quantifying tracking in low q formulations-are discussed. In formulations otherthan those with hiahnand moderate to high G' Recoveries, roll tracking ass&sments correlate with quantitative drawdown bar/profilometer evaluations, which simulate brush flow and leveling.

Journal of Coatings Technology 3

PRI Presentation at 1978 Annual Meeting - To Cover Variety of Research Topics

One of the featured presentations at the 1978 Federation Annual Meeting, to be held Nov. 1-3 at the Conrad Hiiton Hotel, Chicago, Ill., will bea three-hour session sponsored by the Paint Re- search Institute.

The PRI session. scheduled for Thursday morning. Nov. 2. will present the following:

"Solubility"-E.B. Bagley. of Northern Regional Research Center. U.S. Dept. of Agriculture.

"Rheoiogy"-Raymond R. Myers, PRI Research Director.

"Color and Hiding"-Fred W. Billmeyer, Jr., of Rensselaer Poly- technic Institute.

"Corrosion ControlM-Dean M. Berger, of Gilbert Commonwealth Companies.

"Mildew Defacement"-Donald J. Siehr, of Dept. of Chemistry. Uni- veristy of Missouri-Rolla.

Theme forthe 1978 Annual Meetingis "Coatings: The Search for Oppor- tunities." and Program Chairman Fred Schwab, of Coatings Research Group. Inc., Cleveland. Ohio, has announced the following papers selected for presentation:

"New Concepts in the Formulation of Gloss Latex Paintsu-John Bax, of Scott Bader Co. Limited.

"Cementitious Coatingsw-Joseph Lavelle, of Rohm and Haas Co.

"Opportunities in Air Force Coatings Research and Developmentv-Daniel E. Prince. of Air Force Materials Labo- ratory, Wright-Patterson Air Force Base.

"Coatings as Vapor Barriers in House Insulation and Their Effect on Heat Transmission"-Douglas M. Burch. of National Bureau of Stan- dards.

"Solar Collector Performance: A Dependence Upon Coatings"-Rich- ard E. Wolf, of DeSoto, Inc.

"Polyesteramide Modified Water- Dispersible ResinsM-Wilma J. Schneider. of Northern Regional Re- search Center. U.S. Department of Ag- riculture.

"New Coatings from Monomers that Cure without ShrinkingM-William J. Bailey. of University of Maryland.

"APS-A New Coatings Sys- tem"-Edward G. Bozzi. of CIBA- GElGY Corp.

"Information-A Vital Paint Raw Material3'-D. Dasgupta, of British Paint Research Association.

"Latex Based Universal Primer9'-

Andrew Mercurio, of Rohm and Haas Co.

"Today's Coatings and Our Needs in the Futureu-Members of Painting and Decorating Contractors of America.

Also featured will be the Mattiello Lecture by Dr. Kenneth L. Hoy, of Union Carbide Corp., "The Effect of Reaction Pathway on Emulsion Polymer Structure," and a session sponsored by the Federation's Man- ufacturing Committee on "Disposal of Water-Thinned Solids."

Other planned program presentations include:

Keynote Address Constituent Society Papers Roon Awards Papers Educational Seminar Technical Information Systems Workshop

Paint Show

To be held concurrently with the An- nual Meeting at the Conrad Hilton. the Paint Show is the only national exhibit of raw materials and equipment used in the formulation, testing. and manufacture of paints and related coatings.

All available booth space has already been resewed for the 1978 event. which will be the largest in Paint Show history.

Show hours will be 12:30 to 6:00 pm on Wednesday. November 1; 10:00 am to 6:00 pm on Thursday. November 2; and 10:W am to 4:00 pm on Friday, November 3.

Room ReSe~ationS

All requests for rooms and suites must be on the official housing form and sent to the Conrad Hilton Hotel. These forms have been mailed to Federation members. and additional copies are available from Federation headquarters.

Registration Fees

Regular "on-site" registration fees will be $40 for Federation members and $55 for non-members. Advance registration will be available for $35 for members and $50 for non-members.

Once again, there will be a special $15 advance registration fee for retired Fed- eration members.

Registration forms will be included in future issues of the JOURNAL OF COAT- INGS T ~ C H N O L O G Y . and will also be mailed to all members of the Federation in August.

NPCA Meets Same Week

The National Paint and Coatings As- sociation will hold its Annual Meeting on October 30. 3 1, and November I at the Palmer House in Chicago.

NPCA registration badges will be honored for admission to the Federation Annual Meeting and Paint Show on Wednesday, November 1.

Luncheon

An awards luncheon will be held at Noon on Friday. November 3. at the Conrad Hilton.

Presentations will be made to recipi- ents of the George Baugh Heckel Award (outstanding individual who has con- tributed to the advancement of the Fed- eration) and the Flynn Awards (firms judged to have the best exhibit booths in the 1978 Paint Industries' Show). A ce- lebrity guest speaker will be featured.

The luncheon. to be open to all reg- istrants, is being held in place of the traditional banquet.

Spouses' Program

A schedule of activities has been planned each day for spouses attending the Annual Meeting, and a Hospitality Room will be maintained at the Conrad Hilton.

A get-acquainted Wine Tasting Party is scheduled for Wednesday afternoon. A continental breakfast will beavailable on Thursday morning. preceding an all-day tour which will include high- lights of the city. luncheon at the Ritz- Carlton Hotel. fashion show, and a shopping spree at the Water Tower Place.

Continental breakfast will be sewed again on Friday morning, followed by the Awards luncheon.

Registration fees are $20 in advance and $25 on-site.

Program Steering Committee

Assisting Chairman Schwab on the Program Steering Committee are: Mor- ris Coftino (Vice-Chairman), of D.H. LitterCo.. Inc., New York. N.Y.; Har- vey Beeferman, of DeSoto Coatings Ltd., Toronto, Canada; Gordon Bier- wagen, of Sherwin-Williams Co., Chicago. Ill.; Hugh Lowrey, of lndurall Coatings, Inc., Birmingham, Ala.; and Thomas J . Miranda, of Whirlpool Corp., Benton Harbor, Mich.

Vol. 50, No. 641, June 1978 17

Nalco From a broad selection of non-silicone and silicone types, you can select the right defoamer for trade sales coatings or industrial finishes. Like all Nalco defoamers, it's designed to glve you effective foam prevention or destruction while m~nimizing risk to film qual~ty, color acceptance

Uamers and persistancy. Contlnulng research In process foam control keeps our people ahead of developments In coatings technology. And while we're new to palnt, we're old hands at lickina foam problems. There probably isn't a foam problem i n work. production or application that we haven't seen before. For fast answers on foam questions, call our "hotllne" number, 31 2/887-7500, ext 1214. Nalco Chemical Company, Specialty Chemicals Group. 2901 Butterfleld Road, Oak Brook, Illinois 60521

50 k a f s of Leadmhp in Chenlic-a1 Technok%y 1928 - 1978 N A LC o


Federation of Societies for Coatings Technology

AUDIOIVISUAL PRESENTATIONS

(All A/V presentations include slides, cassette tapes and scripts)

CAUSES OF DISCOLORATION IN PAINT FILMS Some of the common causes of paint discoloration, such as mildew, sulfide staining, dirt retention and staining by cedar or redwood are illustrated on houses and on painted panels. Chemical tests for distinguishing between these types of stains are shown. A test for distinguishing between efflorescence and chalking of paint films is also described. 15 Minutes (37 Slides) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .$30

HIGH SPEED DISPERSION Produced by the Manufacturing Committee, Montreal Society for Coatings Technology

High speed dispersion is widely used in the manufacture of protective coatings. The show covers theoretical and practical techniques used for dispersion in paint plants. Color slides show laboratory test equipment and plant scale manufacturing procedures. 20 Minutes (60 Slides) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . $40

FEDERATION TRAINING SERIES ON TEST METHODS Prepared by the Federation Educational Committee

Volume 1 (12 Lessons) Lessons vary from 7 to 20 minutes (300 slides) . . . . . . . . . . . . . . . . . . . . . . . . .$loo

Lessons Producing Society Stormer Viscometer Cleveland Stormer Viscometer - Stroboscope Golden Gate Specular Gloss Los Angeles Acid Number Pacific Northwest, Portland Section Non-Volatile Content of Resin Solution Louisville Porosity of Paint Films Pacific Northwest, B. C. Section Surface Tension Pittsburgh Flash Point - TCC Golden Gate Weight Per Gallon Cleveland Sag Resistance Rocky Mountain Leveling Rocky Mountain Hardness - Sward Rocker Houston

Volume 11 (3 Lessons) Lessons vary from 7 to 11 minutes (79 slides) . . . . . . . . . . . . . . . . . . . . . . . . . . . $50

Lessons Producing Society A Simple Method to Determine Philadelphia

Microbiological Activity A Salt Spray (Fog) Testing Cabinet Golden Gate Wet Film Thickness Gages Golden Gate

Causes of Discoloration in Paint Films . . . . .$30 High Speed Dispersion . . . . . . . . . . . . . . . . . . .$40

Volume I, Test Methods . . . . . . . . . . . . . . . . . .$I00 Volume 11, Test Methods . . . . . . . . . . . . . . . . . .$50 (Sh~pping Charges Extra)

Company Name

Address

City State Zip

PLEASE MAKE ALL CHECKS PAYABLE TO

Federation of Societies for Coatings Technology 1315 Walnut Street Suite 830 Philadelphia, Pa. 19107

Pennsylvania residents pleame add 6% sales lax

ORDER FORM

Federation of Societies for Coatings Technology 1315 Walnut Street Suite 830 Philadelphia, Pa. 19107

Please enter my order for the following Units at the price of $1.50 each:

Number Of Copies Unit Title

Price (@ $1.50)

. . . . . . . . . 1 "Introduction to Coatings TechnologyM-W. R. Fuller. (Oct. 1964) (Revised May 1973) . . . . . . . . . . $

"2 "Formation and Structure of Paint FilmsM-W. R. Fuller. (June 1965)

. . . . . . . . . 3 "Oils for Organic Coatingsu-F. L. Fox. (Sept. 1965) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . $

. . . . . . . . . 4 "Modern Varnish Technology"-A. E. Rheineck. (May 1966) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . $ . . . . . . . . .

. . . . . . . . . 5 "Alkyd ResinsW-J. R. Blegen. (Mar. 1967) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . $ . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . 6 "Solvents"-W. R. Fuller. (May 1967) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . $

. . . . . . . . . . 7 "White Hiding and Extender Pigments"-W. H. Madson. (Oct. 1967)

"8 "Inorganic Color Pigmentsw-W. R. Fuller and C. H. Love. (Mar. 1968)

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 "Organic Color Pigmentsw--J. G. Mone. (July 1968) .. $

"Black and Metallic Pigmentsu-W. S . Stoy. E. T. Usowski, L. P. Larson, D. Passigli, W. H. . . . . . . . . . . 10 Byler, R. Evdo, and W. von Fischer. (Jan. 1969) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . $

. . . . . . . . . 11 "Paint Driers and Additivesu-W. J. Stewart. (June 1969) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . $ . . . . . . . . .

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 "Principles of Formulation and Paint Calculations"-W. R. Fuller. (June 1969) $

. . . . . . . . . 13 "Amino Resins in Coatings"-W. L. Hensley and W. E. McGinty. (Dec. 1969) . . . . . . . . . . . . . . . . . . . $ . . . . . . . . . .

. . . . . . . . . 14 "Silicone Resins for Organic CoatingsM-R. W. Clope and M. A. Glaser. (Jan. 1970) . . . . . . . . . . . . $ . . . . . . . . .

. . . . . . . . . . . . . . . . . . . 15 "Urethane Coatingsw-D. Lasovick. (July 1970) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . $

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16 "Dispersion and Grinding"-M. H. Schaffer. (Sept. 1970) $

. . . . . . . . . . . . . . . . . . . 17 "Acrylic ResinsM-Gerould Allyn. (Mar. 1971) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . $

. . . . . . . . . . . . . . . . . . . 18 "Phenolic Resins"-R. D. McDonald. (Mar. 1971) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . $

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19 "Vinyl Resins"-G. M. Powell (Apr. 1972) $

. . . . . . . . . . . . . . . . . . . 20 "Epoxy Resinsu-R. A. Allen (Apr. 1972) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . $

"Nitrocellulose and Organosoluble Cellulose Ethers in Coatings"-E. C. Hamilton and . . . . . . . . . . . . . . . . . . . 21 L. W. Early, Jr. (Sept. 1972) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . $

. . . . . . . . . . . . . . . . . . . 22 "Plasticizers"-J. K. Sears (June 1974) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . $

. . . . . . . . . 23 "Interior Finishes8'-Murray Abriss and Oliver Volk (Apr. 1976) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . $ . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . 24 "Exterior House Paintv-G. G. Schurr (May 1977) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . $

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25 "Automotive FinishesN-Ralph Williams (July 1977) $

. . . . . . . . . 26 "Corrosion and the Preparation of Metallic Surfaces for Paintingw-Clive H. Hare (Feb. 1978) . . $ . . . . . . BINDER (S)

Handy flat back blade-type binders which will hold 18 units in the "Federation . . . . . . . . . . . . . . . . . . . Series on Coatings Technology." . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . $6.00 each, or 2 for $11.00 $

"Not available at this time; out of stock. TOTAL $ . . . . . . . . . . Terms of Orders: PrepiGAdd 5% to total amount of order to cover handling and postage

Orders Requiring Bil l lnFA handling charge of 50C will be added to each order requiring bllling. Postage charges will be additional.

Name

Company

Address

City State Zip Code

Pennsylvania residents please add 6% sales lax PLEASEMAKEALLCHECKSPAYABLETO"FEDERATIONOFSOClETlESFORCOATlNGSTECHNOLOGY"


I Gentlemen: Please send more information about REACTOMER ACRYLIC MONOMERS and 21 UVITHANE URETHANE OLIGOMERS.

ThiokollChemical Division, Marketing Communications, Dept. JCT P.O. Box 8296, Trenton, N.J. 08650

P.O. Box 8296, Trenton, N.J. 08650 I

I I Name thermoplastic urethanes urethane oligomers, prepolymers and rubbers I Title acrylic monomers polysulfide polymersand rubbers I plasticizers epoxy modifiers and curing agents I company

I I Address I I City I

State Zip-

Government and lndustry

MCA Cites Chemical Industry Efforts on Safe Handling of Hazardous Materials

The chemical industry's long and continuing dedication to safe transportation o f hazardous materials was cited recently i n testimony before the House Subcommittee on Transportation and Commerce by David L. Rooke, Vice- President of The Dow Chemical Co., who testified for the Manufacturing Chemists Association.

The subcommittee, concerned over the increase i n rail transportation accidents, was advised that MCA's safety interests date from its founding i n 1872. Its first technical committee was organ- ized in 1918 to coordinate an industry effort for container improvement, stim- ulated by a series o f rail accidents involving shipments of corrosive liquids. This interest i n all aspects of shipping, from the smallest o f vials to tank cars, continues today.

Mr. Rooke described some o f MCA's comprehensive programs:

(1) Chemical Safety Data Sheets - These cover more than 100 chemical

products and set forth the physical and chemical characteristics o f the product, its hazards, instructions on safe handling, first-aid treatment, required labeling and methods o f loading and unloading. More than 70,000 copies are distributed annually.

(2) Chemical Transportat ion Emergency Center (CHEMTREC) - Described as the "world's most completely equipped and qualified center geared to provide prompt information on proper response to emergency situations involving chemicals," CHEM- TREC relies on a widely publicized toll-free nationwide telephone number, which also is shown on shipping papers, to provide round-the-clock emergency service. Since its inception i n 1971, CHEMTREC has received more than 58,000 telephone calls and provided initial support i n more than 10,000 inci- dents involving chemicals. Follow-up aid is provided by shippers, manufacturers o r industry-sponsored emergency units in major accidents.

(3) Chem-Curds -These are carried by transportation personnel and provide information on emergency handling and first-aid related to the product. More than 800,000 have been distributed.

(4) Proper precautionary labeling of chemicals - M C A first published a manual on this i n 1945. I t became the basis i n 1976 for Standard 2129.1, developed b y the American National Standards Institute.

Despite these efforts, Mr . Rooke said, there still are tragic accidents. H e expressed the belief that there must be mutual cooperation between the rail- road and chemical industries. Because o f this, M C A and the Association of American Railroads recently established a task force to work on the problems o f safety i n the rail transportation of hazardous materials. Appointed groups wil l study i n detail the safety status o f equipment, all facets o f transportation, data analysis and accident response.

Regulatory Agencies: How Do You Influence Them?

The following suggestions for dealing with governmental until proven otherwise, that a well-informed regulator will agencies were submitted by Ralph Williams (Technical Di- write the fairest and most equitable regulation. rector) and Barry Brodt (Environmental Coordinator) of In- Offer to assist the regulator(s) gain knowledge in the fieid mont Corp., Anaheim, Calif. affected by his or her decisions. You can arrange meetings

Recent and continuing regulatory activity in California will (information sessions) with known experts, supply literature have an effect on every coatings manufacturer expecting to such as journal excerpts, and provide access to knowledge. do business in the state. Coatings manufacturers have re- Aboveall, besureyour own technical knowledge isup-to-date acted in a variety of ways; some have been more successful and accurate. than others in shaping the final form of regulations. In our It is helpful to follow regulatory activity not directly related participation in this process, we've made certain 0bSe~ationS to your industry. This can provide you with topics of conversa- which may help those involved in similaractivity in California tion and opportunities to indicate your opinion of regulatory or elsewhere. objectives.

Regulatory staffs function to carry out what they believe to The activities listed above will mark you asa reasonableand be mandates resulting from Federal, State, and local legisla- capable person in the minds of stafflagency members. You tion. In our experience, staff members are reasonable people may be offered the opportunity to serve the staffiagency in an trying to do agood job. Like most people, they do not respond unofficial or advisory capacity. We recommend that you ac- well to public criticism; comments of a critical nature should cept the opportunity. The considerable time required by such be given on a one-to-one basis in a private meeting. Your service will ultimately prove well-spent. individual effort may not besuccessful, but as others reinforce Confrontation tactics should be used only as a last resort. your position, questionable areas may be resolved. The probability of success is not great, and costly measures

Do not expect to have significant influence on the outcome will be required if there is any hope of reaching what you of a regulation by showing up for the first time on theday of a consider to be a satisfactory conclusion. public hearing. People who have influence have developed Finally, follow the activities of legislators who are involved rapport with the individuals who develop the regulations. with regulatorystaffs. Don't hesitate to write to them on topics Facts should be presented as clearly, accurately, and as early about which you are knowledgeable. aspossible. Evasivetactics orinaccurateinformation can only In short, become politically active! serve to damage credibility and diminish influence. Assume,


FEDERATION OF SOCIETIES FOR COATINGS TECHNOLOGY

1978 ANNUAL MEETING AND PAINT INDUSTRIES' SHOW CONRAD HILTON HOTEL, CHICAGO, ILLINOIS

NOVEMBER 1,2,3,1978

"COATINGS:

SEARCH

OPPORTUNITIES"

Conrad Hilton Hotel 720 South Michigan Ave. Chicago, 111.60605

APPLICATION FOR ACCOMMODATIONS

RESERVATION: Please reserve the following accommodations: See reverse side for room rates. Room reservations cannot be guaranteed unless this form is received by Oct. 3, 1978. Reservations accepted only on official housing form.

CHOICE OF HOTELS: 1st choice

2nd choice

ACCOMMODATIONS Single (1 person) Double (2 persons) Twin (2 persons) Suite (parlor and 1 bedroom) Suite (parlor and 2 bedrooms)

ARRIVAL AND Arrival: Date Hour

DEPARTURE: Departure: Date Hour

Reservations held only until 6 p.m. unless later arrival is indicated.

NAMES AND ADDRESS OF ALL OCCUPANTS OF ROOMS (Please "bracket" those rooming together). Incomplete information WILL DELAY assignment of room. Type additional names on a separate sheet, or on reverse side.

.A'

NUMBER REQUESTED

SEND CONFIRMATION TO: NAME -

PLEASE PRINT

OR TYPE STATE ZIP

RATE REQUESTED

Vol. 50, No. 641, June 1978 23

LIST ADDITIONAL NAMES BELOW

HOTEL INFORMATION AND RATES

The Conrad Hilton and Pick-Congress Hotels have reserved blocks of rooms specifically for the 1978 Annual Meeting and Paint Industries' Show of the Federation of Societies for Coatings Technology, November 1, 2, 3, 1978, at the Conrad Hilton.

The Pick-Congress is located two blocks from the Conrad Hilton

All room rates are subject to additional 6.1% charge to cover Illinois Hotel Operators' Occupation Tax and the Chicago Hotel Operators' Tax, as well as a 2% Chicago Hotel Accommodations Tax imposed by the City of Chicago.

You will receive confirmation from the hotel to which you have been assigned. If you wish to cancel or change the date of your reservation, contact that hotel directly. If the rate requested is not available, the next available rate will be confirmed.

Conrad Hilton Hotel Conrad Hilton Towers Pick-Congress Hotel 720 S. Michigan Ave. 520 S. Michigan Ave.

Chicago, 111.60605 Chicago, 111.60605 31 2-922-4400 312-431-1 102

Singles $35 41 44 47 62' $44 67' $29 34 39

Doubles $47 53 56 59 $56 $41 46 51

Twins $47 53 56 59 62' $47 56 67'

Suite (P&l) From $67 to $285 From $70 to $255 From $65 to $1 50

Suite (P&2) From $1 85 to $650 From $190 to $400 From $105 to $250

'Deluxe Twins


Photo courtesy of De Solo, Inc.

Slurry Systeh ... It makesa good thing even better. Take the tank used in the Hockmeyer Slurry To help you with your slurry usage, we Svstem.. . It's ~erfectlv round. so ~iament provide complete instrumentation, cleaning Gn'tbuild up.'~nd th i ~ockme~er Bystem nozzles, even a complete unloading station. comes with a powerful, heavy-duty agitator, For detailed facts, use the coupon. Do it now. as well as pumps and piping; proper And avoid slurry's disadvantages. circulation is assured, the slurry is

Val. 50, No. 641, June 1978

Three ways to assist coating quality.

1. WitcoB driers. Our metallic carboxylates are manufactured to insure control led metal concentration, low viscosity and light color. Their high quality is the result of long experience, continuous research and rigid laboratory control. Let us suggest which of our many grades are best for your needs.

2. Witco metallic stearates. Our stearates are noted for their uniformity of composition, color and particle size. Try our recommended aluminums or ca lciums in oleoresinous coatings for improvement of pigment suspension and modification of flow properties. Special zinc grades are available to enhance lacquer sanda bility. Only Witco operates four metallic stearate plants in North America to serve you better. Only Witco offers you such a broad selection.

3. Keycide@ X-10. A stabilized form of tributyltin oxide, Keycide X-10 is an effective antimildew additive especially useful in polyvinyl acetate latex paints.

For further information, please contact us at (3 12) 458-0765, or send the coupon below.

Witco Chemical Corporation Organics Division, Dept. H2

I 6200 West 5lst Street I Chicago, Illinois 60638 I

witco i Chemical 1

I I -

I I Please send me information on the following materials for coatings: 1 Witco driers Witco metallic stearates Keycide X-10

I I

I I I Name I I 1 Title Phone

I I

i company I I 1 Address

I I

I city State Zip I I I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 I I I 1 1 1 1 ~ 1 ~ 1 1 1 I I m


Device for Weathering Sealants Undergoing Cyclic Movements

K.K. Karpati National Research Council of Canada*

A manually operated device has been designed and produced that will enable individual sealant specimens to be subjected to cyclical movements. This simple device can be used in accelerated testing where one of the aging factors is cyclical movements that can be accelerated by increasing the amplitude of the cycling. Simultaneously, other aging factors can be varied. The same principle of testing involving this type of device can be applied to any material that is subject to cyclic, tensile, or compressive stresses in service.

INTRODUCTION

Laboratory testing to characterize the mechanical capability of building sealants (one-part silicones and two-part polysulfides) has been developed to a considerable degree by the Division of Building Research, National Research Council of Canada.'-4 Movements of various types of joints in buildings have also been measured to provide information regarding the rates of strain and the elongation or compression to which sealants may be subjected in service.', s To study the behavior of sealants undergoing normal aging conditions, a weathering rack was constructed6 to simulate service conditions by imposing continuous movement on the specimens attached to it: compression at high temperatures and tension at low temperatures. The movement is imposed as a differential movement between aluminum bars and the steel frame of the rack undergoing outdoor temperature changes. Although the thermal coefficient of linear expansion of aluminum is twice that of steel, sufficiently large differential movements can only be attained with a large size rack.

Because few users or manufacturers can afford the construction of a relatively expensive rack, there is need for a simple, cheap device that can subject sealant specimens to extension and compression while exposed outdoors or to various artificially produced conditions. The device to be described was developed to meet this requirement.

'Materials Scaion. Div~sion of Building Reqearch. Oltawa. Canada.

DESCRIPTION OF DEVICE

The device is designed to impose intermittent movement on asealant specimen by manual adjustment of its width. Each device holds a single specimen (the weathering rack cycles more than 200 specimens). Figure 1 shows the device with and without a specimen of standard size (M x M x 2 in., or 1.25 x 1.25 x 5.08 cm) sealant bead mounted on it. A failed specimen is used toallow a view of the adjusting screw behind the sealant bead. The screw traverses the center of the aluminum blocks and is locked at one end (Figure 1). The distance between the blocks can be adjusted by means of this screw from 0 to 2 in. (5.08 cm) with an accuracy of k0.005 in. (0.013 cm), measured by means of calipers at the ends of the sealant specimen. The regulating action is similar tothat of a vice, and will be referred toas such. A mechanical drawing of the vice is shown in Figure 2.

Once a specimen has been tightened to the aluminum blocks of the vice, tension or compression can be imposed on the sealant bead by varying its width. On a standard one half inch wide specimen, a maximum of 300% extension can be produced. The compression that can be imposed is limited, for at 100% compression the sealant bead would be completely extruded. For a specimen with a width of less than one half inch the maximum percentage extension would be greater; correspondingly, for a specimen with greater than one half inch width the maximum percentage extension would be less, produced with a vice having a two-inch total travel.

The 2 % movement that a sealant can withstand without failure, i.e., its movement capability, isits most important characteristic. Sealant manufacturers suggest that joints should be designed with not more than 225% (that is 25% extension and 25% compression, starting with a relaxed material) yearly movement for high performance sealants. This value is based on the service performance observed by manufacturers in the last two decades, the period during which such products have been available. (When the products were first marketed, greater movement capability was claimed.)

Vol. 50, No. 641. June 1978

K.K. KARPATI

The vices provide a test facility for determining the movement capability of existing sealants and should be more reliable than observations of buildings where such irregularities as joint width, off-plane twisting of the sealant, and poor workmanship may influence performance. These factors are difficult to observe objec- tively, partly because their occurrence may be erratic and partly because when failure is noticed the failure- causing joint configuration may not still be present. In addition, during the time lag between the occurrence and notice of failure, any clear evidence of poor adhesion due to application on a dirty surface may be obscured by more recent dust or deposits from soiled water from adjacent areas. Vices are also helpful in developing sealants based on new types of polymers or modified formulations of old ones. For studies of sealantlpaint systems, the test sealant can be painted at various times during its life.

In addition to the factors usually investigated in connection with aging of polymers-heat, light, water- cyclical movement, which imposes alternating tensile and compressive stresses, can be studied through the use of vices. A polymer under stress and a relaxed one may react quite differently to the usual factors of aging. In addition, relaxation of stress occurs in varying degrees, depending on type of polymer, value of stress, temperature, and length of time under stress. As a result of stress relaxation, the interaction of stress with the agingfactors changes continuously. Another aspect of the effect of relaxation associated with cvclical stress is that it may result in permanent deformaiion, causing unwanted local thinning of the sealant bead.

EXAMPLE OF USE OF VICE

Consider the exposure to outdoor weathering of a sealant that has undergone no movement and is, therefore, in a relaxed state. Exposure could be initiated at a time when average air temperature is equal to the mean annual value for the region. At arbitrarily chosen time intervals the width of the specimen should be changed in proportion to the total yearly movement planned for the specimen, and to the time interval during which the yearly maximum temperature difference will occur, that is, halfa year. With *25% yearly change, a one half

Figure 1-Cyclic movement device

28

KLARA K. KARPATI has been associated with the Division of Building Research of the National Research Council of Canada since 1965. Previously, she was employed in paint research and development by I.C.I., England, and by Trimetal Paint Co., Belgium. She obtained the License Speciale en Chimie lndustrielle from the University of Brussels and graduated in Chemistry from the University of Sciences of Budapest. In Hungary, Mrs. Karpati worked in the Central Paint Research Laboratories.

inch wide specimen requires 0.5 x 0.2513 = 0.042 in. (0.107 cm) width change each time if changes are made at monthly intervals. As the maximum error of the adjustment (0.005 in.) is not cumulative. shorter intervals and correspondingly smaller width changes are quite practical. Upper limits of ?80% were successfully used without affecting the stability of the vice.

Cycles can also be started with an initial tensile or compressive stress already imposed. A test of this type is designed to simulate situations arising for various reasons on the outside of buildings. One possibility is that the temperature at installation is close to one of the yearly extremes instead of the preferred annual mean temperature. If the temperature is close to the yearly maximum. the sealant will work mainly in extension. and about double the amount it would if installed at the mean temperature. If it is close to the yearly minimum (although this is less likely), the sealant will work mainly in compression.

Another question often raised by designers is whether joint width should be designed on the basis of temperature at the time of installation of the sealant or on the basis of temperature at the time the curing process of the sealant is completed. The curing process takes time, and the sealant may have an initial stress imposed on it even if it is installed at the mean temperature. Sealants cure at various rates depending on chemical composition and formulation. (Being tack free on the surface does not necessarily mean that the bulk of the sealant bead has cured to the same degree.) If a sealant is applied early in the morning, most of the curingprocess may be completed by the afternoon after a temperature increase of perhaps 10 to 30°F (5.6 to 16.7"C). If applied in the afternoon, the same temperature change. but now decreasing. may occur during the night. slowing the curing process in comparison with the rate during the day. On a large building. where caulking of joints may take several days, curing will take place at various temperatures in joints of different widths, resulting in a variable stress condition at any given time of year. The effect of the initial stress state has not yet been investigated, and the vice could be helpful in elucidating the problem and providing an answer to the designer's question. "How should variations in curing time be taken into consideration when designing joint width?"


DEVICE FOR WEATHERING SEALANTS

01111 l l b o i a I*""

Figure ?Mechanical drawing of vice

Vol. 50, No. 641, June 1978

K.K. KARPATI

SUMMARY ACKNOWLEDGMENT

A vice has been designed and produced that will enable sealant specimens to be subjected to cyclical movements. Such movements are intermittent, and are imposed on sealant specimens through manual adjustment at arbitrarily chosen intervals. The simplicity of the vice enables not only the sealant manufacturers but also designers and users to make quick tests. The sealant manufacturer can use it as a tool in accelerated testing where one of the aging factors is cyclical movement, and this can be accelerated by increasing the amplitude and frequency of the cycling. Simultane- ously, other aging factors can be varied. It can be used for comparative testing of possible products for a specific job or to check batch-to-batch variations.

The same principle of testing involving this type of vice can be applied to any material that is subjected to cyclic, tensile, or compressive stresses in service. Examples are roofing materials, various rubber and plastic products, and paint applied to sealant. The size and shape of the sample to be tested can vary without limitation provided appropriate adjustments are made to the size of the vice. It can also be used to investigate the most practical shape for the prototype of a product or the desirable size for a sample.

The author acknowledges the contributions of H.F. SIade and R. Tetu who realized the concept of the cycling device and produced it.

This paper is a contribution from the Division of Building Research, National Research Council of Canada and is published with the approval of the Di- rector of the Division.

References (1) Karpati. K.K.. "Mechanical Properties of Sealants: 11. Be-

haviour of a Silicone Sealant as a Function of Rate of Move- ment." JOURNALOF PA~NTTECHNOLOGY.~~. NO. 569.58 (1972).

(2) Karpati. K.K., "Mechanical Properties of Sealants: 111. Per- formance Testing of Silicone Sealants." JOURNAL OF PAINT T E C H N O L O G Y . ~ ~ . NO. 571, 75 (1972).

(3) Karpati. K.K.. "Mechanical Properties of Sealants: IV. Per- formance Testing of Two-part Polysulfide Sealants," JOURNALOF PAINT TECHNOLOGY.~~ . NO. 580, 49 (1973).

(4) Karpati, K.K. and Handegord. (3.0.. "A Rational Approach to Building Sealant Testing."AdhesivesAge. 16. No. 11.27 (1973).

(5) Karpati. K.K. and Sereda, P.J.. "Joint Movement in Precast Concrete Panel Cladding." ASTM. Journal of Tesfing and Evahafion. 4. No. 2, 151 (1976).

(6) Karpati. K.K. and Sereda. P.J.. "Weathering Rack for Seal- ants." JOURNAL OF COATINGS TECHNOLOGY. 49, NO. 626. 44 (1977).


Progression of Microorganisms On Painted Panels in Puerto Rico

Thomas B. O'Neill and Richard W. Drisko Civil Engineering Laboratory*

Microorganisms were removed from painted panels in Puerto Rico after 0,2,4, and 8 weeks of exposure. A total of 30 different genera were thus isolated and identified. They include 13 molds, 2 yeasts, and 15 bacteria. Aureobasidium sp. was not detected as early as other microorganisms suggesting that it requires an adaptive period during which time the paint surface is conditioned by other microorganisms or weathering.

INTRODUCTION In an earlier study,' microorganisms were isolated from six-month-old painted surfaces of wooden panels at Puerto Rico. While Aureobasidium pullulans was isolated f rom all 26 surfaces tested, other microorganism species were found on as many as 20 to 22 of the surfaces. It was suggested that some of these organisms, although less easily detected than A. pullulans, might play a significant role in paint deterioration. In the present study, the progression of microorganisms on newly installed painted panels at the same test site of Caribbean Testing, Inc., Caguas, Puerto Rico was investigated.

EXPERIMENTAL PROCEDURE AND RESULTS

Isolation and identification techniques similar to those utilized in the previous study were used in the present study. Sterile cotton-tipped swabs were rubbed over the surfaces of each of three paints (Paint 1, Paint 2, and Paint 3) after 0,2,4, and8 weeks. They were then streaked on two agar plates containing different media-potato dextrose agar and trypticase agar. Potato dextrose agar is an acidic medium containing large amounts of dextrose and is used for isolation and

"aterials Science Div.. Naval Construction Baltalian Center. Pun Hucneme. Calif.. 43043

growth of fungiincluding yeasts; trypticase soy agar is a neutral medium without significant amounts of sugar and is used for isolation and growth of bacteria. The mixed cultures were airmailed to Port Hueneme where isolation of pure colonies was performed by transfer to appropriate media, incubation a t 25OC, and identification. Microorganisms were also isolated from soil at the base of the exposure rack and from air at the test site by exposing agar plates for 10 minutes.

The microorganisms isolated and identified according to above procedure are listed in Table I . This table also indicates the number of paints on which each species was isolated. By comparing this table with the similar one from the previous study, many significant differences are apparent. The most notable difference is the absence ofAureobasidium sp. from all of the panels of Table 1 except for one panel after 4 and 8 weeks. Indeed the relative number of different species of each type of microorganism isolated from the paints has changed. More species of bacteria were found in the present study (15) than in the previous study (9) while fewer species of mold and yeast (13 and 2, respectively) were found in the present than the previous study (19 and 4, respectively).

DISCUSSION

The relatively greater number of bacterial species and lesser numbers of mold and yeast species on the newer panels suggests that bacteria are more compati- ble with freshly painted surfaces than molds or yeasts. It also suggests that some of the molds (notably Aureobasidium sp.) and yeasts have an adaption period during which time the paint surface is conditioned by other microorganisms or weathering before they can predominate. The bacterium, Bacillus sp., the mold, Aspergillus sp., and the yeast, Rhodotorula sp., which were found so often in the previous study were also found quite often in the present one.

Vol. 50, No. 641, June 1978 31

T.B. O'NEILL and R.W. DRISKO

Table 1-Mlcroorganlsms Isolated from Painted Surfaces at Puerto Rlco

Of the 20 microorganisms isolated from soil near the of the 26 panels used in the previous study has the test rack, 11 were found in the air and 1.5 on painted greatest number of species. panels. This suggests that wind blown particles of soil are the chief source of contamination of the painted References surfaces with microorganisms. This is further ( 1 ) O'Neill, T .B. and Drisko, R.W., JOURNAL OF COAT~NGS substantiated by the fact that the closest to the ground T E C H N O L O G Y . ~ ~ . NO. 624, 54 (1977).

Molds Yeasts Bacteria Surface From Number Total Which of Number

Organisms Weeks of

Isolated


Paint I

Paint 2

Paint 3

Times Found on

Paint Air Soil

0 2 4 8 0 2

8 0 2 4 8

0-8

- -

. • • • .

e m m e * . * * e e

4 e . e * * * * * e m e m

* * .. e . . . * *

e e e e e e e

e e e e e e

•

e e e e e e e e e

•

e m .

rn

. • • •

e . . . . . . e e e e e e • • a

. * m e • • •

e e e e

• • • . . . . . . e e e e e • •

7 1 0 2 1 2 3 3 3 2 1 0 2 2 0 8 5 7 1 6 2 1 0 0 2 3 4 8 0 0 7 5 0

e e e e e e

e e e e e e e e e e e e e m . 0

3 8

1 1 15 I

13 14 14 I 9

12 14

15

Conservation Through Higher Solids, Lower Energy Cure Coating Resin Systems

Robert N. Price Ashland Chemical Company*

Higher solids polyester and alkyd resins have been developed which, when crosslinked with amino resins, provide coatings which have performance comparable to currently used lower solids systems. Paint formulating, preparation, and application were found to bevery similar to that of conventional coatings. When crosslinked with an aliphatic polyisocyanate resin, low temperature cure systems are obtained. Two-package polyester-epoxy systems which offer a combination of higher solids along with low temperature cure are also described.

The coatings industry today is faced with a number of serious challenges precipitated by intensified pollution control regulations and increasing energy shortages. Simply stated, the resulting challenges to the industry are: (1) Todevelop low or non-pollutingcoatings; (2)To develop more energy efficient coatings; (3) To minimize wasteful use of solvents; and (4) In spite of constraints, to continue supplying high quality coatings.

Although these challenges are simple to state, their consequences to our industry are immense. Con- ventional, low solids, solvent-thinned coatings which are still the backbone of the industrial finishing market, must necessarily be replaced with more ecologically oriented and energy conserving systems.

A variety of approaches, designed to meet these challenges, are being investigated throughout the industry. The most widely pursued of these and estimates of near-term growth versus conventional solvent-thinned systems are given in Table 1 .

The industry recognizes that switching from conventional to exempt solvent systems is, at best, only a stop-gap measure. Even though exempt solvents may be. photochemically. less reactive, the total amount of solvent used in such coatings remains essentially the same as when using conventional solvents. This is a -

Prc>cnrr.dat rhr. '\lh Annual Mcet~ngofthc Fedcrdtion ~ ~ S ~ I C I L . ~ ~ L S br( '~al ing~Tcchnul . og! !n Hou\lc~n. T c h . . Outohcr Zh. 1977.

P O Box L2lY. <alumbu\. Oh#$, 43216.

waste of our petroleum resources. The industry must develop coatings systems which have as a high priority the conservation of this vital resource. Likewise, energy efficient coatings systems must be developed which require minimal energy for curing and solvent disposal.

With respect to energy conservation, much attention has been focused on the energy required during the actual curing of a coating. This is appropriate and, obviously, a significant amount of energy could be saved if, for example, a given coating could be cured in 30 min at 150°F (65°C) rather than 30 min at 350°F (176°C) or even higher. However, to realize the total energy savings possible in a finishing line operation, one must consider the potential savings at each finishing stage. Figure 1, which shows the relative amount of energy consumed during the various stages of a typical coating line operation,' brings into clearer focus the energy required at each stage.

The specific percentages will, naturally, vary considerably from one finishing operation to another; however, it is important to recognize the much greater potential energy savings which are possible in such stages as metal pre-treatment, incineration, or make-up air reduction than in the actual baking stage. From a resin design point of view, it is possible to effect energy reduction at each of these stages. To offer one example, an idealized resin system, which permitted formulation of a paint at 80% volume application solids in acceptable solvents, had excellent adhesion, and was cured at 150°F in 20 min, could:

(1) Eliminate or reduce type metal pre-treatment required if adhesion is adequate without;

(2) Reduce make-up air required to remain below lower explosive limit in curing oven;

(3) Reduce baking energy; and (4) Possibly eliminate the need for incineration.*

'If coaling can be applied at 80% volume solids. incineration is not required by current legjslation.

Vol. 50, No. 641, June 1978

R.N. PRICE

Btu -50-

(Numbers given areon a relative basis and are not intended to total 100%. Many lines, for example, do not use an incinerator; however, when they are used they can consume more energy than the entire remainder of line. This too can be altered if energy derived from incineration products is used as auxilliary source of heat.

The broken lines in the curelmake-up air block indicate energy required for metal and make-up air heating. Energy needed for actual curing of paintfilm is minimal.asshown.)

p q p - p x z p q ~ ~ ~ Pre t rea tmen t D r y i n g Make-uo A i r :,lake-uo A i r C lean lnq

Other than exempt solvent, all systems referred to in Table 1 offer viable approaches in varying degrees towards achieving these goals on a long-term basis. This discussion, however, will focus its attention on high solids liquid and low thermal energy curing systems.

HlGH SOLIDS LIQUID RESIN SYSTEM

There is as yet no universally accepted definition of high solids coatings. Perhaps the most widely used definition, however, is that based on legislation now in effect in certain parts of the United States, stating, in essence, that the coatings shall contain a minimum of 80% solids by volume at application and the volatile solvent shall be exempt. This would be typified by California's South Coast Air Quality District's Rule 442. There are efforts within the industry to have legis- lative groups drop the 80% acceptable limit to 70%. There is considerable logic in this since the greatest portion of solvent savings has already been accomplished, for example, in going from 30% to 70% (an 82% reduction). Going to 80% saves only about another 7%. For the purpose of this report, however, we will use the 80% volume minimum definition for high solids and define lower solids coatings as given in Table 2.

The case for high solids coatings has been thoroughly covered in recent industry publication^.^,^ However,

Table 1-4ndustrial Flnlshes Usages

Exempt solvent-thinned .......... . I5 3 1 Water-thinned ................... . 4 30 High solids solvent-thinned ........ .2 15 Powder .......................... 3 5 Radiation cured.. .......... .. .... 1 4 Conventional solvent-thinned . . . . . .75 15

Flgure 1-Coatlng line energy consumption

Figure 2 is presented to dramatize the magnitude of solvent conservation made possible by the use of high solids coatings.

This figure illustrates the varying amounts of solvent required to apply the same amount of paint solids (0.8 gal) for coatings systems with varying solids contents. Observe that to apply this volume of paint from an 80% solids system requires only 0.2 gal of solvents, whereas from a 30% solids solvent system, 1.86 gal are required. In terms of percentages, this means 930% more solvent is required by the 30% solids system.

The water-borne coating example is based upon a system which contains 14% of its volatile as coupling solvent. As the illustration clearly shows, it is possible for such systems to actually emit a higher level of organic solvent to apply the same volume of paint than would be emitted when applying an 80% volume solids coating.

While solvent conservation is aprimary benefit, high solids coatings provide related savings as well. These are capsulized in Table 3.

HlGH SOLIDS RESINS

The same generic families of resins, established in conventional coatings systems, are contenders for high solids coatings: alkyds, polyesters, urethanes, acrylics, epoxies, etc. General technology, thus, remains very similar. The primary difference between resins designed for high solids use and those for use in con-

Table 2-Volume Solids Definitions

Percentage Range

. . . . . . . . . . . . . . . . . . . . . . High solids 80-100 . . . . . . . . . . . . . . . Intermediate solids 60-80

.................. Standard solids 30-45 ...................... Low solids 10- 15


CONSERVATION IN COATING RESIN SYSTEMS

Table &Related Savlngs 6 1 Consemtlon ol:

Less material to handle ............. Manpower Fewer containers ............... FreightIDrums Less storage ............ SpaceIWorking capital Fewer passes to get film build . . Time-Manpower Less solvent to evaporate.. . EnergylSolvent cost Lower air throughput .................. Energy

0 ventional coatings is molecular weight. In order to = * achieve high application solids in solution type coatings, the viscosity of the resin must necessarily be low; 1 and, the principal means to achieve low viscosity in a resin is through low molecular weight. Lowering the molecular weight in coatings resins is not without at-

Coatim tendant problems. Two major concerns are: - ( I ) Thermal sag, and (2) Lowering of resistance char- Vo'.So'

acteristics.

msohrenu 0.8 gal. 0.8 gal 0.8 gal 0.8 gal. ~o l i ds %lids Solids Solids

&gal. 293gal.

piiq Solvent

High tJ?&TS - I ustrial

SOII~S Ecquer k 80% 30% 30% 15 %

4.53 gal. Solvents

Coatings Thermal sag is the term applied to a condition of

sagging or running caused by heat being applied to cure paint films coated on vertical substrates. As the solvent is driven out of the films during the baking of a highly polymerized coating, the film immediately develops a structure which reduces its sagging tendency. On the other hand, low molecular weight systems tend to fluidize more readily during the application of heat; hence the greater sagging tendency. As will be discussed later, this problem can be minimized through formulating and resin design.

For years, our industry has been improving resistance properties of coatings by building bigger and better molecules. Now, in order to develop high solids in coatings we are forced to reverse this trend and rely on lower molecular weight resins. It follows that it will be more difficult to achieve the same degree of high performance and resistance properties from the low molecular weight counterparts. Optimization of per-

Figure 2-Comparlson of gallonage i n coalngs

formance is accomplished through careful balancing of polymer backbone design and crosslinker selection.

That performance rivaling that of current standard systems can be achieved from intermediate and high solids coatings is illustrated by the data which follow.

A range of polyester and alkyd resins have been developed as candidates for intermediate and high solids coatings. Table 4 gives typical resin constants, approximate molecular weight, and an indication of the degree of polymer linearity. The general direct relationship between these parameters and paint solids can be seen from the data. For example, Polyester A has the lowest molecular weight and provides the highest paint solids. Polyester D has higher molecular weight, is less linear, and yields the lowest paint solids.

Table 4--Higher Solids Resins

Polyestem Non-Oxidlzlng

A B C D Alkyd

Resln Data: 7% Non-volatile (weight) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90 80 80 80 80 Solvent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... ..... . . . . . . . . . . . . . . . . . . . . . . EEAa EEA EEA EEA EEA Viscosity (Gardner) . . . . . . . ,. ........................................ Z-Z, ZZ-Z, Z,+-ZS+ z~+-z, z4.t 2-Zs Molecular weight (calculated Mw) ..................................... 1450 1700 1600 1650 1500 Degree of linearity (96)". . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70 90 100 65 60

Palnt Data: (whlte enamel, plgmentibinder ratlo d 0.811.0) R Volume Solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82 73 69 65 66 Viscosity. sec. #4 Ford Cup

room temperature: ................................................. 11 1 106 106 110 87 @ 130°F: 37 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38 30 40 26

la) kthory crhanol acetalc Ih) Welphl perccnt ofpolymr.r dcrivrd from rcaulantr having a functionality ofnot greater

than 1-0.

Vol. 50, No. 641, June 1978 35

R.N. PRICE

Table 5--Polyester A - High Solids White Enamel

Lb Gal - - 482. I 14.49 Rutile titanium dioxide

4.0 0.27 Suspending agent - amine treated clay 2.8 0.34 Sag control agent - soya lecithin

192.9 21.67 Polyester A 36.9 5.50 Methyl ethyl ketone 35.7 4.75 Butoxy ethanol

275.9 31.00 Polyester A 180.8 18.08 Melamine resin (100%)

9.0 1.25 Catalyst 1.5 0.17 Flow control agent - silicone

20.9 2.78 Butoxy ethanol - - 1242.5 100.30

0.8 ..... PigmentIBinder ratio 138 ..... Viscosity, #4 Ford Cup, sec. @ 77°F 24 ...... Viscosity, #4 Ford Cup, see. @ 160°F 88.2 .... Percent total solids - weight 80.2 .... Percent total solids - volume 30 ...... Percent melamine (on resin solids)

PAINT FORMULATING CONSIDERATIONS

All paints were intentionally formulated to an initial viscosity of about 100 sec #4 Ford cup. At this viscosity, four of the paints were in the range of 65-73% solids by volume and the one based on Polyester A had a true high solids figure of 82%. It has been our general experience that high solids paints having an initial viscosity of about 100 sec fall to about 30-40 sec when heated to the 120-130°F (49-55°C) range, and spray apply very well at this viscosity. Because resins for these paints are relatively low in molecular weight, they tend to atomize more readily than conventional paints and can be spray applied at appreciably higher viscosities. An enamel based on Polyester A, for example, has been spray applied satisfactorily at approximately 80 sec viscosity with an ordinary suction gun.

I 1 I SO XX) 110 120 130 140 150 160 l70 180

Temperature ( O F )

A

cn'"'='

'SI 8 ,5 Q, U) Y

2, .z 50

0 8 5 25

Figure &Temperature vs. viscosity (Polyester B white enamel Ford Cup viscosity)

Ideel spray -Viscosity Range -

ROBERT N. PRICE received the M.S. De- gree In Organlc Chernlstry from North Dakota State Unlverslty, and for 20 years has been engaged In technical servlce ac- tlvlty for the Coatings Industry, worklng wl th both solvent-based and water-

I

thlnned coatlngs He IS currently Group --r"

Leader In Technical Service for Ashland Chemlcal Co 's Standard Solvent- Thlnned, Coil and Hlgh Sollds reslns

i A\

It is also worth noting that when the enamels were reduced to 25 sec with solvent, all remained in a respectable 60-70% volume solids range.

Figure 3 graphically illustrates typical viscosity reduction of an intermediate solids polyester enamel as the temperature is increased. As can be seen, viscosity drops quite rapidly as the temperature is increased to about 120-13O0F, at which temperature it reaches spray viscosity.

Choice of solvents can also have a significant influence on the viscosity reduction of high solids enamels. Figure 4 shows viscosity reduction curves of Polyester D when reduced with either ethoxy ethanol acetate or methyl ethyl ketone. Both are considered active solvents, but the ketone provides considerably faster reduction, which, of course, results in higher solids in a finished paint. Naturally, other factors such as evaporation rate, odor, exempt status, etc., must also be taken into consideration in choosing appropriate solvents, but influence on viscosity reduction should not be overlooked.

A typical paint formulation used in our study is shown in Table 5. Formulation and paint preparation with high solids resins is straightforward and essentially the same as with conventional enamels. Dispersion was carried out in a pebble mill without difficulty and a variety of colored enamels have been prepared in a similar manner with equal success. Difficulties are not anticipated with other commonly used dispersion equipment.

Table &Electrostatic Handguna Spray Conditions of High Sollds Finish

Voltage, K V . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70 constant Air atomizing pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .40

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Material pressure (psi) 50 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Material Temperature. "F 160

Viscosity, sec.. #4 Ford Cup Ambient . . . . . ................ 138 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . @ 160°F 24

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Number of passes 2-3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Flash-off time (min) 5-10

. . . . . . . . . . . . . . . . . . . . . . . . . . . .. Bake schedule (minPF) .. 201350

(=)Handgunused was Nordson NAE-IM (Circu1alingHraler)Type EB. Pump: Mudel 18.

Journa l o f Coat ings Technology


Table 7-Comparative Performance Data - White Enamels

Percent melamine.. ........................ Bake schedule (minPF) ..................... Gloss 60"12O0 .............................. Pencil hardness.. .......................... Reverse impact (in.llb) ..................... Solvent resistance:

xylol, acetone. alcohol (4 hr) .............. Chemical resistance:

20% NaOH (24 hr) ...................... 15% H,SO, (24 hr) .......................

Control Alkyd Tall Oil

15 201350 88148 H

< 10

2P

5 2

Polyester Hlgh Solids Alkyd

Control Alkyd

Coconut

30 201350 90173

F < 10

2

0 I

(a) Rating scale: 0 - No effec t . 5 - Total failure.

One obvious inconveniencein the preparation of high noted in films up to a dry thickness of 2 mils. The film solids enamels results from the fact that very low levels appearance was very good, although a very slight of solvent are employed. This allows a minimal amount orange peel effect was observed in films less than 2 mils of solvent for mill washing and may mean wash solvent thick. Paint was heated to 160°F (71°C) for hot-spray will have to be re-used or used in succeeding batches of application and held at this temperature for several similar paints. hours during test trial. There was no significant in-

The only formulating irregularity to point out is the crease in viscosity during this time. use of soya lecithin. While lecithin is frequently used to aid pigment wetting and dispersion, its primary purpose in this formulation is to imorove thermal sap control. A - marked improvement in this property was observed when used at a level of approximately 0.5% based on POLYESTERS AND ALKYD Polyester A resin solids. With the intermediate solids resins, normal thixotropes have been found to provide In Table 7, the intermediate and high solids resins adequate thermal sag control. crosslinked with monomeric methylated melamine are

comoared to a tv~ ica l short tall oil alkvd and a coconut

HIGH SOLIDS PAINT APPLICATION

Most high solids spray paints will be applied with electrostatic equipment to minimize the loss of these highly loaded paints through over-spray; however, they have also been successfully applied by other common methods, such as flow and roll coaters. The 80.2% volume solids enamel shown in Table 5 was applied with a hot air electrostatic hand gun under the conditions shown in Table 6.

Very good wrap-around was obtained under these conditions and no thermal sag or solvent popping was

alky'd to demonstrate relative These resins illustrate the wide range of properties

achievable with current technology from higher solids coatings resins. Polyester A, for example, has a good balance of film properties and, as pointed out earlier, at a true high volume solids of 82%. Polyester B shows very good flexibility with superior exterior durability based on accelerated weathering data (Table 8). Polyes- ter C has the best flexibility, along with good solvent and chemical resistance. Polyester D, while giving a somewhat lower volume solids paint (65%), is of special interest because of its lower temperature cure

Table 8-Accelerated Weathering Dataa

Control Alkyd Polyester Control Tall Alkyd Oil A B C D Coconut

Percent Melamine ....................... .. ........... 15 30 30 25 30 30

Expowre Time: Gloss Readings 60'120" Initial . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80143 93178 97193 92/70 97/79 85159 300 hr . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70128 72142 85/66 70130 71/40 76142 500 hr . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5017 67/30 7614 1 67/30 4014 6513 1

la) Weather-OmeleP carbon arc type XW-R (Atlas Electric-Devices. Inc.)

Vol. 50, No. 641, June 1978 37

R.N. PRICE

M e t h y l Ethyl Ketone ---- Ethoxy Ethanol Acetate L "1

20.0

1 ."o l:o 7.0 6.0 5.0

4.0

3.0

2.0

1.0

2 8 8:% 0.5 0.4

0.3

0.2

80 75 70 65 60 55 50

PERCENT SOLIDS

Flgure 4--Vlscoslty reduction (Polyester D)

capability-10 min at 250°F (120°C). Although cured at a much lower bake schedule, Polyester D still provided the hardest film with superior solvent and chemical resistance. Performance of the nonoxidizing alkyd is very similar to the control coconut alkyd, but at a considerably higher solids.

When the data are studied in detail, it becomes evident that, in many instances, the performance of the higher solids resins equals or exceeds that of widely used current industrial alkyds.

Figure CPolyesterlepoxy hardness vs. time Em and temperature (Polyesterlepoxy ratio 47153)

u

Table 9-Melamine vs. Isocyanate Cmssllnked Polyester A

Cnwsllnkw Mel6mlne I6ocy.nate

% Crosslinker on solids 30 37 NCOIOH ratio - I.OlI.0 PigmentlBinder ratio 0.811.0 0.811.0 % Volume solids 81 7 1 Pot-life (room temperature) 6 months 0.5 hr Cure schedule (minPF) 201350 201 180 60"/2O0 gloss 91/71 97192 Pencil hardness H HB Reverse impact (in.llb) 10 160 Solvent resistance (4 hr) 3a 3 15% H,SO, (4 hr) resistance 0 2 20% NaOH (4 hr) resistance 0 2

(a) Rating scale: 0 = Na EtTecl. 5 = Total Failure

POLYESTERIURETHANE SYSTEMS

The polyester resins used in this study all contain free hydroxyl groups which are readily crosslinked with adducts containing free isocyanate groups. Table 9 illustrates cure and film performance differences to be expected when the same polyester resin is crosslinked with a methylated melamine o ra urethane pre-polymer.

Results from Table 9 show that when Polyester B is crosslinked with an isocyanate containing resin rather than melamine, cure can be achieved at a much lower bake schedule. This is accomplished, however, at the expense of reduced pot-life and would require the use of a two-component system. Somewhat lower volume solids in the finished paint can also be expected. It should be noted, however, that even with the lower solids, the percent volume solids still remains at avery respectable 71%. The urethane crosslinked film was somewhat softer but much more flexible.

0 10 20 30 40 50 80 70 80 90 100

Baking Time (minutes 1



Table lO-Polyester-Epoxy White Enamel

Part l Lb Gal - - 142.0 16.86 Oxirane ester resin (100% NV)

8.0 1.10 Suspension and sag control agent 5.0 0.68 Flow control agent

36.8 5.00 n-Butyl acetate 325.0 9.81 Rutile titanium dioxide

Disperse to 7+ Hegman, then add: 139.0 - 16.55 Oxirane ester resin (100% NV) - 655.8 5O.M)

Part I1 Lb Gal - -

430.6 40.25 Polyster solution (60% NV) 65.4 9.75 Ethoxy ethanol acetate -

4Y6.0 50.00

52/48 ... PolyesterIEpoxy ratio . 58 ...... Viscosity sec. #4 Ford Cup

78.3 . . . . % Non-volatile - weight 66.0 . . . . % Non-volatile - volume 0.55 . . . . PigmentIBinder ratio 98/93 . . . 60"/20" Gloss

POLYESTERIEPOXY SYSTEMS

It has been found that certain organic acids, because of their electronic structure, are sufficiently reactive to crosslink with oxirane esters at room tempera t~ re .~ Among these acids were chlorendic, tetrachlo- rophthalic, monochlorophthalic, and chloroma- leic acid. Such acids, however, were found to have limited solubility, which made their use unaccept- able in practical coatings systems. Subsequent development of carboxyl terminated polyesters containing these reactive acids improved solubility so workable coatings could be formulated.? These polyesters remained sufficiently reactive for crosslinking to occur with epoxy groups at ambient temperatures. Cure speed of such systems could, of course, be greatly accelerated by the application of heat.

The described polyester-epoxy systems have been available for many years and have found wide use in high performance architectural and maintenance coat-

Table 11--Polyester-Epoxy White Enamel Performance

PigmentiBinder ratio.. ................................... 0.55 PolyesterIEpoxy ratio.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52/48 6W120" Gloss . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98193 Pencil hardness ................................. .. .... . . H Reverse impact (in./lb) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30 Xylene resistance ( I hr) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . VG 10% H,SO, Resistance (4 hr) . . . . . . . . . . . . . . . . . . . . . . . . Excellent 5% NaOH Resistance (4 hr) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Good Stain resistance - variety (24 hr) ........................... VG Exterior durability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . VG

ings. Recently, however, they have attracted considerable interest in industrial coatings because of their ability to crosslink at low bake schedules and provide film properties equal to or better than baked alkyd systems.

Low Temperature Cure

Figure 5 shows the cure response of a polyester- epoxy system as heat is applied. Typically such systems cure to a Sward Hardness of about 20-30 after 24 hr at room temperature. As the graph shows, similar hardness can be achieved after a forced cure of 30 min at 150°F (65°C) or about 5 min at 200°F (93"C), or even shorter times at higher temperature schedules. Full cure is, of course, not immediately achieved at these schedules, but the films are sufficiently hard and tough to be handled without marring. Since the polyester- epoxy systems can cure at ambient conditions, crosslinking then continues at room temperature until cure is complete. This typeof cure can effect considerable energy savings in many coatings line operations whereby that coated object is force cured to the point of handleability, packaged or stored, and full cure al- lowed to develop upon standing.

Paint Formulation

A typical enamel formulation based on a polyester- epoxy resin system is shown in Table 10.

Note that these are two-component paint systems. The polyester-epoxy components are reactive, and when they are blended a reaction begins to take place in the package. The blended components, however, exhibit a long pot-life of 8 to 48 hr, which permits their use in many conventional industrial line operations such as spray, roll, flow, and curtain coaters. Another feature of the polyester-epoxy systems is their higher solids capability. The formulation shown has a percent volume solids of 66 and the solvents are of the exempt type. It is therefore, possible to combine lower temperature cure and higher volume solids in a single system.

Pigment dispersion can be accomplished on all current milling equipment. Dispersion is usually carried out in the epoxy component because its low order of reactivity with most pigments assures a long shelf life.

Performance

Performance data on a typical fully-cured polyester- epoxy white enamel is given in Table 11.

Outstanding properties of polyester-epoxy systems include excellent gloss and stain resistance. Their films also have a good balance in hardness and flexibility along with very good chemical and solvent resistance. Polyester-epoxy's very good exterior durability has been established through years of exposure testing and actual field use in the areas of transportation, maintenance, farm equipment, and commercial and residential buildings.

Vol. 50, No. 641, June 1978 39

R.N. PRICE

The polyester-epoxy systems offer a unique combi- ACKNOWLEDGMENT nation of low temperature cure capability, inter- The author acknowledges the assistance ofR, Hang, mediate-high and per- S. Hudak, Dr. A, Mohar, S. Leyrer, G . Wilhelm, and J. formance. Blegen in the development of the data and the gathering

of information to make this report possible. SUMMARY

Challenges face the coatings industry today because of intensified pollution control regulations and mount- ing energy shortages. Several higher solids and/or low temperature curing resin systems designed to meet those challenges were discussed. Resin systems include alkyd-amino, polyester-urethane, polyester- amino, and polyester-epoxy. Some of these systems have already found commercial use to help solve energy related or pollution control problems-others offer potential solutions for the near future.

References (1) Lukes, R.M.. Prod. Finishing, 40. No. 1 1.48 (1976). (2) Antoneili. J.A., Am. Point Coatings J . . 59, No. 42. 44 (1975). (3) Morgan, G . . Appliance. 32, No. 10. 60 (1975). (4) Price. R.N.. Can. Poinr Finish. 50. No. 3. 48 (1976). (5) Lunde. D.I.. High Solids Coorings. I , No. 2. 13 (1976). (6) U.S. Patent 3,050,480. (7) Graver. R.B.. JOURNAL OF PAINT T~:C'HNOLOGY.~Y. No. 505. 71

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Vol

. 50,

No.

641

, Jun

e 19

78

B.G. BUFKIN and J.R. GRAWE

Table 1 Y . S . Industrial Coatings Sales (Estimated)

Coating System 1974 1975 1980

Solvent-borne ..................... (90.81% (88.7)% (69.3)% Conventional 66.6 63.2 36.4 Conforming 24.2 25.5 32.9

Water-borne . . . . . . . . . . . . . . . . . . . . . . . (6.4) (8.2) (22.6) Electrodeposition 1.4 1.6 2.2 All others 5.0 6.6 20.4

Powder coatings .................... 2.0 2.1 4.7

Radiation curing .................... (0.4) (0.5) ( 1.6) Ultraviolet 0.3 0.4 1.5 Electron beam 0.1 0.1 0. I

are limited to 396 pounds per hour and not to exceed 2970 pounds per day unless such emissions have been reduced by at least 85%.'

In addition to the present trend of complying with more stringent environmental legislation, industry is also recognizing the active role which the enforcing or controlling agencies have assumed. For example, the EPA is broadening its present emphasis to include controls over stationary sources which were estimated to be responsible for 47% of the 29 million tons of hydrocarbons emitted in 1976. Of this 29 million tons, solvent evaporation accounts for approximately 5.5 million tons while surface coatings emissions account for

3.5 million tons. These two processes alone are responsible for 30% of the controllable stationary source hy- d roca rbon~ .~

Besides meeting the challenges required by environmental legislation, industry is also facing product limitation impasses resulting from shortages in raw materials and energy.

The impact that these forces have had on the status of conventional systems and on the development of new generations of industrial coatings is illustrated in Table

These estimates reflect the growing emphasis which is being placed on the development and utilization of conforming high-solids and water-borne systems as the application of conventional systems becomes more re- stricted. Other sources have estimated that water- borne systems will capture 40% of the world-wide industrial market by 1978 and increase to 60% by 1983.'

Recently, however, other changes have developed which may limit the usefulness of the above projec- tions. For example, an EPA policy statement on the use of the concept of photochemical reactivity indicated that solvent substitution was useful only as an interim measure and would not be considered a reduction in organic emissions for purposes of estimating attainment of the ambient air quality standard for oxi- d a n t ~ . ~ Aligned with this policy, recommendations are now being given for new control technology which makes no allowances for solvent substitution.Vn addition, the EPA is presently recommending that only methane, ethane, methyl chloroform, and trichlorotri- fluroethane be exempt from regulation under state im-

Table 2-Properties and Characteristics of Water-Borne Systems

Colloidal Emulaion Dispersion Water-Soluble

Physlcal Appearance opaque transluscent clear Particle size 0.1 to I .Opm 0.01 to O.Ipm <0.001pm Molecular wt. 0.1 to I x 10" 10 to 50 x lo3 5 to 10 x lo3 Viscosity low. independent somewhat dependent viscosity dependent

of molecular wt. on molecular wt. on molecular wt.

Formulation Pigment

dispersability Pigment

stability Viscosity

control

Film formation ability

Performance Solids at

application viscosity

Gloss Resistance

properties Toughness Durability

usually better than others

requires thickeners

may require coalescent

high

lowest excellent

best excellent

good-excellent excellent

pigment dependent pigment dependent

thickened by addition governed by of co-solvent molecular wt. of

polymer good. requires excellent

minimum coalescent

intermediate low

high good-excellent

highest fair-good

intermediate lowest very good-excellent very good


SURVEY OF CROSSLINKING EMULSIONS

Table 3-Performance of Thermoplastic Emulsions in Industrial Applications

Top Coat Primer Exposure Composltlon Composition Location

Exposure to Fallure (Yesn)

Gas storage acrylic inorganic Gulf Coast > 10 tank emulsion zinc

Water tower acrylic acrylic Gulf Coast >Y emulsion emulsion

Chemical acrylic zinc-rich Gulf Coast >I2 storage tank emulsion

Old galvanized acrylic zinc-rich West Virginia >3 steel bldg. emulsion

Chemical styrene-acrylic styrene-acrylic West Virginia >5 storage tank emulsion emulsion

Conc. acid tanks acrylic acrylic Gulf Coast > 12 emulsion emulsion

Caustic tank car acrylic acrylic - 2 2 emulsion emulsion

plementation program^.^ Thus. the utilization of con- Thermoplastic Emulsions forming systems will cease to be a viable option for Emulsion paints were introduced into the coatings meeting governmental regulations, and water-borne market over 30 years ago, and their wide appeal and and higher-solids coatings will be the only choices acceptance has resulted in sales representing 90% of the available for many industrial applications. flat interior trade sales market and 60% of the exterior

trade sales market.Y While these same emulsion systems account for onlv a small percentage of the indus-

Water-Borne Systems

Water-borne systems are usually subdivided into three categories: (I) water-soluble; (2) colloidal dispersions; and (3) emulsiuns. Each of these categories can accommodate a broad spectrum of polymer compositions, and many classes of polymers are amenable toall three categories; both alkyd and acrylic polymers are commercially available in emulsion, dispersion, and water-soluble forms. For a single polymer class, the property differences which exist between these categories are a result of differences in polymer particle size and molecular weight. The properties and characteristics generally displayed by coatings from these three categories are summarized in Table 2.8

trial coatings market:their excellent performance in the area of industrial maintenance coatings can be seen from the data presented in Tables 3 and 4.1°

The above emulsions are being touted to afford "twice the life at half the cost" as compared to industrial alkyd coatings. Yet, in comparison with the better industrial coatings, thermoplastic emulsions lack the tensile strength; abrasion and mar resistance; acid, alkali, and solvent resistance; temperature resistance; and general durability many applications require.

Crosslinkable Emulsions

Fortunately, emulsion systems can be designed to provide the properties required of an industrial coating

Table 4--Chemical Resistance Of Thermoplastlc Latex vs. Epoxy Ester Fllma

Aclyllc Emulslon Epoxy Ester

Age of film 5 days 5 days Motor oil unaffected unaffected Sodium hydroxide. 5% discolored. discolored

slightly soft and lifted

Ammonium hydroxide, 10% unaffected slightly discolored Water unaffected unaffected Sulfuric acid. 20% unaffected discolored, slightly

swollen and lifted Hydrochloric acid, 5% unaffected very soft and lifted Sodium hypochlorite. 5% unaffected discolored Perchloroethylene unaffected fine blistering Methyl ethyl ketone slightly soft fine blistering Xylene unaffected fine blistering,

slightly soft Varsol thinner unaffected blistered and soft

Vol. 50, No. 641, June 1978


Table %Effect of Crosslinking on the Film Properties 01 a Chelating Poly(2-Acetoacetoxypropyl Methacrylate) Ernulslons

Tensile DMF Wstw Croesllnklng Hardneas Mandrel StrengIh Elongation Dwble Blush

Agentb Sward Pencll Flexlblllty (Kglcm3 (%I Rubslmll Time (see.)

None 12 B pass 1%" 33.8 496 70 240 20% Zn ( 0 A c ) ~ 27 F fail 1" 102.1 8 pass 500 2400

hardness=6B

(a) The emulrions were dried for 35 days at ambient cond~tions. (b) Percent metal ion based upon total concentration of chelating group present in polymer.

by introducing functional groups which are capable of forming crosslinks. The increased integrity which crosslinking provides is illustrated in Table 5 which compares the properties of uncrosslinked and ionically crosslinked films of a chelating, poly (2-acetoacetoxypropyl methacrylate) emulsion.ll

While these data are indicative of the general property increases that crosslinking affords, the properties displayed by other crosslinkable systems will depend upon the chemical and physical stability of the crosslinks, the crosslink density, the nature of the curing agent and the weight percent of curing agent required for a specific crosslink density, the physical properties that the curing agent imparts to the system, and the location of the crosslink sites.

Through the proper choice of functional groups, it is possible to control the location of the crosslink sites and produce emulsion systems with homogeneous crosslinking, interfacial crosslinking, interstitial crosslinking, or combinations of these. Homogeneous systems contain crosslink sites which are statistically distributed throughout and between the polymer particles. Interfacial systems contain a preponderance of crosslink sites on the particle surface with a gradient decrease in the number of sites in the direction of the particle core. Interstitial systems are comprised of thermoplastic emulsion particles embedded in a matrix of crosslinked polymer.

Industry is presently investigating all three of these categories in order to develop systems with the integrity needed for the industrial coatings market. While encouraging results have been generated with crosslinkable emulsions from each of these categories, certain applications require a unique balancing of all three modes of crosslinking in order to achieve the properties required for a specific end use. For example, thermosetting vinyl emulsions which are useful as plywood adhesives and binders and which incorporate all three modes of crosslinking have been developed by combining a carboxylic acid and/or hydroxyl- functional emulsion with a water-soluble melamine or urea-formaldehyde resin. The emulsion's hydroxyl functionality usually consists of a mixture composed of from 30% to 40% N-methylolacrylamide and from 60% to 70% 2-hydroxyethyl acrylate. Thus, in this system, homogeneous crosslinking occurs as the reactive methyl01 groups of N-methylolacrylamide condense with the functionality available in the interior of the

particle and at the interface formed by coalesced particles; interfacial crosslinking occurs as the aminoplast resin condenses with the functionality on the particle surface or in the outer shell areas which have become exposed as a result of flow and deformation; interstitial crosslinking occurs as the aminoplast resin, which usually constitutes between 12% and 20% of the total resin solids, condenses with itself.

If the above system is modified so that all of the N-methylolacrylamide is replaced by 2-hydroxyethyl acrylate and if hexakis(methoxymethyI)melamine is used as the sole aminoplast resin, the homogeneous and interstitial methods of crosslinking will be suppressed, and interfacial crosslinking, resulting from a condensation of the melamine resin with the functionality on the particle surface, will become the predominant mode of reaction. Obviously, because of the domain nature of colloidal systems, subtle changes in chemical composition can result in a profound change in the properties associated with the physical, structural, and topo- graphical parameters of these systems.

While current efforts are focused on the development of ambient-curing emulsions which crosslink through autooxidation, or by other means, most of the present commercial systems utilize aminoplast resins to achieve the desired degree of crosslinking. Since these systems require a thermal cure of at least 15 min at 121°C. aminoplast cured emulsions have been limited to such applications as exterior can and container coatings, metal furniture and fixture coatings, automotive parts coatings, coil coatings, certain appliance coatings, wood finishing, and adhesive compositions for plywood.

An additional factor limiting the utilization of aminoplast-cured emulsions is associated with the domain nature of these systems and the possible lack of uniformity in the microstructure of the cured film. Yet. contrasting this concern are data which indicate that the physical properties of aminoplast-cured emulsions are comparable to the properties displayed by composi- tionally similar solvent-borne systems or to systems of other waterpborne ~ategories. '" '~ Typical physical properties of a melamine-cured emulsion which crosslinks predominantly through an interfacial mode are presented in Tables 6 and 7.14

While the replacement of conventional systems with thermosetting emulsions has not occurred without a measure of resistance, in many applications the emul-


SURVEY O F CROSSLINKING EMULSIONS

Table G F l l m Performance of a Melamlne Cured Styrene-Acrylate Emulsion

Baked at 275°F (135°C) and 300°F (149°C)

Curing temperature ("C) ..... lS"l135 Curing agent ............... Cymel 373= Amine promoter . . . . . . . . . . . dimethylethanol

amine Coalescentc ................ PGiTEX Gloss (60120) ............... 97/88 Pencil hardness ............ H MEK dbl. mbs . . . . . . . . . . . . . 100 Mar resistance . . . . . . . . . . . . . good Reverse impact

10130 in. Ib. .............. passlpass Salt sprayd (hr) . . . . . . . . . . . . . 300 Humidity resistanceQ (hr) .... 500

lS"l149 Cymel 303b dimethylethanol

amine PGiTEX YO178 F 100 excellent

passlpass 150 800

la) Percent melamine bascd on resin solid?= 15%. pigment lo bindcr ratio=0.7 with TiO,. (b) Percent melamine bared on resin sol,ds= Im. pigment to bindcr ratro=0.7 with TiOz. lc) 111 blend of ~ r u ~ v l e n e ~ lvco l IPG) and Texanul ITEX). Id) Hours at which amini&m 'A I". creep developed ( r ) Hours at which hlistrring began.

sion systems have been found to provide qualities which could not be attained with products based on conventional coatings. Some of the major advantages which thermosetting emulsions offer as a substitute for solvent-borne systems are:

(1) Equivalent adaptability to conventional paint manufacturing equipment and processes;

(2) Adequate paint stability to heat, shear, chemical contaminants, aging, and freezing;

(3) Broad acceptability to conventional application equipment;

(4) Good adhesion in direct-to-metal applications; ( 5 ) Achievement of high-build coatings without

popping imperfections; (6) Improved flexibility and toughness in compari-

son to alkyd-melamine industrial finishes; (7) Longer term exterior durability resulting from

the high molecular weight of the polymer; (8) Good resistance to chemicals and solvents; (9) Attainment of high gloss coatings with gloss re-

tention in the category required for automotive topcoats;

(10) Energy savings due to reduced oven air flow requirements and the absence of afterburners or incinerators; and

(1 1 ) Exemption from air pollution control^.'^ Obviously, as the technology of crosslinking emul-

sions advances, the advantages which these systems offer in comparison to conventional systems will also increase.

CONVENTIONAL EMULSIONS WHICH PRODUCE HOMOGENEOUSLY CROSSLINKED COATINGS

Homogeneously crosslinked systems require crosslinking sites which are distributed statistically throughout and between the polymer particles; such systems are produced by the conventional emulsion polymerization of monomers which are capable of self-condensation or autooxidization. For example, self-condensable monomers include N-methyl01

Table 7-Exposure Durability For Melamine Cured Acrylic Resin Systems

45" South, Florida Exposure

Duntlon ot Exposure Solvent- Water- Borne Soluble Emulsion

Original gloss (60120) . . . . . . . . . . . . 90171 86/69 89/72 6 months ....................... 80159 85153 76/50 12 months ..................... ,69143 67/39 71/39 I2 months (polished) ............ .93178 82142 89161

(meth)acrylamide, N-(isobutoxymethyl)acrylamide, hydroxymethylated diacetone acrylamide, t-butyl peracrylate, and acryloxyalkylsilanes, while au- tooxidizable monomers include cyclohexenyl acrylate, ally1 acrylate, and vinyl condensation products of drying oils.

If future-generation industrial emulsions are to possess the product characteristics and integrity displayed by the present conventional systems, the functional monomers used to develop the crosslinking emulsion must satisfy the following criteria:

(I) The crosslinking monomer must copolymerize with monomers whose overall characteristics comply with the requirements of the application.

(2) The crosslinking groups of the monomer must be insensitive to free-radical polymerization and the environment of the emulsion.

(3) The conditions required for crosslinking should be.in accord with conventional practices.

(4) The aging characteristics and film integrity of the product must satisfy the application requirements.

Of the functional monomers which meet these requirements, N-methylolacrylamide (N-MA) is presently one of the most commonly employed functional monomers used to develop vinyl-type crosslinking emulsions. The methylol groups of N-MA are insensitive to free-radical polymerization and readily self-condense upon conventional thermal curing. More- over, the crosslinks formed by the condensation of two methylol groups have been found to increase great1 y the thermal stability of the systemx5 as indicated by the activation energies of thermal decomposition presented in Table 8.'"

Table &Thermal Decomposition Activation Energies Of Crosslinked N-Methylolacrylamide/Polymers

Polymer Composltlon Actlvatlon Energy

(Kcal/mole)

100% . Poly(acry1onitrile) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22.2 9515 . AcrylonitrilelN-MA . . . . . . . . . . . . . . . . . . . . . . . . . . . 27.4 90110 . AcrylonitrilelN-MA . . . . . . . . . . . . . . . . . . . . . . . . . .34.3 100% - Poly(viny1 acetate) . . . . . . . . . . . . . . . . . . . . . . . . . . .20.1 9713 . Vinyl acetate1N-MA .......................... .22.6 93fl - Vinyl acetatelN-MA ........................... 26.4 YO110 - Vinyl acetatelN-MA . . . . . . . . . . . . . . . . . . . . . . . . . .31.8

Vol. 50, No. 641, June 1978


Table %Physical Properties of a N-MA-Based Acrylic Emulsion Externally Cured with a Melamine Resin

Pencil hardness" Initial ........................................ H 16 H r water soak @I0O0F ...................... B % Moisture pickup . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1

Impact resistancea (in. Ib) Direct . . . . . . . . . . . . . . . . . . . . . . . . . .... .. . . . . . . . 20 Reverse ...................................... 12

T-benda . . . . . . . . . . . . . . . . . . . . . . . . . . . .. .......... 2-T M E K rubsa ..................................... Passed 100 6 Months Florida exposureh

Initial gloss ................................... 22 Washed gloss ................................ 22.5 % Gloss retention ............................. 100+

Embedded dinc ................................. 8 Chalk resistancec ................................ 10 Tint Retentionc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . None --

(a) Cure condilions: 316°C. high vcloeity oven for 35 aec; PMT 213°C. (h) Curt conditions: 232'C for 4 mrn (c) Rated on a scale of I lo 10 where I ind1cr1c.i failure and I0 indicalrr rnl effect.

The amount of N-MA used in copolymer compositions varies in accordance with the property requirements of the end application. To obtain coatings with acceptable chemical resistance and enhanced physical integrity, typical copolymer formulations employ between 3 and 7 weight percent N-MAs6 with 6.6 mole percent providing the best balance of physical properties.I4' In compositions exceeding 10% by weight N-MA the emulsion viscosity greatly increases, the rate of premature gelation increases, and the crosslinked films become more sensitive to water as a result of the hydrophilic nature of the amide groups.

Although the amount of N-MA may represent only a minor portion of the total copolymer composition at its optimal crosslink density concentration, the property

advantages associated with N-MA-based emulsions include increased tensile ~ t r e n g t h , l ~ - ' ~ impact resis- tan~e,~O. 21 wet and dry abrasion r e ~ i s t a n c e , ~ ~ - ~ ~ peel strength,25 ~ a t e r , ~ ~ - ~ l d e t e r g e r ~ t , ~ ~ . ~ ~ alkali,35* 3%hem- ical r e s i ~ t a n c e , ~ ~ - ' ~ heat r e ~ i s t a n c e , ~ ' - ~ ~ dirt pickup re- ~ i s t a n c e , ~ ~ . 's and g l o ~ s . ~ T o achieve the potential properties associated with efficient crosslinking, N-MA emulsions require curing by means of catalysis or through conventional thermal processes.

Catalysis or Thermal Curing

Several modes of catalysis have been used to promote the crosslinking of N-MA-based emulsions at ambient conditions or at low temperature^.'^-^' For example, a 56/40/2/2-butyl acrylatelvinyl chloride/acrylic acid/N-MA copolymer emulsion produced room temperature cured films which demonstrated a tensile strength of 74 Kg/cmZ, an elangation of440%, and 100% and 300% moduli of 46 Kg/cm2 and 67 Kg/cm2, re- s p e c t i ~ e l y . ~ ~ A vinyl acetate/N-MA emulsion catalyzed with 0.04% ammonium sulfamate produced crosslinked films which were 61% insoluble in water after drying four days at 23OC. The same emulsion cured with Zn(N03)~ produced films which were only 14% insoluble after the same drying period.53

Thermal curing is more efficient than catalyzed curing in achieving the maximum degree of crosslinking, and thermally cured coatings usually display superior physical properties and greater integrity. For example, Kraft paper impregnated with a 64/20/10/3/2/1-ethyl acrylate/vinylidene chloride/butyl acrylate/acrylonitrile/acrylamidelN-MA copolymer emulsion displayed a wet and dry tear strength of 0.71 Kg/cm and 6.97 Kglcm, respectively, after drying 48 hr at room temperature while the same system after curing for five minutes at 13S°C displayed a wet and dry tear strength of 4.1 Kglcm and 8.0 Kglcm, r e ~ p e c t i v e l y . ~ ~

Table 10-Eflect of Polymer Composition on Absorbency and Tensile Strength oi Unwoven Fabricsa

Water Absoaencyr (Sec) Wet Tensile

Strength (din.) Rewet Sink

PdVmer P m l Water Wlpe Perchlorcr Composition Surtactant lnltlal 1 Wash 10 Washings Ratlnga HA ethylene

%I21 1.210.8 EANSIN-MAIAA 95131111 EANSIN-MAIAA !%I212 EAIN-MAIAA

%I212 EAIN-MAIAA

93.512.51212 EAIIAIN-MAIAA

I% Dicapryl Sulfosuccinate <I 2 5 5 <I 4 1-2 5.5 4.8 0.67% Sodium Lauryl sulfate I 2 1 5 < I 3 1 6.0 9.6 0.67% Sodium Lauryl sulfate 315 >600 >300 >300 2300 >300 5 8.3 7.1

0.67% Sodium Lauryl sulfate; I 3 141 141 7300 >300 4 6.1 7.2 5% Dicapryl Sulfosuccinate

0.67% Sodium Lauryl sulfate 395 >600 530 >6M) - - 5 6.8 9.2

(a) Sampler were cured for 3 min a1 I49C. (d) The sample's ability to wtpe up wiltrr was r;&led on a tiale ~cd L l a 5 usng Ih.; lb) EA = ahyl acrylale. VS = a'dlum vinyl sulfonalr. AA = acrylamide. I A = ilaconic eompletenessofthewipc, whrlherafilmdwalcr war left or whether bcadsofwalrrfi~rmrd

acid. on thcsurfacc.ascriteria. A terry cloth IowcI would rank I . i.e..lhr hcal.unbonded ccc~toni~ Ic) Rrwet lime is the ltme required by Ihr nonwoven la become raturald by water Sink ranked 1-2. and if Ihe water is no1 wiped upat all but smeared inloa lhln film the rdnk 15 5

lime is the lime requ~red for the sample lo sink lo the bottom of lest container



The conditions employed for thermal curing vary in accordance with the compositional nature of the emulsion and the application but typically range from one minute at 177°C55 to 30 min at 149°C.56 A 8 1.5/14.3/3.2/ 0.510.5-vinyl acetatelbutyl acrylate1N-MAIdiallyI maleatelitaconic acid copolymer emulsion produced films which were 79% insoluble in 24°C benzene after curing three minutes at 2 7 0 T s 7

Potential Applications

Because of the many advantages and broad formulation latitude offered by N-MA-based emulsions, a variety of potential applications have been investigated for these systems. The more commonly recommended areas of application include fabric ~ o a t i n g s ~ ~ - ~ ~ and b a ~ k i n g s , " ~ . ~ ~ textile finishes,6567 binders,18 and fire- proof c o a ! i n g ~ ; ~ ~ - ~ ' leather coatings72* 73 and substi- t u t e ~ ; ~ ~ paper coating^^^-^' and ink binders;78. 7Y and adhesives for w ~ o d , ~ O - ~ ~ metaIva3 and general use.84.

Protective Coatings

The coatings industry has devoted considerable time and resources to develop N-MA-based emulsions with properties suitable for a broad range of protective coatings applications. And while this effort has produced crosslinking emulsions with properties competitive to those of such systems as water-soluble oil-based and oil-free alkyds,86 the greater acceptance of the latter has limited the protective coatings applications of N-MA-based emulsions mainly tocoil coating markets.

Coatings for coil application find their largest use in building products such as exterior siding, soffits, rain gutters, patio covers, roof decking, and sheathing for mobile homes. For these applications the coating must display excellent adhesion and flexibility, mar and scratch resistance, chemical resistance, and, for top coats, long-term exterior d ~ r a b i l i t y . ~ ~ Presently there are several thermosetting acrylic emulsions commercially available which satisfy these requirements for coil applications. These emulsions normally employ both N-MA and an external aminoplast resin to effect crosslinking and to achieve the balance of properties required in such applications. Table 9 illustrates the typical performance properties of a N-MA- melamine- cured commercial emulsion used for coil coating.88

Protective coatings based upon N-MA emulsions have also been suggested for other applications. For example, coatings useful as reflowable automotive paints, interior can coatings, or anti-friction glass bottle coatings were prepared from a 81.6/9.2/6.7/2.5-methyl methacrylatelbutyl acrylate1N-MAImethacrylic acid copolymer which utilized 1.6% Tritonm X-200 as the emulsification surfactant. The monomers were polymerized in the presence of a nonreactive dibenzyl diethylene glycol adipate polyester which served as a plasticizer. The N-MA-based emulsion was catalyzed with 0.25%, based on total resin solids, of monoethanol amine and mixed with a white tinter to form a paint with

a pigment to binder ratio of 571100. The paint was sprayed ontozinc phosphated steel and cured 30 min at 149°C. The resulting coating displayed a specular gloss of 60 and provided excellent resistance to condensing humidity at 66°C. The coating demonstrated satisfactory sanding with 600 paper and reflow was possible after a 10 hr bake at 60°C. Reflow was inhibited by baking 15 hr at 121°C.8Y

N-MA-based latex paints, which provided improved water and chemical resistance, were prepared from a 75.512012.611.9-methyl methacrylatelethyl acrylatel acrylamide1N-MA copolymer emulsion which was catalyzed with 16.6% Cymela 303 and 16.6% Beetlea 65, urea-formaldehyde resin. The catalyzed emulsion possessed good stability after neutralizing to pH 8 with Et3N and displayed Brookfield viscosities of 125, 130, 130, 135 and 150 cps after 0, 3, 31, 56 and 90 days, respectively. When Beetle 65 was removed and the emulsion contained 33.2% by weight Cymel 303, the catalyzed emulsion became a thick cream after 13 days.YU

N-MA-based paints were formulated from a methyl methacrylatelacrylonitrilelmethyl acrylatelmethacrylic acid1N-MA copolymer emulsion which was neutralized with 2-(dimethylamino)ethanol and blended with a methylated melamine-formaldehyde resin. The composition was applied to cold-roll steel and cured to provide a coating with excellent physical properties and good corrosion resistance. Y '

Strippable coatings with improved resistance to chemicals and water and useful for protecting finished goods during storage and transportation were prepared from a 90/10/3/2/0.5-methyl acrylatel acrylonitrilel methacrylamidel 2-hydroxyethyl methacrylatel N-MA copolymer which utilized 15% by weight polyethylene glycol nonylphenyl ether fumarate and I% by weight ammonium polyoxyethylene alkylether sulfonate as the emulsifier mixture.92

A subbing coating for corona-treated polypropylene film was formulated from a 84181414-ethyl acrylatelacrylonitrilelacrylic acid1N-MA copolymer emulsion which utilized 2.1% sodium lauryl sulfate and 0.7% polyethylene glycol oleyl ether as the emulsifier mixture. The N-MA emulsion provided good heat-seal strength for bonding an acrylate-vinylidene chloride copolymer to polyolefin substrate^.^^

A subbing coating for polyester photographic sup- ports was prepared from a 50/42/310.4/0.09-butadienel styrene1 N-MA1 acrylic acid1 methacrylic acid copolymer emulsion. The emulsion was cured for 10 min at 120°C and provided coatings with improved wet adhesion to photographic emulsions.94

Textile Applications

Besides providing the physical integrity needed in various protective coatings applications, N-MA-based emulsions have also demonstrated excellent potential as binders for nonwoven fabrics. For this application the main requirements of the binder include the ability

Triton is a registered trademark ef the Rohm and Haar Cu

Vol. 50, No. 641, June 1978

Cymel and Beetle are registered trademarks of the American Cyanamtd Co.

47


to provide softness, flexibility, resistance to chlorinated hydrocarbon dry-cleaning fluids, and resistance to laundering. For apparel applications involving skin contact, the product must possess the proper hand, feel, and comfort. Hand and feel are usually associated with the tensile, modulus, and elastic qualities of the fabric, while comfort is associated with heat capacity, water sorption, porosity, and moisture retention. Ob- viously, since the binder requirements are so numerous and sometimes conflicting, the formulations for fabric coatings are usually designed to achieve the best balance of overall properties. Table 10 presents several N-MA-based formulations and illustrates the effect that polymer composition has on various fabric properties.

These data illustrate the primary function of N-MA, which is to provide increased coating integrity and environmental resistance. The property enhancement resulting from the crosslinking ability of N-MA is reflected by the fabric's ability to retain adequate wet tensile strength after 30 min immersion in water or perchloroethylene, and by the fabric's ability to be virtually unaffected after 10 wash cycles in detergent water at 60°C. These data also indicate that N-MA contributes less to the water absorption of nonwoven fabrics than does the type of surfactant which is employed in the f o r m ~ l a t i o n . ~ ~

A variety of other advantages have been reported for fabric binders which utilize N-MA-based emulsions. For example, an adhesive for laminated fabrics which provided solvent resistance and cold flex characteristics was prepared by blending 100 parts of a 92/81 2-butyl acrylatelacrylonitrile1N-MA emulsion with I5 parts of 781151512-ethyl acrylatelacrylic acidlmeth- acrylic acid1N-MA water-soluble resin. An adhesive film of the blend displayed a 187% area increase after a two hour immersion in perchloroethylene, good cold flex at -18'C, a tensile strength of 2.03 psi, and an elongation of 730%. A similar film prepared without the water-soluble resin showed a 314% area increase, a tensile strength of 0.67 psi, and an elongation of 695%.96

An impregnate for cotton, rayon, and polyester- rayon blends which provided increased abrasion resistance and tensile strength was prepared from a ethyl acrylate/acrylonitrile/acrylamide/N-MA copolymer emulsion which was blended with tris (methoxy- methy1)melamine and catalyzed by NH4OH. A cotton fabric impregnated with the mixture and cured 10 min at 150°C yielded a fabric with five times the abrasion resistance of an untreated control f a b r i ~ . ~ '

Coatings for nonwoven fabric-pressed foam laminates which provided good abrasion resistance were prepared by blending a 741201313-ethyl acrylatelrnethyl acrylatelmethacrylic acid1N-MA copolymer emulsion with a nitrocellulose emulsion. The emulsion blend was applied to a laminate consisting of a polyurethane pressed foam and a nylon 66 nonwoven fabric and cured 20 min at 150°C to yield a coating that exhibited no abrasion damage after 250 revolutions in the SATRA abrasion resistance test No. STMlO2 in two test areas.Y8

An adhesive for bonding nonwoven fabrics was prepared by blending three parts of a 94.513.312.2-ethyl

acrylatelvinyl acetatem-MA copolymer emulsion with one part of a 62.3/34.7/2.0/1.0-ethyl acrylatelmethyl acrylatem-MAIitaconic acid copolymer emulsion. The blend was catalyzed with citric acid and impregnated in a rayon nonwoven to yield a fabric with a tensile strength of 9.19 psi after three dry cleanings compared to a tensile strength of 7.0 psi for the same fabric impregnated with the emulsion which did not contain itaconic acid. 99

Solvent and wrinkle-resistant finishes for textiles were prepared from a 371241201151311-vinyl acetate1 ethylenelacrylonitrilelethyl acrylatelN-MAIacrylic acid copolymer. A polyester textile impregnated with the N-MA-based emulsion displayed 94.1% insolubility in trichloroethylene and 86.8" wrinkle resistance compared with 91.9% insolubility and 79.8" wrinkle resistance for a textile impregnated with a 901713-ethyl acrylatelmethyl methacrylate1N-MA copolymer which did not contain acrylic acid as the internal catalyst.'00

In a similar application, a polyester textile impregnated with a 7 11251311-vinyl acetatelethylenem-MA1 acrylic acid copolymer emulsion displayed 92.2% insolubility in Triclene and 85.5" wrinkle resistance as compared to 91.5% insolubility and 80.4" wrinkle resistance for a textile impregnated with a 901713- ethyl acrylatelmethyl methacrylatelN-MA copolymer emulsion.Iol

Binders for impregnated polyester or nylon nonwoven fabrics were prepared from a 9512.512.5-ethyl acrylatel3-butene-l,2,3-tricarboxylic acid1N-MA copolymer emulsion which employed 5% polyethylene glycol octylphenyl ether and 0.5% sodium lauryl sulfate as the surfactant mixture. A Tetoron web immersed in the emulsion and cured five minutes at 140°C gave a nonwoven fabric with a tensile strength of 55.8 g/cm2 and a stiffness of 125 mg compared with a tensile strength of 40.8 glcm2 and a stiffness of 141 mg for a nonwoven fabric bonded with an emulsion which substituted acrylic acid for N-MA and 3-butene - 1,2,3-tricarboxylic acid.lo2

Washfast adhesives for textile laminates were prepared from a 841101313-ethyl acrylatelacrylonitrilel acrylic acid IN-MA copolymer emulsion which was catalyzed with 1.5% oxalic acid. A cashmilon jersey laminated on a nylon taffeta lining using the N- MA-based adhesive displayed a peel strength of 950 gl2.5 cm initially, 540 gl2.5 cm after washing, and 360 gl2.5 cm after dry cleaning. A similar laminate using a 941313-ethyl acrylatelacrylic acidlN-MA emulsion adhesive displayed a peel strength of 700 gl2.5 cm initially, 370gl2.5 cm after washing, and 250gl2.5 cm after dry cleaning.lo3

A fabric coating which provided improved heat resistance was prepared from a 67.512513.7513.75-ethyl acrylatelbutyl acrylatelglycidyl methacrylate1N-MA copolymer emulsion which was blended with a methyl dimethylolcarbamate resin and catalyzed with tartaric acid. A tropical polyester fabric was immersed in the mixture and cured one minute at 150°C to give the impregnate. The heat resistance was determined by dropping heated 1.5g glass balls onto the fabric. The minimum temperature required for causing holes in the



Table 11-Effect of Various Formulation Parameters On Adheslve Properties

01 a 90110 - Vlnyl AcetatelEthylene Emulsion

Adhwlve Psel Sample StrengW Cold-Flow Rate Number Panmeter InvaWgItcd (Ib) Rwlstan&(mm/hr)

None-control Addition 5% polyvinyl

alcohol Lower molecular weight Addition of 1% N-MA Combined parameters of

sample 3 & 4 Combined parameters of

samples 2 & 4 Combined parameters of

samples 2 & 3 Conv. polym. method

plus parameters of samples 2. 3. & 4

Seed polym. method plus parameters of samples 2. 3. & 4

Parameters of samples 9 plus reduced conc. of surfactant

Parameters of sample 9 plus substitution of (NHa)~S208 initiator

la) Adherive slrenglh was measured as the average force required to peel a standard laminate of cotam cloth and vinyl lilm bonded wilh the adhesive.

(hl Rcsinance to cold-flow war measured as the lhrerhold temperature required la cause separation "fa cloth lapjoint made with Ihe adhesive and suspended undera standard force. The hlpher Ihe temperalure. the greater the cold-flow rcnnancc.

tcl Peel was measured as Ihe raleal which two rlripr dr loth laminated with theadhesive were reparaled under a M i 8 pull at bPC. The larger this slandard peel rate. the poorer the peel resistance.

impregnate was 370°C; whereas an untreated fabric displayed a minimum temperature of 27O0C.Io4

Heat sealable fabric adhesives were prepared from a two-stage polymerization process which generated latex particles with a core of poly(viny1 chloride) and a shell consisting of a 90/5.1/2.9/2.0-ethyl acrylatelacryl- onitrilelN-MAlacrylic acid copolymer. The core to shell weight ratio of the emulsion was 45/55. A nylon fabric impregnated with the emulsion and cured at 142"Cgave aproduct withanadhesive strength of 1021g and 12470 after 0 and 16 hr at 85°C. The adhesive strength was reduced to 170-227g after a 16 hr immersion in water at room temperature. The same fabric bonded with an 80120-vinyl chloridelmethyl acrylate emulsion produced a product with an adhesive strength of 0-57g and Og after 0 and 16 hr at 85'C. After a 16 hr immersion in water at room temperature, the adhesive strength of the control remained 0-57g.Io5

Besides serving as binders and adhesives for nonwoven fabrics, N-MA-based emulsions have also been used as conventional and foamed backings for fabrics. For example, a backing for polypropylene or nylon pile carpeting with improved adhesion was prepared from a mixture consisting of four parts of a 7612113-vinyl acetatelethylene1N-MA copolymer emulsion and six parts CaC03. The mixture was applied to a polypropylene tufted pile carpet and cured 10 min at I1WC to give

a laminate with a peel strength of 3.3 Kg. The same carpet backed with a 50150-vinyl acetatelbutyl acrylate copolymer displayed a peel strength of 1.5 Kgzo6

A foam backing for textiles with low-temperature crack resistance, good resilience, and good dry- cleaning fluid resistance was prepared from a mixture consisting of 300 parts of a vinyl acetatelethylenel acrylamide1N-MA copolymer emulsion, 150 parts TiOz, 15 parts of a melamine resin, and 7.2 parts ammonium stearate. The mixture was mechanically blown to generate a foam with a density of 135gil. The foam was coated on the back of a rayon-acetate upholstery fabric, dried to a moisture content of 12%, pressed at 2 ton1871 cm2, and cured for three minutes at 1WC. The resulting laminate did not debond after five launder- ints and had good resistance to cracking at low temp- e r a t u r e ~ . ~ ~ ~

Commercial Uses In addition to protective coatings and textile applica-

tions, N-MA-based emulsions have also found commercial use as wood finishes and adhesives. For example, an adhesive for plywood consisted of 200 parts of a 84.2114.910.9-vinyl acetate1N-MAIacrylic acid copolymer emulsion, I5 parts of a 5% solution of Methocel HG-D.G.S., and 10 parts AICI,*6H20. Plywood, glued with the adhesive, demonstrated a shear strength of 25.2 Kg/cm2 and 18.7 Kglcm2 in cold and hot water tests, respectively.lo8

An adhesive for wood was prepared from a mixture consisting of a 83.3115.711.0-vinyl acetate1N-MA/ acrylic acid copolymer emulsion, a resorcinol-formaldehyde resin, poly(oxyethylene), and Cu (NO&* 9H20. The catalyzed mixture possessed a potlife of % hr. Birchwood sheets bonded with the adhesive demonstrated a shear strength of435 Ib/ i~~.~af ter immersion in boiling water.Io9

An adhesive with improved cold-flow resistance was prepared from a vinyl acetatelethylene1N-MA copolymer emulsion which employed a 88-9% hydrolyzed poly(viny1 alcohol) resin as a protective colloid and adhesion promoter. The latex provided an adhesive strength of 3.0 Kg and a cold-flow resistance of 188°C.110

Because of the competitive nature of adhesive markets, the emulsion compositions most frequently employed in these applications are based either on vinyl

Table 12--Suggested Levels ot Poly(vlnyl alcohol) Required For the Polymerizatlon ot Vlnyl AcetatelN-MA Emulsions

~oly(vIny1 alcohop N-MA Vinyl Acetate % by Wt. of Monomer 46 by Wt. of Monomer %by Wt. ot M o n m

(a) Poly(viny1 alcoholl having a Hoeppler viscosity d I 5 to 25 cps.

Vol. 50. No. 641. June 1978


acetate or their ethylene copolymers with a weight ratio of 9218 to 85115-vinyl acetate to ethylene. These compositions normally include from 1-5% N-MA to reduce cold-flow and increase peel strength since cold-flow can lead to bond failure as the adhesive joint gradually displaces or shifts position, while low resistance to peeling often results in delamination of the adhesive system.

Some of the formulation parameters which influence cold-flow, peel rate, and adhesive strength have been determined for a 8911011-vinyl acetatelethylenelN-MA copolymer. The emulsion parameters investigated were:

(a) Conventional monomer addition; (b) Seed polymerization where N-MA was added in

the later stages of polymerization; (c) Reduced surfactant concentration; (d) Lower molecular weight by means of increased

initiator concentration; (e) Addition of 5% by weight 'poly(viny1 alcohol)

(88-89% hydrolyzed); and (f) The effect of various cations introduced by dif-

ferent persulfate initiators. The results of this study are presented in Table I I.

These data indicate that a synergistic effect exists for a system incorporating the three parameters of the presence of N-MA, the addition of polyvinyl alcohol, and an increase in initiator concentration. The incorpo- ration of two of these parameters with the omission of the third provided no benefit in adhesive strength, cold-flow resistance, or peel rate as compared to the control which was independent of all three of these parameters. The three synergistic parameters were found to be independent of the method of polymerization, reduced level of surfactant, and the initiator cation."' One rationale for this effect could be associated with an increased rate of condensation between the methyl01 groups and the hydroxyl groups of poly(viny1 alcohol) as a result of the increased concentration of sulfate end groups.

Besides enhancing the application properties of adhesive compositions, poly(viny1 alcohol) has also served as the sole emulsifier in the preparation of N-MA-based emulsions. The most useful grades of poly(viny1 alcohol) are those which are hydrolyzed between 80 and 90% and which d i s~ lav a H o e ~ ~ l e r viscosity range of 10-25 centipoise. he amount bipoly(vinyl alcohol) required for effective stabilization of the latex was found to be a function of the N-MA content in the copolymer. Table 12 suggests some starting point relationships for polymerizing varying concentrations of N-MA using poly (vinyl alcohol) as the protective colloid.

The same procedures employed for the polymerization of surfactant-stabilized emulsions can be used for the polymerization of N-MA copolymers which utilize poly(viny1 alcohol) as the emulsifier. A typical procedure which illustrates a delayed addition technique of N-MA is given in Table 13.

The delayed addition of N-MA helps to provide an increased concentration of N-MA in the shell area of the particle thereby enhancing the cohesive strength of

the product. Films of the above 9416-vinyl acetatem- MA emulsion were cured by bakingfor 30 min at 130°C and by adding 3% ammonium p-toluene sulfonate and aging the film for one week at 20°C. The thermally cured sample produced crosslinked films which were 93% insoluble in refluxing acetone and which displayed a swelling ratio of 3.5, while the catalyzed films showed an 80% insolubility in refluxing acetone and a swelling ratio of 5.3.

The swelling ratio is an indication of the efficiency of the cure and is defined as the ratio of swollen to unswol- len volume of afilm after its immersion in a solvent. The swelling ratio is directly proportional to the molecular weight between crosslinks and is inversely proportional to the crosslink density.

For adhesives based on vinyl acetate and N-MA, it is recommended that the swelling ratio not exceed a value of 8 if the product is to provide adequate water, solvent, and creep resistance. While some difference exists in degree of cure attained by the methods previously indicated, the extent of crosslinking as provided by either method of curing is within the range which should afford acceptable overall properties. This fact was substantiated by a practical evaluation of both curing methods. Laminates using the 9416-vinyl acetatelN-MA emulsion were subjected to both curing methods and were found to provide strong adhesive bonds with no cold-flow and with good resistance to water and organic solvents. These results suggest that either method of curing can provide the crosslink density needed in this application.

The delayed addition technique used to prepare the 9416-vinyl acetatem-MA emulsion was also used to prepare a compositional ladder of vinyl acetate1N-MA copolymers containing varying amounts of poly(viny1 alcohol) as the stabilizer. The resulting emulsions were evaluated for their ability to crosslink under thermal and catalyzed conditions. The results from this study are presented in Table 14.

These data provide a further indication of the advantages offered by thermal curing as compared to

Table 13--Poly(vinyl alcohol) Stabilized Polymerization Of a 9416 Vinyl AcetatelN-MA Copolymer

Main Reactor Charge Ingredients Palls

Deionized water ........................................ 70 Poly(viny1 alcohol) (83.5%

hydrolyzed. 4% Hoeppler viscosity of 9.0 cps) ................................... 4

Ammonium persulfate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.3 Vinyl acetate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94.0

Delayed Monomer Addition Deionized water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30 N-MA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 Reaction temperature 78°C.

addition time 2 hr. Characteristics

Solids content . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49.89 Particle size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-2 microns Viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1500 cps

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Stability >3 months



Table 14-meet of N-MA Concentration on the Degree of Crosslinking Cured 30 Min Camlned Fllms

Parcent Percent M I ~ W C 7 D ~ Y S at me

WMeI & Polymer Composltlon Poly(viny1 Resln %Acetone Sweillng %Acetone Swdllng Solvent Ratlo VAIN-MAa alcohol)b Solids lnsolubles Ratlo 1n.olubles Ratio Resistance

10010 ................. 4 55 35 25 36 28 Very poor 9911 ................. 6 56 70 7.5 55 8.0 Good 9812 ................ 10 45 85 5.5 77 7.6 Good 9515 ................. I Complete coagulation of emulsion 9515 ................. 4 53 9 1 4.0 81 6.5 Very good 90110 ................ 3 45 95 2.7 82 5.0 Excellent 84/16 ................ 5 42 98 2.0 90 3.5 Poor water;

Excellent Solvent

la) VA = vinyl acetate. lb) Polylvinyl alcohol) having a Hwppler viscosity of 8 cps and 83% hydrolyzed. lc) Calalyzd films contained 2% by wt. ammonium ptolurne sulfanate.

catalyzed curing. In order to produce films with 85% insolubility and a swelling ratio of about 5, thermally cured films require 2% or more N-MA while catalyzed films required 10% or more N-MA. However, since films containing the 16% level of N-MA were found to be water sensitive, the useful range of N-MA for a proper balance of properties was recommended to be from 2% to 10% by weight of the total composition.

The delayed N-MA addition technique used to prepare the 9416-vinyl acetate1N-MA copolymer emulsion was also used to evaluate other emulsifiers as potential substitutes for poly(viny1 alcohol). The emulsifiers used and the results of the investigation are presented in Table IS.

The limited stability provided by these emulsifiers reflects the disparities which exist between the chemical nature of the above surfactants and the surface characteristics afforded by emulsion particles consisting of N-MA and vinyl acetate. Apparently the hydrophilic surface associated with these systems allows a greater degree of interaction with a hydrated poly(viny1 alcohol) molecule than it does fora molecule possessing lipophilic and ionic moieties.l12

The limited stability associated with certain anionic surfactants can be ameliorated by using a combination of nonionic and anionic surfactants t o effect the polymerization. For example, a 82.5/14.5/2.910.1-vinyl

Surfactant

Table 15-Emulslon Polymerization Of 9416 - Vinyl AcetateIN-MA Copolymer

Using 4% Conventional Surfactants

Time Required for Complete Coegulatlon (min)

Sodium dioctyl sulfosuccinate .................. 115 Sodium lauryl sulfate .......................... 205 Sodium dodecylbenzene sulfonate . . . . . . . . . . . . . . . 130 Ctz-Cl, Straight-chain sodium sulfonate .......... 170 Castor oil sodium sulfate ....................... 40 Corn starch ................................... 45 Gum arabic ................................... 135 Hydroxyethyl cellulose ........................ 75

acetatelbutyl acrylatelN-MAldiallyI maleate copolymer emulsion was prepared by using a surfactant combination consisting of 6.5% Triton X-405 and 1% di-n-hexyl ester of sodium sulfosuccinic acid (Aerosol@ MA 80). The resulting latex displayed a solids content of 52%, a pH of 5.0, and a viscosity of 800 cps at 24°C. The latex was catalyzed with 1% by weight of emulsion solids orthophosphoric acid, and films of the catalyzed latex were cured by aging at room temperature for four hours and bv thermallv curinefor 20 min at 132OC. After a 16-18 hr iknersion in 24"Cbenzene, the film aged at room temperature retained 46.8% of its initial weight while the thermally cured film retained 91% of its initial weight.

The Triton X-4OS/Aerosol MA 80 combination was also used to prepare a 86.5110/310.5-vinyl acetaten- ethylhexyl acrylateM-MAldiallyl maleate copolymer emulsion. This latex possessed a solids content of 49.1%, a p H of 3.2, and aviscosity of 550 cps at 24'C. A portion of the latex was catalyzed with 1% by weight of emulsion solids phosphoric acid, and films of the catalyzed and uncatalyzed latex were dried both at room temperature and at 132OC for 20 min. After curing, the percent insolubles were determined by immersing the films for 16-18 hrin 24°C benzene. The results of this test are given in Table 16.

These results indicate that N-MA systems require a combination of catalyzed and thermal curing in order to attain the degree of crosslinkinginherent in the system.

Aerosol is a registered trademark of the American Cyanamid Co.

Table I b E t f e c t of Catalysis On Ambient Cured and Baked Films of N-MA

Catalyst Cure Schedule %Benzene lnsolubles

None 4 hr at ambient None 20 min at 132°C 1% H3POe 4 hr at ambient I% H~POI 20 min at 132°C

Vol. 50, No. 641, June 1978


Table 17-Emulslon Polymerization Of 9515 - Ethyl AcrylatelKMA Copolymer

Pfocsdure Pa* by Weight Main Reactor Charae

Aerosol 501 (50%) ..................................... 8.8 Aerosol A- 103 (34%) ................................... 4.7 Methanol ............................................ 30.0 Sodium bicarbonate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.0 Ammonium persulfate .................................. 6.0 Water .............................................. 340.2

Pre-Emulsion Mixture Aerosol 501 (50%) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.8 Aerosol A- 103 (34%) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.7 Methanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30.0 Sodium metabisulfite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.2 Water .............................................. 160.0 Ethyl acrylate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 570.0

Delayed Monomer Addition N-Methylolacrylamide (60%) . . . . . . . . . . . . . . . . . . . . . . . . . . . 50.0 Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30.0

Characteristics % Surfactant based on latex solids % Solids pH Viscosity Particle size % Coagulum Shear stability

Film clarity Film clarity after baking 10 min at 177°C

2% 50% 6.4 1000- 1 150 cps 1500-3200 A" >90% 10.10 no creaaing after 10 min. mixing in Waring blender clear and continuous clear, no yellowing observed

In addition to using a combination of nonionic and anionic surfactants, N-MA-based emulsions have also been prepared by using a nonionic mixture of surfactants. For example, a 88.25/10.5/1.0/0.25-vinyl acetatelethylene1N-MAIdiallyl maleate copolymer emulsion was prepared at 60.2% solids and at a viscosity of 1050 cps by using 5.7% Triton X-405 and 1% Pluronic" F68 (a block copolymer of ethylene and propylene oxides having apolyoxypropylene molecular weight of 1,500-1,800 and 80% of the molecule being polyoxyethylene). Films of this latex were found to be 76.4% insoluble in 24°C benzene after curing three minutes at 132'C. An equivalent latex which omitted the 1% N-MA was found to display only 8 to 9% insolubles after the same treatment.

These emulsions were recommended as being useful binders for nonwoven fabrics, as sizes for textiles, and as coatings for wood paneling app1 i~a t ions . l~~

A 75.6/19/4.9/0.5-butyl acrylatelacrylonitrile/N-MA1 itaconic acid copolymer emulsion was prepared using 7.1% Triton X-405 as the only emulsifying agent. The resulting polymer displayed a glass transition temperature of -20°C, an intrinsic viscosity of 2.56, and was found to produce films which were 98.4% insoluble in perchloroethylene after baking for five minutes at llO°C. This emulsion was claimed to be useful as an

Pluronic i s a regstered trademark of the Wyandotle Chemicals Curp

adhesive for anchoring flock to fabric substrates or as a paste for the dying and printing of textiles.'14

N-MA emulsions which utilize all nonionic surfactants have also demonstrated superior physical characteristics in foamed coatings applications. For example, when Triton X-405 was employed as the surfactant for the polymerization of a 85.711 1/2/1/0.3-ethyl acrylatel acrylonitrileIN-MAImethacrylic acidlitaconic acid copolymer, the resulting emulsion was found to possess all of the processing and end-use properties needed for an acceptable product. However, when other surfactants were utilized to polymerize the same composition, the resulting emulsions were found to possess a variety of processing deficiencies. Alkyl sulfates produced foams with poor rolling bank, crushing characteristics, and some surface cracking. Alkylaryl sulfates did not afford satisfactory cell structure while alkylaryl polyester sulfates produced poor cell structure and foam collapse. The phosphate esters of ethylene oxide adducts of nonylphenol were found to generate up to 25% coagulum during the p o l y m e r i z a t i ~ n . ~ ~ ,

In addition to these examples, other surfactant systems which have produced stable N-MA-based emulsions include sodium lauryl sulfate-co-poly(viny1 al- ~ o h o l ) , l ' ~ dioctyl sulfosuccinate-co-ethylene oxide C8.1s-p-alkylphenyl condensates,l18 disodium sulfosuccinate half-esters of Alfonic" 1012-60 (ethoxylated CIO-12 alcohols)-co-polyethylene-glycol mono(nony1- phenyl)ether (Surfonic N-95),llg and iso-Bu3C6H2- ( O C H Z C H Z ) ~ O S ~ ~ N ~ . ~ ~ ~ Since N-MA usually com- prises less than 10% of the total monomer composition, the choice of surfactants is usually predicated upon the HLB requirements of major constituents comprising the polymer composition.

While N-MA can be polymerized with a broad spectrum of comonomers producing thermosetting systems with a wide range of physical properties, the aforemen- tioned applications have limited the reported compositions mainly to include vinyl acetate,lzl. l Z 2 ethyl acrylate, methyl methacrylate,lZ3 butyl acrylate,lZ4. lZ5

styrene,Iz6, lZ7 a ~ r y l o n i t r i l e , ~ ~ ~ vinyl c h l ~ r i d e , ~ ~ ~ - ' ~ ~ and small amounts of hydroxyalkyl acrylate with methacrylic acid.133

Some of the more common initiation systems which have been used to polymerize N-MA-based emulsions include the conventional ammonium persulfate- KzSz08-FeS04 redox ~ o m b i n a t i o n , ' ~ ~ HPOZ-FeSO4 system,135 and ascorbic acid-KzSz08-FeS04 combinations. 136

N-MA has been found to be both kinetically and thermodynamically suited to emulsion polymerization producing latices with high yields and with enhanced shear and freeze-thaw stability. 137

The storage stability of N-MA-based emulsions can be extended by adjusting the pH of the latex from about 8.5 to about 9.5 with ammonium hydroxide138 or by adding such agents as N H z O H . ~ W Z H ~ , trimethyl- enediamine, ethylenediamine,13%r a-aminocarboxylic acids.140

Alfonic in a rrsrtered trademark of the C'cmtinental Oil Co



Table 18--Physical Properties Of a 93.416.6 Ethyl AcrylatelN-MA Copolymer Emulsion

Cast from Latex and Solution

Cast From Cast From Propeq Latex Solution

Gas permeability (CM2S-'atm-') 2.01 x I@R 2.65 x Diffusion coefficient (CMxS') 1.3 x iW7 2.1 x lo-' Water absorption (% swelling) 18% 200% Tensile strength 50 Kg/cm2 20 Kg/cm2 Elongation 320% 500%

While polymerization techniques, such as (1) the emulsified monomer-feed process, (2) the monomer- feed process, (3) the monomer-seed process, and (4) the single-feed process, have been used to produce N-MA-based emulsions with identical overall composition but with microstructures of markedly different na- t u r e ~ , ~ ~ one of the most commonly employed techniques for the polymerization of N-MA involves a combination of pre-emulsion and delayed monomer addition techniques. Table 17 illustrates a starting point formulation for the emulsion polymerization of N-MA which employs both techniques.I4l

Polymerization techniques employing a delayed addition of N-MA help to provide an increased concentration of crosslinking sites on or near the particle surface thereby insuring a greater degree of cohesive energy density between coalesced particles and greater product integrity. While shell enrichment with N-MA provides products with greater crosslink densities per mole of functional monomer, recent studies have shown that delayed monomer addition techniques may serve only to augment the natural tendency of water- soluble monomers to concentrate at the particle-water interface. Water-soluble monomers such as acrylic acid are partitioned between the organic and aqueous phases prior to polymer particle formation and tend to concentrate in the shell area of the particle as the monomer swollen micelles are converted into polymer p a r t i ~ 1 e s . l ~ ~ While the partitioning effect between phases may not be as great for N-MA as it is for acrylic acid, the water solubility displayed by N-MA is suf- ficient to promote the formation of polymer particles with an enriched shell of methylol crosslinking groups. The existence of such a heterogeneous distribution of crosslinking sites has been supported by infrared absorption data, electron micrograph and tensile strength data, and crosslink density measurements.

Crosslink density was inferred from gel fraction determinations and network chain length measurements conducted on a series of ethyl acrylate copolymers containing 2.6,6.6,8.7, and 12.0 mole percent N-MA, respectively. These determinations indicated that a four-fold increase (from 2.6 to 12 mole percent) in functional group concentration resulted in a 17-fold increase in the degree of crosslinking. In a homogeneously dis- persed system the crosslink density is directly proportional to the concentration of functional groups, and a four-fold increase in functional group concentration should result in a four-fold increase in the degree of crosslinking.

A second indication of a heterogeneous distribution of crosslinking sites was provided by infrared spectroscopy. In comparison to solution cast films derived from dissolved latex polymer, films cast from latex displayed an increase in the number of hydroxyl and amide groups linked by intermolecular hydrogen bonds. Since both films contained the same concentration of functional groups, the increased amount of intermolecular hydrogen bonding was attributed to localization of functional groups in the shell area of the particle.

A third indication of a particle shell with an enriched concentration of methylol groups was provided by tensile strength data which were augmented by electron microscopy. Thermally cured latex films containing 2.6, 6.6, and 8.7 mole percent N-MA demonstrated a loss in tensile strength as compared with their ambient cured counterparts. For example, thermally cured films containing 6.6 mole percent N-MA produced a tensile strength of about 51 Kg/cm2 while the analogous ambient cured film produced a tensile strength of about 67 Kg/cm2. Electron micrographs showed that ambient cured films retained their hexagonal packed structure, thereby allowing particle surface to surface contact; thermally cured films lost the particle toparticle surface boundary and produced structureless films. The loss of the interfacial boundary, with the subsequent loss of tensile strength upon thermal curing, reflects the importance of interparticle interactions in systems which possess a shell region with an enriched concentration of crosslinking groups.

As a result of the greater crosslink density at the particle to particle surface boundary, films cast from latex medium were found to possess better physical properties than those cast from a solution of the dissolved latex. Table 18 compares the properties of a solvent cast film with those of a latex film for the 6.6 mole percent N-MA copolymer.

Within the compositional range evaluated in this investigation, the copolymer containing 6.6 mole percent N-MA demonstrated the best balance of physical properties. For example, the copolymer containing 6.6 mole percent N-MA displayed a water absorption of 18% while 0 mole percent [poly(ethyl acrylate)] and 2.6 mole percent N-MA copolymers displayed water ab- sorptions of 190% and 125%, r e~pec t ive ly . '~~ Concen- trations of N-MA above 6.6 mole percent showed further increases in water ~ensi t iv i ty . '~~. 145

N-MA-based emulsions have also been modified by the addition of external curing agents, such a s melamine resin^,'^"^^^ urea-formaldehyde resins,lo4 phenol-formaldehyde water-dispersible epoxy resins,1s0. 15' polyisocyanates,'~ polyacrylic acid,51 and A I C h 81. lo8. "7

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84: 1836111. (120) Anrdt, P.J., et al., German Patent 2,402,494; Chem. Absfr.

84:5849c. (121) BordenChemical,Inc.,French Patent2,157,03l;Chem. Abstr.

79: 147001~. (122) Stehle, P.F. and Dickstein, J., U.S. Patent 3,730,933; Chem.

Abstr. 79:6147f. (123) Aigner, H. and Lehmann, J., German Patent 2,434,382; Chem.

Abstr. 84: 136870a. (124) Weitzel, E.W. and Hamby, C.H.. French Patent 1.4%,878;

Chem. Abstr. 69:44534f. (125) Mikoflavy, B.K. and Knechtges, D.P. German Patent

2,145,495; Chem. Abstr. 72:35227w. (126) Taniguchi, H., Japanese Patent 70 34.029; Chem. Abstr.

75399289~. (127) Kulagina, T.G., et al., Sin. Vysokomolekul Soedin., 9, (1972);

Chem. Abstr. 79:5692t. (128) Endrenyl, F., U.S. Patent 3,616,136. (129) Terada, S. and Yamada, K., Japanese Patent 71 33,573; Chem.

Abstr. 76:60473k. (130) Terada, S. and Yamada, K., Japanese Patent 71 04,834; Chem.

Abstr. 76:453 Ir. (131) Terada, S. and Yamada, K., Japanese Patent71 04,831; Chem.

Abstr. 76:4533t. (132) Terada. S. and Yamada, K., Japanese Patent 71 04,832; Chem.

Absrr. 76:4534u. (133) Suetsugu, M. and Kishida. K., Japanese Patent 70 08,553;

Chem. Abstr. 733572%. (134) Lindemann, M.K. and Volpe, R.P., U.S. Patent 3,345,318;

Chem. Abstr. 67: 109570~. (135) Nashiki, H., et al.. Japanese Patent 68 00.626; Chem. Abstr.

69: 11480g. (136) Brunold, M., et al., German Patent 2,420,212; Chem. Abstr.

84: 19365d. (137) Eliseeva, V.I., et al., Lakokrasochnye Materialy i ikh

Primenenie, I , 1 1 (1%8); Chem. Abstr. 69: 11465f. (138) Wax, L.W., U.S. Patent 3,740.357, Chem. Absrr. 7954638~. (139) Uchida, I., et al., Japanese Patent 76 01,737; Chem. Abstr.

85:65110k. (140) Plettner, W., French Patent 2,005,407; Chem. Abstr.

73: 15794. (141) American Cyanamid Co.. Technical Bulletin. 1976. (142) Muroi, S., J. Appl. Polymer Sci., 10, 713 (1966). (143) Eliseeva, V.I., Br. Polymer J., 7, No. 1, 33 (1975); Chem.

Abstr. 84:60397d. (144) Eliseeva, V.I. and Pinskaya, I.S., Vysokomolekul Soedin. 12,

No. 9, 1%2 (1970); Chem. Abstr. 74: 13713n. (145) Eliseeva, V.I., et al., Vysokomolekul Soedin., Ser. A, IS. No.

9. I931 (1973); Chem. Abstr. 803714981, (146) Horiguchi, S., et al., Japanese Patent 75 24.382, Chem. Abstr.

83:60411h. (147) Huber, H. and Schaefer, P., German Patent 2,504,514; Chem.

Abstr. 84:643%. (148) Yura, M., et al., Japanese Patent 71 41.457; Chem. Abstr.

77:10271 Iq. (149) Feldman, H.D. and Fleischfresser, B.E., British Patent

1,361,243; Chem. Abstr. 83: 116878k. (150) Pinskaya, I.S. and Eliseeva, V.I.. Probl. Sin., Issled. Svoistv

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Abstr. 84: 165687b.

Vol. 50, No. 641, June 1978

Dynamics of Roll Spatter and Tracking Part Ill: Importance of Extensional Viscosities

J. Edward Glass Union Carbide Corporation*

Interior paints thickened with different molecular weights of either acrylamide/acrylic acid copolymers (PAMC) or ethylene oxide homopolymers (PEO) were formulated for roll application studies. Both water-soluble polymertypes have been reported to exhibit high extensional viscosities at low solution concentrations. Paints formulated to Stormer viscosities of 120 and 90 KU gave filaments with high apparent extensional viscosities. Differences between the shear deformational responses of these paints and formulations thickened with other water-soluble polymers prepared from the same grind were not evident. On rollout, the paints with high apparent uniaxial extensional viscosities (q) exhibited extremely large ribs and associated tracking patterns and either extremely stable roll fibers or a high degree of spatter.

Ribbing is the precursor of tracking, i.e., surface irregularities in roll-applied coatings. The sizes of the rib structures leading to tracking patterns are related to the formulation's extensional viscosity, and the ribs are capable of growing, with increasing roller velocities, to mag- nitudes comparable with the roll'sdiameter. In addition to the striations generated by such ribs, tracking patterns are complicated by partial substrate-connected filaments which fall back upon the coated surface, with the dissipation of extended roll fibers.

Newtonian fluids exhibit ribbing and fiber stability. However, as noted in investigations of paints with comparable q and in formulations containing mixed thickener combinations, elasticity can be important in roll application performance. The contribution of a purely elastic effect appears to be dependent upon the magnitude of the paint's q and the roll's application velocity. Elasticity contributes directly10 a broad distribution of spatter drop sizes when high q filaments dissipate via a ductile failure mechanism and indirectly through statjlization of droplet-thread networks as the filament's decreases. Spatter, i.e., roll fiber dissipation, is observed to occur via capillaryforce, ductilefailure, and hybrid combinations of these two primary mechanisms.

Using differential techniques, equations for the rates of extension are derived for roll application conditions. The

Resented ~n part at the 54th Annual Meeting of the Federation af Societies for Coatings Technology in Washington. D.C.. October 29. 1976.

'Chemncalsand Plastics. Researchand Development Dept..S. Charleston. W.Va. 25303.

rates of extension (i) at a constant roll velocity are inversely related to the filament's length. At typical trade application rates, i.e., 13ftlsec, i is predicted tovary from 360 to 20 sec-' for filament lengths of 0.2 to 2 in. (observed in flow visualization studies). In the paint filaments examined apparent uniaxial extensional viscosities were not obtainable over the total predicted application e. Some of the complexities associated with measurement of non-steadv state. "verv amarent uniaxial extensional viscositie$' are djscusied.'~he data are presented on a comparative basis to impress upon the paintchemistoren- gineer that extensional deformations and flows are important in understanding coating performance in roll applications.

INTRODUCTION The shear deformational responses o f seven commercial latex trade paints were examined i n Part I' of this series. The study was not successful i n relating any shear response parameter with roll spatter or tracking. Over the past several decades a similar lack o f success has also been observed i n relating shear deformational parameters with the flow behavior of bulk polymers during processing. I n two process areas, e.g., the spinning of textile fibers and the blow-molding fabrication of polymers, extensional v i sc~s i t i es~-~ have proven useful in predicting the behavior of materials.

Flow visualization studies, via high speed (ca. 2,000 frameslsec) cinematography, of roll-applied commercial paints suggested that the deformational stresses associated with tracking or spatter are extensional in nature. However, extensional stresses i n the commercial paints could not be measured, due i n part to the nature of paint filaments and i n part to the complexities of the measurements. Therefore, experimental paints were formulated with water-soluble polymers previously noted to exhibit high extensional stresses, to as- certain whether extensional responses could be measured i n paint filaments and, if so, to assess the effect of extensional viscosities on coating performance in roll applications. The results are discussed in this article.

56 Journal of CoatingsTechnology

DYNAMICS OF ROLL SPATTER AND TRACKING

Figure I--Spinning-flber apparatus with laser sensing device for extensional vlscosity measurements

EXPERIMENTAL

The general experimental techniques and materials employed in this study are described in the preceding parts's6 of this series. The water-borne latex paints in- ;estigated were based almost exclusively upon interior formulation. I-1212.7The thickeners examined in detail were a series of partially hydrolyzed acrylamidelacrylic acid copolymers (Pushera 500,700 and 1000) with approximate weight-average molecular weights (M,) of 2.5,6.0, and 11.0 x lo6 and a series of ethylene oxide polymers (Polyox@ WSR-301, WSRN-3000 and WSRN-750) with approximate M, of 3.0 and 4.0 x lo5 and 4.0 x lo6.

Paint filament extensional responses were investi- eated via the s~innine-fiber t e c h n i a ~ e . ~ - ' ~ Paint filaments were extruded &rough an orifice (0.05 in. diameter) at the end of afloating arm fitted with an adjustable counterbalancing system. A takeup wheel extended the filaments. The force on the filament was measured by either a laser-beam deflection technique for filaments with weak responses (Figure I) or with apressure trans- ducer (UniMeasure 80)lohmmeter (Hewlett Packard 3490A Multimeter) modification to the floating arm. Weight-displacement calibrations, including the gravitational constant, for both sensing techniques permitted the calculation of tensile forces for the filaments in extension. Ten filaments per paint were measured and the results averaged.

In addition to the tensileforce (F), the mass flow rate, Q, and density, p , of the paint,.a series of radii (r,, rl, r, . . . r,) as a function of displacement distance (z,, z,, z, . . . z,,) are required for each fiber. The radius-

Pusher~sarepisteredtrademarkofthe Dow Chemical Co. Polyoxisa registered trademark of the Union Carbide Corn.

distance data were obtained via comparator measurements from photographs of the fibers in extension. With these data the axial stress at position n, (a,,)., was calculated via equation (1).

The axial velocity at position n, V,, is given by equation (2)

V" = Q nPn (2)

from which the rate of extension at position n,@) , i s approximated from equation (3).

where Az (=z ,,+,, - z,,-,J is twice the spacing between two adjacent positions. The rate of extension will be symbolized as in this report. The-apparent uniaxial extensional viscosity in position n, r), is approximated by equation (4).

Figure %Apparent uniaxial extensional viscosity dependence on rate of extension tor interior (1-1212) paints (120 KU) containing vinyl la cry!^ latex. Thickener: 0, acrylic acidlethyl acrylate copolymer, M, unknown; A, acrylamidelactylic acid copolymer, 8, = 6 x 106; 0, poiy(ethylene oxide), M, = 4 x

10'

Vol. 50, No. 641, June 1978

J.E. GLASS

Figure 3--Rlb and fiber develqvment in high extensional viscosity 1-1212 palnts, 120 KU. Horizontal rollouts, -37 Wsec. Thickener: acrylamide/acrylic acld copolymer (PAMC),

M, = 6.0 x 1W

Figure 4--Rib and fiber development in high extensional viscosity, 1-1212 paint, 120 KU. Horizontal rollouts, -37 ftls~c. Thickener:

poly(ethy1ene oxide) (PEO), M, = 4 x 106



SHEAR RATE,^^^'

Figure -hear rate dependence of steady state viscosity, 1-1212 paint containing vinyl/ac_ryiic latex. Thickener: 0, mod- ifled acrylic copolymer (MAP), Mw unknown, but presumed low based on amount required (Table 2) to thicken formulation to 90 KU;O, HEC,m, = 3 x 105,gKU; 0, PAMC,M- = 110 x lo5, 95

KU; 0, PEO, M, = 40 x lo5, 90 KU

The equations cited result from several assumptions made to simplify the mathematics and reduce the number of variables. Many of the assumptions, e.g., neglecting surface tension effects, may not be valid with respect to the materials examined in this study. Some of the difficulties in analyzing afiber in extension are discussed in the text of this report; the reader is referred to the references cited8-12~40 for more detailed discussions. Other techniques, i.e., tubeless syphon,13 capillary streamline,14 or triple jet,I5 for studying the extensional flows of low viscosity liquids do not appear to resolve most of the difficulties and limitations noted in application of the spinning-fiber technique to paint filament analysis. The data and observations recorded in this article are made on a comparative basis to impress upon the paint chemist or engineer that extensional deformations and flows are responsible for the behavior of coatings applied by roll application.

RESULTS AND DISCUSSION

Shear viscosities (reported in Parts I' and 116) are associated with the stresses required to slide one plane of fluid past an adjacent, parallel plane of fluid, and the stress levels are determined primarily by the recent deformation-history of the fluid. An extensional v i s~os i ty~-~ (7) differs from a shear viscosity in that it is associated with the stress required to increase a nor- malized distance between two material entities in the same plane, and the stresses are dependent upon the fluid's more distant past deformational histories.I3 Of-

ten, these differences reflect themselves dramatically. For example, polymeric materials decrease in viscosity with an increase in the rate of shear, but many increase in viscosity when the deformation rate increase is extensional in nature.

The dominant role of thickener molecular weight over latex median particle size, formulation total volume solids, etc. in roll spatter is easy to visualize with the extensional viscosity concept. If the distance between two entities associated either by chemical bonds or through macromolecular entanglements is increased, the resistance to the stretching force will be greater than the response to stretching forces in systems where the resisting forces will be purely physical in nature (e.g., systems increasing in total volume solids, undergoing minor formulation changes, etc.). It also follows that as the conformation in solution stiff- ens, for a series of thickeners, e.g., PEO to PAMC to PAAC to HEC, due to a changing ionic charge density in the backbone or to conformational rigidity inherent in its chemical structure, the resistance to stretching will decrease due to less entanglements. Within a given chemical family of thickeners, the same effect would be evident with decreasing thickener molecular eight.^

I I 5 0 6 0 70 W) 90

RATE OF EXTENSION.S~C-~

Figure &Apparent uniaxial extensional viscosity dependence on rate of extension for 1-1212 paints, 90 KU. Thick- ener: PAMC;O, mK= 11 x lo6; A, Mw = 6 x lo6; 0, &= 2.5 x lo6; 0, PEO, I, = 4 x lo6. The apparent extensional viscosities of paints thickened with lower Mw PEO could not be measured under the experimental conditions em-

ployed

Vol. 50, No. 641, June 1978

J.E. GLASS

Two factors impeded the measurement of tensile forces in the commercial latex trade paints1 studies:

(I) The predominant thickener in all of the formulations was hvdroxvethvl cellulose. a conformationallv < . . rigid polymer in aqueous solutions and the thickener; were intermediate to low in weight average molecular weight (M,).

(2) The spinning f&er technique lacks the sensitivity to measure the low q of such paints. Therefore. to assess the significance of extensional viscosities on roll coating performance, experimental paints were formulated with two different high molecular weight, water-soluble polymers, i.e., acrylamidel acrylic acid copolymer (PAMC) and poly(ethylene oxide) (PEO), previously noted to exhibit extensional stresses in solution with a number of measuring technique^.^-'^. 14-17

Extensional Viscosities And Roll Performance

To ensure a tensile force response in paint filaments, high Stormer viscosity (120 KU) formulations were prepared with PAMC and with PEO as thickener. Ten- sile forces were recorded in each paint filament; the related apparent uniaxial extensional viscosities (7) are illustrated in Figure 2. The q are high, e.g., lo4 poise, and the coatings on rollout exhibit very large rib structures and very stable fibers (Figures 3 and 4). Perpendicular protrudingfilaments were noted (Figure 4, arrows), presumably arising from extensional stress hardening behavior due to high rates of extension early in the fiber's growth. The paints required a strong arm and stable substrates for application, although nothing unique in their shear viscosity responses (Figure 5) was noted. Spatter was not observed at an application speed of 1 ftlsec; the fibers were too stable. Only strings of paints appear on the spatter charts and these occur as the roller is withdrawn from the wallboard. As an after- thought, the acrylic acidlethyl acrylate copolymer (PAAC), noted to impart heavy spatter in both exterior and interior formulations." was studied in interior for-

Table 1-Roll Application High Extensional Viscosity Thickener Study: Interior 1-1212 Formulation

Stormer Cone., KU,

Thickener w l % ca. 24 hr -

Type M. (XIW) - PAMC . . . . . . . . l I0 0.3 1 9 ja

60 0.68 I ISa 0.32 9Xa

25 0.34 9Ba

la) On rlandlng patntr form gelallnous mrlnx. must be $ticred vigon,ualy befitre manwru- men!.

-

PAMC Mw=1l X106 7

PAMC

PAMC Flgure 7--Influence of PAMC M,., on flber development, 1-1212

paints, 90 KU. Vertical rollouts, -2 Wsec.

mulations thickened to 120 and 90 KU. La rge7 were noted with the 120 KU formulation (Figure 2) but not with the 90 KU paint. In other studies. tensile forces were not observed in paint fibers thickened to 120 K_U with hydroxyethyl cellulose, even the 1.5 x 106M, polymer. Due primarily to the unexpected production of very stable roll fibers which would not spatter in the PEO and PAMC thickened paints, subsequent studies examined formulations thickened to a lower Stormer viscosity. 90 KU.

In the lower viscosity formulations, a series of variable M, PAMC and PEO products were examined. The amount of each thickener required to obtain a given Stormer viscosity paint are recorded in T(ible I . Tensile forces were recorded with all three PAMCs. which did not vary over a broad M, range; the respective q are illustrated in Figure 6 . Fiber stabilities correlating with the q differences are observed (Fi~qurc, 7) and the stabilities complicate the spatter patterns noted after one (Figure 8) and three (Figure, 9) continuous applications to a vertical wallboard. With three continuous applications, the ropiness (due to withdrawal of the roller from the substrate) decreases-This suggests a lowering of the fiber's stability (and q ) through degradation of the thickener's highest molecular weight components. To properly assess this effect. particularly with respect to



Figure 1-1212

! a-Sp palnts,

atter dependent ,90 KU. Vertical

at -2 Wsec.

ce on rollo

re %Spatter depe~ 2 paints, 90 KU.

passes at -

~dence 01 Vertical

-2 Wsec.

n PAMC M rollouts,

c Pw, pass

comparative studies with other thickeners, the percentage of higher molecular weight fractions in each product should be known, rather than a general weight average.

In the PEO thickened paints a tensile f o r c e i s recorded only with the highest molecular weight (M,) polymer; Lhe two remaining PLOs are significantly lower in M, than the lowest M, PAMC. The PEO thickener with M, > 10" like its PAMC equivalents, imparts a subs tanal tensile force to the 90 KU paint fiber (Figure 6, as 7) and roller fibers with oustanding stabilities (Figure 10) are observed. A decrease in the ropiness of the paint with continuous application also is

evident (Figure 11 vs. 12). In viewing the results (Fig- ure 2-12) 4 total, qualitativ~relationships between thickener M,, paint filament 7, and roll coating performance are observed.

The Quantitative Problem: Simulating Roll Application Conditions And Complexities in 7 Measurements

As a simple, comparative spatter test, free-fall experiments from a capillary orifice might appear as an expe- dient method for predicting relative performance. For example, formulations thickened with PAAC form extended fibers in such experiments (Figure 13a) and

Val. 50, No. 641, June 1978

impart significant spatter to both interior and exterior form~lat ions .~ However, with other thickeners in the same formulations. the general observation (Figure 13b) is droplet formation, whether the thickener is a heavy spatter inducing polymer. i.e., high M,PEO. or a negligible contributor, i.e., intermediate M, HEC. Thus. this simplistic approach does not correlate with performance. A stretching force must be exerted on the fiber to obtain filament behavior approximating application performance. and when viewed theoretically, it becomes apparent that the viscosity response over a changing spectrum of deformation rates is important.

During roll application, a filament will undergo rates of extension proportional to its length and the velocity of the roll applicator. Using differential techniques, equation ( 5 ) . derived for small filament lengths. predicts extension rates of 120 to 360 sec-I

dV = sin x d;

where x = 1-0; x .0 - the linear distance and angle. respectively. defined by the distance between the vertical point of contact ofthe roll with the substrate and the point of filament attachment.

r - radius of roll t - time of traversement

fora 2 in. diameter roll. filament length ( I ) of0.2 in.. and application velocities of I to 3 ftlsec, respectively. As the roll leaves the area of application and a given filament grows in length. the rate of extension on the filament (and generally its extensional viscosity) will decrease in magnitude. Equation (6). an approximate

Figure velopn

-Influence of PEOM, 1-1212 paints, 90 KU.

outs, -2 ftlsec.

on fiber de- Vertical roll-


DYNAMICS OF ROLL SPAllER AND TRACKING

palter depende 90 KU. Vertical

at -2 Wsec.

nce I roll

on P outs

'EO 911

ure 12--Spatter !12palnt, 90KU.

at

dependence on Vertical rollouts -2 tvsec.

PEO , 3 par

relationship for large values of x, predicts lower values of E, 20 to 70 sec-', for application velocities of I to 3 ftlsec., 1 = 2.0 in.

- An attempt to quantify roll coating performance with 7 is complicated by three observations:

( I ) The rates of extension (E) (Figures 2 and 6) vary with the thickener (in formulations prepared from the same grind);

(2) None of the data fit the total spectrum of E calculated via equations (5) and (6) for the variable filament lengths noted in the flow visualization studies; and

(3) Most of t h e y increase dramatically as a function of E.

These problems, in part, relate to experimental difficulties. For example, a spectrum of E was not obtained due to: (a) the use of a large orifice required to avoid plugging caused by pigments, extenders, etc., contained in the formulations and the fact that is related to r [equation (3)l; (b) measurements of the radii must be made below the extrusion swell area to avoid the en- larged exit radii caused by relaxations (Figure 13c) upon exit from the confining "extrusion tube"; and (c) instabilities (Figure 13d) in some fibers, when the stretching force is increased. Even if these limitations,

Vol. 50, No. 641, June 1978

J.E. GLASS

largely indigenous topaintfilaments, were not in effect, the spinning-fiber technique has other serious limi- t a t i o n ~ . ~ * ~ . ~ ~ ~ h e most serious shortcoming with respect to obtaining q over a spectrum of E is rippling or draw r e ~ o n a n c e ~ ~ . ' ~ (Figure 13e). The calculations of either [equation (3)] or [equation (4)] involve radii measurements. Sectional averaging of radii values for a continuously decreasing radius with extension was employed when needed to avoid discontinuities in r)as a function of .i. If elimination of theseproblems were accomplished, the steepness of the q i relationships (Figures 2,6, 16) might resolve into the more Gaussian dependence noted in melt polymer studies.20 This additional complexity would necessitate computer simulation of the extension rate profiles and correspond- ing improvements in q~antifyingl.~ spatter beyond visual rankings, and in classifying tracking profiles be- yonithe shadow reflection approach, in order to quantify q - coating performance relationships.

Due to the complexities of the problems discussed above, the extensional responses recorded in Figures 2, 6, and 16 are presented as "Very Apparent Uniaxial Extensional Viscosities."

Ribbing, Tracking, And Biaxial Extensional Viscosities

Ribbing occurs in the roll application of a fluid. Rib- bing, a major problem in industrial coatings, is a result of cavitation, a subject recently reviewed by S a ~ a g e . ~ '

Figure 1SElongation behavior of interior (1-1212) paints (90 KU). a,b: freefall from syrings a - PAAC thickener, b - PEO thickener, M, = 4 x lo6. c,d: Extension in the spinning-flber apparatus; c - typical of photographs used in ii calculations, d - fiber breakage often noted under a variety of measurement conditions. e: example of draw resonance (i.e., nonuniform variance

in fiber radius with distance)

Generally, the number of ribs and conditions for the onset of ribbing are discussed in terms of a dimension-

less r a t i 0 , 2 ~ - ~ ~ $ , where q is the viscosity of the fluid,

S is the peripheral speed of the roll, and u is the surface tension of the fluid.

Ribbing occurs with trade paints at consumer application velocities (1-3 ftlsec). In formulations with low molecular weight thickeners, the phenomenon is ob- servable only to the discerning eye; in high molecular weight thickener formulations it is evident, if looked for, but can often be obscured under a dense array of fibers. In paints thickened with high molecular weight PAMC or PEO, ribbing is an unquestionable phenomenon, particularly with increasing roll velocities.

Based upon the extreme rib sizes in PAMC- and PEO-thickened paints (Figures 3 ,4 ,7 , and 10) and the lack of distinctive differences in their shear viscosities (Figure 51, extensional viscosities appear to play an important role in the surface irregularities generated via ribbing. Extensional viscosities are directionaP5 in nature, i.e., uniaxial, biaxial, and planar. The deformational flows noted in the visualization studies are best approximated by biaxial extensional viscosities which were not investigated in this effort. The relative mag- nitudes of the shear and biaxial extensional viscosities of the paint would be important in defining the total tracking phenomena, i .e. , the onset of ribbing, maximum size of the striations, and flowout behavior of



Figure 14--Spatter dependence on viscosity of Newtonlan fiulds. Vertlcal rollouts, 3 passes at -2 Wsec. Uniaxlal extensional vls- cosities of Newtonlan fluids are 3x shear

viscosities (recorded on spatter panel)

Figure 15--Influenceof elasticity on spatter drop size. High speed flow visualization studies (-2,0Wframes/sec), roll velocity -37Wsec. Arrows in third frame, second row denote simultaneous breakage to form "cylinder" which contracts within 4 milliseconds

Vol. 50, No. 641, June 1978 65

J.E. GLASS

RATE OF EXTEKSlON,sec~'

Figure 1GApparent uniaxial extensional viscosity dependence on rate-of extension, 1-1212 paints. Thickener:O, 0.31 wt.%, PAMC,Mw = 11 x 106,95 KU;O,0.16wt.%PAMC/0.35wt.%, HEC,

M, = 3 x lo5, 90 KU.

the irregularities. The tracking patterns arising from ribbing will be complicated further by the partial, substrate connected filaments which are freed upon fiber dissipation to fall back upon the coated surface. Often these stress-hardened filaments overlap the rib initiated surface irregularities. Upon cessation of all extensional deformations, the results noted in the commercial1 and experimental formulation6 studies suggest that flowout behaviors, like those observed in brush out^,^^ may be approximated by the shear response parameter, G* Recovery. In summary, roll trackingis a complex function of many factors, with the paint's extensional viscosity (biaxial) and G* Recovery being the dominant parameters. This will be discussed in greater detail in Part IV.*

Performance of Newtonian Fluids

Previous s t ~ d i e s * ~ have noted the viscoelastic properties of paints and the retarding influence of the elastic component on brush flow and leveling. The influence of elasticity in roll applications will depend on the relaxation time of the fluid to the deformation time of the process, i.e., the Deborah Number c ~ n c e p t . ~ ~ , ~ ' To assess the importance of viscosity independent of elastic contributions the performance of Newtonian oils (Can- non Instrument Co.) were investigated.

In flow visualization studies (roll velocity: - 37 ft/

'Pan IV d thir study f ~ l b w s this article.

sec) of the 0.3 and 3.9 poise (shear viscosities) fluids, ribbing and filamentation were observed. Biaxial extensional viscosities (for rib size) of the fluid may be appr~ximated~.~ as six times the respective shear viscosities; uniaxial (for spatter, discussed in the following section) extensional viscosities are a multiple of three.

Spatter profiles (application velocity: - 2 ftlsec) of the Newtonian oils are illustrated in Figure 14. Ignoring the results of the low viscosity (0.3 poise) fluid, due primarily to dripping, a decreasing spatter drop size is noted with increasing viscosity. A given weight of filament fluid will exhibit greater stability to capillary force disruption, i.e., surface tension-induced propagation of disturbance waves, with increasing viscosity. Con- sequently, a greater extension will occur with the high-viscosity fluid before destruction of the fiber, and smaller droplets will be observed upon its final dissipation. The observations, in total, indicate that elasticity is not a prerequisite for the occurrence of tracking or spatter in the roll application of a fluid.

Spatter, Uniaxial Extensional Viscosities And the Role of Elasticity

Uniaxial extensional visc~si t ies ,~.~ the type approximated by measurements (Figures 2, 6, and 16) in this study, have been qualitatively related to spatter in a previous section. The role of elasticity in roller-coating performance has been neglected to this point.

Theoretical and experimental result^^^-^' have established the role of capillary forces in the breakup of low viscosity fluids. The Newtonian fluid spatter profiles (Figure 14) in the previous section are comprehensible in terms of the capillary breakup concept. In the PAMC- and PEO-thickened paints, the filaments are highly viscous and contain thickeners noted for their elastic properties in shear deformational experiments. Viscoelasticity has been shown, both theoretically and experimentally, to be a stabilizing i n f l ~ e n c e ~ ~ - ~ ~ in highly viscous threads. It also has been argued that highly viscous threads break up when their internal elastic energy reaches a level equivalent to their cohesive energy .35

In the high speed flow visualization studies of coatings at application velocities of - 37 ftlsec, the influence of elasticity is evident in the broad distribution of spatter drop sizes. As the paint fibers increase in size, many are observed to break up simultaneously at two points by ductile failure mechanism^.^^.^^ The resulting "cylinders" almost instantaneously snap back (in <5 milliseconds, Figure IS) and while spinning above the recently coated substrate, they generally conform to a spherical configuration, significantly larger in size than other droplets generated from capillary force dissipation of presumably lower viscosity fibers. A general spectrum of observations were made in the high-speed flow visualization studies which parallel a recent inte- grated concept3' for describing behavorial aspects in the spinnability of polymer fluid filaments.

At consumer application velocities (1-3 ftlsec) the same elastic response noted at high roll velocities-the rapid snap back of liberated cylinders to a spherical


DYNAMICS OF ROLL SPAlTER AND TRACKING

Figure 17-Spatter in mixed thickener (PAMC, Mw = 11 x 1061HEC, M, = 3 x lo5) 1-1212 paints. W-SP wt.% and paint Stormer viscosities listed in Table 2. Vertical rollouts, 3 passes at -2 fVsec

Figure 18-Spatter in mixed thickener (PAMC, M, = 11 x 1O6/modified acrylic polymer (MAP), Mw - unknown) 1-1212 paints. W-SP wt.% and paint Stormer viscosities listed in Table 2. Vertical rollouts, 3 passes at -2 ftisec

Vol. 50, No. 641, June 1978 67

-... -- listed In Table 2. Vertical rollouts, 3 passes at - 2 ftlsec

Figure 2C-Spatter in mixed thickener (PEO, Mw = 4 x 1061MAP, M, unknown) 1-1212 paints. W-SP wt.% and parnt Stormer viscosities listed in Table 2. Vertical rollouts, 3 passes at 2 Ftlsec



form-is observed in slow speed (64 fra_meslsec), 8 mm cinematography of 90 KU, PEO (Mw=4 x 106)- thickened paints. This observation reduces the impulse to invoke relaxation times (1-3 sec) calculated from

N shear deformational parameters, i.e., T = -L , and

2 ~ 1 2 r belabor the Deborah number concept for a n elastic contribution in a short deformation time process, i.e., the - 37 ftlsec roll velocities.

In visualization studies of 120 KU and 90 KU paints thickened with PAAC, long filament lengths are observed at consumer application velocities; however, the fibers of either paint do not dissipate in the notable manner of the PEO-thickened formulation. A lack of clarity in the 64 frameslsec (viewed at 16 frameslsec) cinematography does not permit adefinitive conclusion on the primary mechanism of filament dissipation in the PAAC-thickened paints. However, an elasticity contribution to filament stability is evidentin comparing the 120 KU PAAC- and 90 KU PEO (M, =4 X lo6)- thickened paints. These formulations have comparable - 1) (Figures 2 and 6) and approximate shear relaxation times, yet the PEO formulation generates fibers of extreme stability, with associated ropiness, and the rapid snap back of dissipated filament cylinders. Elongated filaments are observed in the 120 KU PAAC formulation, but the extreme fiber stability and associated ropiness are not observed, nor is the snap back mechanism in dissipated fibers clearly in evidence. - Further quantification of the relative contributions of 1) and elasticity to fiber stability is difficult because of their parallel stabilization responses as a function of deformation rate. As demonstrated in an earlier section, the rate of extension decreases as the paint filament grows in l e n ~ t h . Following the trends in Figures 2 and 6, the fiber's r, will decrease as P decreases. Based upon studies in less complicated ~ y s t e m s , 3 ~ , ~ ~ elasticity

Table 2-Roll Application-Mixed Thickener Formulationa Study

Stormer conc., Conc., KU,

Prlmaty Thickener wl % Secondary Thlckener wt % ca. 24 hr - -

-- T Y P ~ M. ( x 1 06) ~ype M. ( x los) - - -- PAMC .... l l 0.31 - - - 95

0.16 HEC 3 0.35 92 0.08 0.41 90

- - - 0.66 89

PAMC . . . . I I 0.16 MAP Unk. 0.42 94 0.08 0.66 90

- - - 1.05 90

PEO . . . . . . . 4 0.46 - - - 90 0.23 HEC 3 0.34 90 0.11 0.54 90

PEO . . . . . . . 4 0.24 MAP Unk. 0.46 97 0. I I 0.68 92

.- (a) lnlenar 1-1212.

will transform from a stabilizing contribution to a de- stablizing factor as the deformation rate approaches zero. With the paralleling effects and our present in- ability to quantify elastic characteristics of low viscosity fluids during an extensional deformation, it is difficult todefine the relative contribution of each variable to fiber stability. Additional support for the importance of elasticity in stabilizing paint fibers is noted in the following section on mixed thickener studies.

Mixed Thickener Formulation Studies

The procedures used in this mixed thickener investigation are similar to those employed in brush application stu~Jies.~~.~~ The amount of a high molecular weight (> 10s M,) thickener (either PAMC or PEO) is reduced to 50 or 25% of the amount needed to obtain a 90 KU paint. A Stormer viscosity of 90 KU is then realized by adding a complementary, lower molecular weight thickener (either MAP or HEC). Both of the lower - M,, complementary thickeners individually provide nonspattering formulations. Thus, the low M, W-SPs were added separately to one of the four partially thickened (with either PAMC or PEO at the 25 or 50% levels) formulations to produce eight 90 KU paints. Formulations from the same grind were also thickened ir.dividually with one of the four W-SPs to bring the total number of paints investigated in this study to 12 (Table 2).

Fibers from both the HEC and MAPformulations did not respond to the extending force in spinning-fiber experiments. Only one of the eight mixed thickener formulations, i.e. the PAMC (5O%)/HEC combination, provided the tensile force response necessary for extensional parameter calculations (Figure 16). The spatter profiles for all 12 paints examined in this series are illustrated in Figures 17-20. Consistent with its higher - r,, the PAMC (SO%)/HEC mixed formulation (Figure 17) spatters more than the PAMC (SO%)/MAP thickened paint (Figure 18). However, without fiber tensile force characteristics, i.e., measurable by the spinning- fiber technique, both PEO (50%) mixed formulations (Figures 19 and 20) exhibited greater spatter than the PAMC (5O%)/HEC paint. The role reversal of the complementary thickeners also is surprising, i.e., the HEC formulation spatters more than the MAP mixed- thickener paint when the primary thickener is PAMC, but less when the primary thickener is PEO (compare second panels in Figures 17-20). The results are comprehensible if an elastic contjbution to fiber stability is not decreasing as fast as the r, function, with variations in thickener compositions.

Evidence that elasticity is contributing to fiber stabilities is seen clearly in the PEO (SO%)/HEC fibers (Figure 21a) and also in the PEO (SO%)/MAP rollout (Figure 21b). The very thin filaments interconnecting paint nodules (Figure 21a) are similar to the filament- droplet arrangements noted in nowNewtonian fluid jet stability studies.39 In the latter investigations the stability of the thin filaments was attributed to elasticity effects, since they were not observed with a vis- coinelastic fluid-a water/Carbopol@ 934 polymer solu-

Vol. 50, No. 641, June 1978

J.E. GLASS

Figure 21-Fiber and spatter development in selected mixed thickener. 1-1212 p~ints. Pri- mary Thickener: PEO. 0.24 wt%, M, = 4 x ye Secondary Thickener: a- HEC, 0.F W.%, M, = 3 x lo5, b - MAP, 0.46 W.%, M, - un-

known

tion. Although stretching motions were observed in the reported jet stability studies, extensional measurements were not conducted. A Carbopol resin (lightly crosslinked water-soluble polymer that cannot be formulated into a trade latex paint) solution does not respond to tensile force measurements conducted in this laboratory. It is probable that the filament-droplet phenomenon is due to elastic stabilizing effects, as the behaviors (Figure 21a, b) are markedly different from the capillary force dissipations noted with Newtonian fluids-and the ductile failure dissipations noted with high r) filaments.

SUMMARY

Paint filaments with high apparent extensional viscosities ( r ) ) were formulated by selecting thickeners from water-soluble polymers noted to resist extensional deformations at low solution concentrations. Rollout of these formulations produced extremely large ribs and tracking patterns, and-the roll fibers produced had exceptional stability. As r) of the filaments were decreased by using less thickener or by employing more thickener of a lower weight-average molecular weight, rib sizes and stability of the fibers decreased. An improvement in tracking, i.e., flowout of the surface irregularities, was observed with decreasing rib size; a dramatic increase in the degree of spatter was noted with decreasing fiber stability.

Carbopol is a registered trademark of Goodrich Carp.

The size of the ribs, precursors to tracking, appears to be related to biaxial extensional flows (high speed visualization studies). Although elasticity is not a prerequisite for the occurrence of ribbing or fiber stability (denoted by Newtonian fluid studies), comparative ex- aminations of viscoelastic paints indicate its importance, particularly in phenomena associated with fiber stability. In ductile failure dissipation of fibers, elasticity contributes markedly to the large distribution in spatter drop sizes, and in filaments with lower 7) the same approximate result is effected by stabilization of droplet-thread networks.

To contribute to the technology needed to improve coatings performance in both trade and industrial roll applications, a significant improvement in measuring extensional deformation responsesis needed. In particular, the sensitivity to measurer), both uniaxial and biaxial, in low total volume solid systems thickened with cellulose ether derivatives under conditions cover- ing a broad spectrum of extension rates is required. Such an achievement would contribute to coatings technology and to associated technological areas, i.e., printing inks, adhesives, etc.

ACKNOWLEDGMENTS

Appreciation is expressed to B.R. Peterson for his assistance in the photographic aspects of this study and to K.R. Ranson. whose careful experimental assistance has been of invaluable aid in all of the coatings studies reported from this laboratory.



References

(1) GI~~~,J.E.,J~URNAL~FC~ATING~TECHN~L~~Y.~O, NO. 610.53 (1978).

(2) Trouton. F.T., Proc. Roy. Soc. Lond.. A77. 426 (1906). (3) Hill. J.W.. and Cuculo, J.A..J. Macromol. Sci-Rev. Macromol.

Chem., C14. No. 1. 107 (1976). (4) Denson, C.D., Polymer Eng. Sci., 13, No. 2, 125 (1973). (5) Dealy. J.M., ibid.. 11. No. 6. 433 (1971). (6) Glass. J.E..JOURNALOFCOAT~NGSTECHNOLOGY.~~. NO. 640.61

( 1978). (7) Formulation suggestion 1-1212. "Interior Flat Wall Paint."

Union Carbide Corp.. Coatings Materials. 270 Park Avenue. New York, N.Y. 10017.

(8) Weinberger. C.B.. Ph.D. thesis. University of Michigan, Ann Arbor, Mich. 1970.

(9) Weinberger. C.B., and Goddard. J.D..Int. J. Multiphase Flow, 1. 465 (1974).

(10) Hudson. N.E.. Ferguson. J.. and Mackie. P.. Trans. Soc. Rheol.. 18. 541 (1974).

(11) Ferguson. J., and Hudson, N.E.. J. Physics E: Scientific In- struments. 8. No. 6. 526 (1975).

(12) Baid. K.M., and Metzner, A.B., Trans. Soc. Rheol., 21, 237 (1977).

(13) Astarita. G. and Nicodemo, L.. Chem. Eng. J . . 1. 57 (1970). (14) Metzner. A.B., and Metzner. A.P.. Rheol. Acta. 9. 174 (1970). ( 15) Oliver. D.R., and Bragg. R., ibid., 13. 830 (1974). (16) Moore. C.A.. and Pearson, J.R.A.. ibid.. 14. 436 ( 1975). (17) Everage. Jr.. A.E.,and Gordon. R.J.,AIChEJuurnal. 17. No. 5.

1257 (1971). (18) Han. C.D.. and Kim. Y.W., J. Appl. Polymer Sci.. 20. 1555

(1976).

(19) D'Andrea, R.G.. and Weinberger. C.B., AIChE Journal, 22, No. 5,923 (1976).

(20) Lamonte, R.R. and Han, C.D., J. Appl. Polymer Sci., 16. 3285 (1972).

(21) Savage, M.D., J. Fluid Mech., 80, 743 (1977). (22) Bretherton. F.P.. ibid.. 10. 166 (1%1). (23) Mill, C.C. and South, G.R., ibid., 28. 523 (1967). (24) Mill. C.C., J. Oil & Colour Chemists' Assoc., 50. 3% (1%7). (25) Glass, J.E., ibid., 58, 169 (1975). (26) Reimer. M., "Deformation, Strain and Flow." 2nd ed.. Lewis,

London (1960). (27) Metzner, A.B.. White. J.L., and Dunn. M.M.. Chem. Eng.

Prog.. 62, No. 12, 81 (1966). (28) Rayleigh, L., Phil. Mag., 34, 145 (1892). (29) Weber, C. ,Z. Angew. Math. Mech., 11. 137 (1931). (30) Middleman, S.. Chem. Eng. Sci.. 20. 1037 (1%5). (31) Goldin,M., Yerushalmi. J..Pfeffer, R..and Shinnar,R..J. Fluid

Mech.. 24, 689 (1%9). (32) Matovich, M.A.. and Pearson. J.R.A.. Ind. Eng. Chem. Fun-

damentals. 8, 512 (1969). (33) Chang, H., and Lodge. A.S., Rheol. Acta. 10. 448 (1971). (34) Lee, J.C., and Rubin. H.. ibid.. 14. 427 (1975). (35) Ziabicki, A., and Takserrnan-Krozer, R.. Kolloid 2.-2.

Polymer, 198, 60 (1%3); 199, 9 (1%4). (36) Nitschmann. H.. and Schrade, J.. Helv. Chim. Acta.. 31, 297

(1948). (37) Yoshiaki, I., and White, J.L., J. Appl. Polymer Sci., 20, 251 1

(1976). (38) Arney. W.C., and Glass. J.E.. J. Oil & Colour Chemists' As-

soc.. 59. 372 (1976). (39) Gordon, M.. Yemshalmi. J., and Shinnar. R.. Trans. Soc.

Rheol.. 17. 303 (1973). (40) Ting, R.Y., and Hunston, D.L.,J. Polymer Sci., 21, 1825 (1977).

Vol. 50, No. 641, June 1978

Dynamics of Roll Spatter and Tracking

Part IV: Importance of G* Recovery and NI in Tracking

J. Edward Glass Union Carbide Corporation'

The interrelationships among rheological parameters, formulation components and roll tracking a r e d i ~ s s e d . Formulations with high extensional viscosities (q 11000 poise over 20-150 sec-' extension rates) and moderate to high complex modulus responses (G' Recovery >I50 dyn cm2 at 0.08 sec-I shear rates) after high shear exposure give2ignificant tracking patterns. However, paints with high q but low G' Recoveries (< 50 dyn ~ m - ~ ) rapidly flow out to provide smooth roll coated surfaces. Rapid relaxation from the high 7 reached during application apparently occurs. Formulations with low to moderate q (150 poiseknd moderate G* Recoveries (3 200 dyn cn2 ) or very low q ( 4 0 poise) and high G* Recoveries (5 800 dyn ~ m - ~ ) provide rollouts of intermediate roughness. Specific examples for each formulation type are discussed.

Chemical composition of the thickener and latex median particle size, particularly important at high total volume solids, are the formulation components of importance in roll tracking. Increasing hydrophilicity in the thickener's structure, with molecular weights <500,000, and increasing biornodal particle size latices are desirable for good flowout. With small monodispersed latices, directional surface irregularities are observed and are be- lieved to be related to yield stress characteristics.

First normal stress differences (N,) are proposed to represent both elastic responses at low shear rates (G' Re- covery) and yield stresses in highly pigmented paints. The merits of G' Recovery and-N, as rheological tools for quantifying tracking in low q formulations-are discussed. In formulations other than those with high q and moderate to high G' Recoveries, roll tracking assessments correlate with quantitative drawdown barlprofilometer evaluations, which simulate brush flow and leveling.

INTRODUCTION

I n Part I of this series,' commercial trade paints were purchased and evaluated. Formulations marketed for the same interior application differed markedly i n their shear deformational responses and ro l l application per- formances, with no obvious association between the

Presented ~n par1 at the 54th Annual Meeting d t h e Federation of Socielies for C~lalings Technology in Washington. D.C.. Ocrobcr 29. 1976.

'Chern~calr and Plastics. Researchand Development Dtpl.. S. Charleston. W Va 25303

two sets o f parameters. This prompted the preparation and examination o f experimental paints for the controlled evaluation (Part 11%) of component influences on roll performance. Through these investigations and l im- ited analysis andlor personal knowledge o f some formulation ingredients used i n the commercial paints, the spatter variances o f the commercial products became comprehensible. However, the interrelationships among individual components, associated rheological responses, and the performance differences o f ro l l applied paints were not quantified.

The importance o f extensional viscosities (q) i n ro l l spatter was delineated i n Part III.3 The thickener's molecular weight and chemical composition (related to r ) i n Part 111). and the formulgion's total volume solids (not clarified with respect tor)) were the most important component influences (Part 11) on rol l spatter. In this concluding part o f the series, the interrelationships important i n roll tracking are considered.

RESULTS AND DISCUSSION

Tracking refers to the irregular patterns which arise and do not flow out when apaint is rol l applied, e.g., the left panel i n Figure 1. The irregularities i n the panel on the right, where total flowout of the striations has occurred, were present i n the original substrate.

If a viscous fluid flows through a narrow passage. such as that between a planar substrate and a compara- tively large roll, the f luid wil l pass through various pressure gradients. When the pressure falls below the saturated vapor pressure o f air dissolved in the liquid an aircavity wil l form. Flow patterns within the fluid In the nip o f the roll are such that eddies are postulated to c'xi-t and form a mechanism for cavity formation. Geneiall) . cavitation can be expected4 to form near the poinr of fluid separation. e.g., as the roll [].>verses beyond the point o f contact with the substrati.. Ribbing, a conse- quence o f cavitation, results in trar king patterns (Fig- ure 2) if the irregularities do not f l o u ~ out immediately after application.



Figure 1-Contrast in rollout tracking patterns. The irregularities in the right panel were present in the original substrate

Generally, the number of ribs and conditions for the onset of ribbing are discussed in terms of a dimension-

less ratio, % , where r) is the viscosity of the fluid, S is

the peripheral speed of the roll, and a is the surface tension of the fluid. A significant research effort has been devoted to the cavitation phenomenon and its consequences in various application areas. Reviews of this problem as it relates to adhesives5 and in the general area of lubrication6 have been published recently. Conditions for the onset of ribbing in the application of printing inks by counter rotating cylinder^^.^ have been quantified in equation (I),

3A

fi = 10.3 g u 6) (1 )

where r is the radius of the roll, and g the gap setting. Paralleling the observations of many, Mill and South6

noted that as the $ function increases the number of

ribs increase sharply until a value of 2.4 is attained; the

rib number then becomes independent of the $ parameter and dependent solely on the radius of the roll and gap setting. In a rigorous theoretical treatment, Savages has recently deduced that the number of ribs also depends only upon two independent parameters,

I & 4 1 r d * 3

Figure 2-Rib and tracking pattern development. Horizontal rollout (-37 Wsec) of 1-1212 paint (90 KU). Thickener: HEC, a, = 1.5 x 106

Vol. 50, No. 641, June 1978 73

lq61am Jeln3alolu mo( 10 ratuAlodoo allhoe Paijlpotu e SI dvw 'nn 06 ol suolwl -ntuJoI Jaw0 :nn 021 01 pauaqqul sem 3wd ql!m xatel awe 6ulu1stuo3 uo!lelnturoj 'E a~n6!j aas uolle3l)ltuapl xalel .stu!ed 2121-1 'sallbo~d lnollol Wll) A~a--p a~n6ij

sJaqg pue squ q~oq jo 'sa!l!l!qels "a.! 'saz!s aql slup2d pauays!q133~ J~MOI aq1 UI '(11 ]led) suo!le[nmJoj ZIZI-I (%EE = SAL) SP!IOS amnloA IeJo) MOI '33H ("K) ~ql!a~ Je[nsa[om q%!q u! pahlasqo s! s!q~ sluam -uxxa uo!)ez![ens!A MOU aq] u~ 'lallel aql jo K%~aua asepns aaq Jarno1 aql jo asnesaq sJaqg olu! unojsue~~ 01 'ssa~ls panu!]uos q]!~ pue 'm~oj 01 squ ~sadxa 1q8!w auo [e~aua% u~ .)uap!r\a SBM uaqg JO squ Klaleu!mop -a~d .taql!a mJoj 01 sluled jo Ksuapual aq] u! 'Ja~aMoq 'asua~ajj!p y '11o.1 Jaqqru qlooms e jo asn aql "a'! 'asuasqe sl! JO JaAos J!eqoK e jo qllual deu aql uodn puadap 01 pauasqo IOU se~ squ jo Jaqmnu aql Kpnls a~!]eJedwos pa]!m!l e UI .uo!le%!lsa~u! s!ql u! pahlasqo aJe (z aln8!~) sqp 'K~%u!PJo~~v .%u!qqujo lasuo aql JOJ

aAoqe paqussap suo!~!puos aq1 paa3xa 01 au!qmos 'sa!l -!solaA uo!jes!lddu ~amnsuos lensn pue 'saz!s [~OJ [e!s -1ammos 'slu!ed ales ape11 jo sa!]~ado~d lwauag aqL

.ssauqs!q~ m[g mnm!u!m aq1 s! ~q aJaqm ' pue $


Figure &Paint drawdown surface profile studies of 1-1212 paints. Latex, thickener and sag ratlng recorded on respective

profiles

were diminished. In commercial paints A and E (Part I), both high in TS (65 and 63%, respectively) and heavy spattering formulations, a noted preference for fiber generation over rib stability was evident. In the investigation of 90 KU formulations with high extensional viscosities, smaller rib sizes were present in the hkh - M, PAMC thickened 1-1212 paint than in the high M, PEO formulation (top panels, Figures 7 and 10, respectively-Part 111) at consumer application velocities (1-3 ftlsec). With increasing extensional viscosities (Figure 2 vs. &Part 111) and faster roll velocities (37 ftlsec), rib growth (Figures 3, &Part 111) was very prominent in both low TVS formulations. Thus, in these three sets of distinctly different paints there are many interacting factors causing variances in roll application behavior, and these are further complicated by variations in roll radii and film thickness in industrial coating applications.

Roll Spatter, Tracking, and Brush Flowouts

Spatter and tracking arise from the same mechanistic origin, cavitation, but as noted above, the two roll performance parameters respond independently to shear and extensional strains. Cohesive and adhesive differences between formulations and their relative in-

Figure 7--Instantaneous rollout profile of 1-1212 paint (90 KU) contalnlng BMD latex and MAP thickener

Vol. 50, No. 641, June 1978 75

J.E. GLASS

-

Flgure 8--Shear rate dependence of first , normal stress difference, 1-1212 palnts (90 KU). For latex and thickener identlflcalon 5 -

see Figures 5 and 3 2 lgr

B I e :

10-1 100 10' 102 10'

SMAR RATE, see-I

fluences on stabilization of rib and fiber forms against "moderate? approximation of 7 50poise is estimated disturbance wave dissipations may be important in the for the high M, HEW-1212 paint on the basis ofFigure performance differences noted. 16 in Part 111 and the comparative spatter of the former

Visual observations of coatings being applied by paint, since present techniques lack the sensitivity to brush do not support a similar mechanistic origin for measure q in the low viscosity range. brushouts and roll tracking, but as will be noted later, brush and roll flowouts generally respond to the same Tracking and the Importance rheological parameters. This trend was reflected in Of G' Recovery and NI commercial ~ a i n t s B and C (Part I). For example, for- In general, roll surface roughness profiles (Figures 3 mulation B spattered heavily with excellent flowout and 4) correlate with G* Recovery responses (Figure 5) (and excessive sag) in both brush and roll applications. and with brushouts, quantified by sensitive drawdown Paint C, with nil spatter, even at high Stormer vis- bar s i m ~ l a t i o n s ~ ~ . ~ ~ ( F i g u r e 6). However, there are sub- cosities and high roll velocities, exhibited parallel tle differences in the qualitative relationships. The (brush and roll), decreasing f l~wouts with increasing 1-1212 formulation thickened with MAP and containing Stormer KU. These results reflect the unimportance of the broad distribution particle size latex has a rough- extensional viscosities in the flowout of most roll sur- ness pattern somewhat unexpected if ribbing, i.e., stria- face irregularities. tions parallel with the direction of flow, is the source of

Extensional Viscosities And Tracking Independence

The roll application of high extensional viscosity (G) paints will result in large ribs and extremely high viscosity fibers, both responsible for irregular surface striations. Once applied, relaxation from the high extensional deformations during application and the shear viscosity and elasticity recoveries at low shearlo after application are important to flowout rates and the final irregularities noted in the dried film. If the formulation's G* Recoveryl0 is moderate [5 150 dynes ~ m - ~ , as in poly(ethylene oxide) thickened 1-1212 formu- lationsl1] to high, the significant surface imperfections generated because of high q (Part 111) will persist.

Formulations with a moderate to high q but low G* Recoveries are reflected in PAAC thickened 1-1212 paints. These formulations spatter appreciably (Part 11) but give no evidence in their rollout orofiles (first oanels - ~ i i u r e s 3 and 4) of relaxation diffilulties frbm the high extensional viscosities (Part 111) attained during application. In comparison, poorerflowout of surface imper- fectkns is evident (second panel - F i g ~ e 3) in a moderate q (<50 poise) formulation (high M, HEC/I-12 12) with a moderate ( - 200 dyn ~ m - ~ ) G* Recovery. The

Figure +Paint drawdown surface profile studies, exterior painr formulation E-1206. Latex, thickener and sag rating recorded on

respective profiles



Flgure 1 M h e a r rate dependence of flnt normal stress difference, exterlor 51206 paints (90 KU). For latex and thickener Iden-

tltlcalon see Figures 5 and 3

SHEAR RATE, red '

tracking. The truncated ribs in Figure 2 generate the e ~ p e c t e d ~ b b i n g patterns, but if the formulation has a very low q, the truncated sheets will not obtain the sizes reached in Figure 2. Under such conditions, if the paint's G* Recovery is high (as in MAP thickened formulations, 9 800 dyn ~m-~-Figure 5 ) , the immediate roll-sheet remnants will dominate the tracking pattern, i.e., a randomized cupiness will obscure the parallel flow rib striations. The second panel in Figure 4 can be envisaged from the instantaneous rollout profiles in Figure 7 where small, truncated, and nontruncated sheets, essentially perpendicular and not parallel to the direction of flow, are observed.

In replacing the broad distribution latex with small monodispersed (SMD) particles, directional patterns become very distinct (Figures 3 and 4). Historically, poor flowouts with SMD latices are associated with yield stress value^.'^.^^ In addition, the plots of first normal stress differences ( N , ) as afunction of shear rate (y) are relatively flat in most of the paints examined in these studies, in contrast to the quadratic responses of aqueous water-soluble polymer solutions. The flatness

in most of the N , - j plots (Figures 10 and 11 in Part I and Figure 8), and in all of the N , - j plots of formulations containing SMD latices, suggests that N , values reflect yield stress (YJ characteristics of paints at low j . Like G* Recovery, N , values also reflect an elastic response. However, roll profile roughnesses and N , values at low j (Figure 8) do not correlate well in 1-1212 formulations in comparison with the agreement noted between G* Recovery and drawdown bar evaluations.

Making the same thickener and latex comparisons, but in an exterior formulation (Figure 9) having a lower PVC and higher alkalinity, twointeresting observations are noted: (1) the brush simulation profiles and sag ratings are higher in certain formulations with the broad distribution latex than with the small monodisperse latex and (2) there is a surprisingly good correlation between N , values at low j and the drawdown profiles (Figure 10).

Finally, the rollout directional surface irregularity differences between broad and small monodisperse latex formulations are dramatically highlighted in high TVS 1-1212 (Figure 11) studies. Appropriate rollout

Figure 11-Drytlim rollout protiles: Hlgh total volum~solid (NS) 1-1212 paints. Thickener: HEC, M, = 3 x lo5. For latex identification

see Figure 3

Vol. 50, No. 641, June 1978

J.E. GLASS

comparisons in Figures 3 and 10 with N, (Figure 11) reveal a notable correlation. The largest Y , values among formulations studied in these investigations would be expected in high TVS, SMD latex paints.

Future studies will report N, at low j as afunction of time after shearing at high rates, i.e., N, Recovery. This should prove to be a rewarding area of research in delineating tracking patterns, particularly in comparative industrial roll applications.

CONCLUSIONS

In the roll application of a paint, the complex shear modulus of the film after application (G* Recovery) is the primary parameter affecting the flowout of trxcking patterns. Only if both the extensional viscosity, r ) , and G* Recovery values during and after application are moderate to high will the tracking patterns in a roll applied coating be excessive. If the extensional viscosity of the formulation is high (>I000 poise) but the G* Recovery parameter is very low ( 4 0 dyn ~ m - ~ ) , flowouts will readily occur and the surface imperfections noted will be those associated with the substrate.

In low to moderate r ) formulations, roll tracking patterns appear to correlate generally with G* Recovery, and with first normal stress differences (N,). The N,- shear rate ( j ) plots of highly pigmented paints are flat, in contrast to those of aqueous thickened latex mixtures. As such, the N,-j dependence probably reflects both elastic properties of the coating and yield stress behavior during recovery. Roll tracking correlates quantitatively with N, when the profile changes are related to total volume solid variations in the formulation.

Good flowout of roll applied tracking are obtained with broad distribution particle size latices and thickeners of high hydrophilicities, without macromolecular interassociations in solution. As such, the components important in roll tracking profiles correlate with those significant in brush flowouts. Improved techniques foyquantifying roll tracking with N, kecov- ery values, i.e., N, at low j after high shear or extensional exposure, are needed to complement these observations in roll performance behavior, particularly for advancing the technology in industrial applications.

n , , , , , , , , , , , , , , , , , , , , , , , , , , , , J 10'

10-I o0 10' I+ lo3

WEAR RATE,

Figure 12--Shear rate dependence of first normal stress dlffer- ence, high TVS, 1-1212 paints. Open symbols- BMD latex - closed symbols - SMD latex. N S : A, A, 33.0%; 0, H, 39.7%; O, ., 42.4%

ACKNOWLEDGMENTS

Appreciation is expressed to S.L. Hager and M. L. Gentry for their assistance in obtaining the N,- j data in this study.

References (1) Glass. J.E.. JOURNAL~FC~ATINGSTECHN~LOGY.~~ . No. 640.53

(1978). (2) Glass. J.E.. JOURNALOFCOATINGSTECHNOLOGY.~~. No. 640.61

(1978). (3) Glass J.E.. J~URNALOFCOATINGSTECHNOL~GY.~~, No. 641.56

(1978). (4) Hopkins. M.R.. Brit. J. Appl. Ph.vs.. 8. 442 ( 1957). ( 5 ) Myers. R.R.. and Knauss. C.J.. "Roll Application of Adhe-

sives." Chapter IV. in Sheist. I . . ed.. "Handbook of Adhe- sives." 2nd ed.. Van Nostrand Reinhold. 1977.

(6) Savage. M.D.. J. Fluid Mcch.. 80. 743 (1977). (7) Mill. C.C.. and South. G.R.. ihid.. 28. 523 (1967). (8) Mill. C.C.. J. Oil & Cok~ur Chemists' Assoc.. 50. 396 (1967). (9) Savage. M.D., J. Fluid Mech.. 80, 757 (1977).

(10) Glass. J.E.. J. Oil & Colour Chemists' Asso<,.. 58. 169 ( 1975). ( l I) Glass, J.E.. ihid.. 59. 86 ( 1976). (12) Dodge. J.S.. J O U R N A L OF PAINTTC(.HNOI.OGY.~~. No. 564. 73

( 1972). (13) Patton. T.C.. "Paint FIOII. and Pipmcvt Disp[~rsion." Intersci-

ence Publishers. ( IY64). (14) Kreider. R.W. . Official D I G I . . s T . ~ ~ . NO. 478. 1244 (1964).


IMC will give you a free sample of this powerful amine. Experi- ment with it in your water- bosed coating formulas and see the improvements for yourself:

In baking systems, its h igh strength will give your finish. outstanding properties. AMP-95 Con interreact with resins so wel l

that the two actually become One. And this can give your finish better water, salt spray,

and detergent resistance. AMP-95 gives you

advantages in both baked and air-dry systems. In air-dry system it can double tank stability time and shorten tack-free time.

For your free sample of

AMP-95, write NP Division, IMC Chemical Group, Inc., 666 Garland Place, Des Plaines, Illinois 60016. Or call 31 21296-0600.

International Minerals & Chemical Corporation,

Val. 50, No. 641, June 1978 79

CABOT BLACKS... The Perfect Start forYour Finish If your black coating formula- When you are developing a new tions require high masstone and formulation, or revising an old extremely jet color, BLACK one, start with aCabot black. It PEARI,Sn 1300 carbon black will give you superior product (or its fluffy form, MONARCH" and processing characteristics 1300) can do the job better, and at the lowest possible cost. more economicallv, than anv other grade in the market.

For complete details, send for These blacks provide a high, Technical Service Reoort S - Z ~ A . sharp gloss, excellent blue tone and a jetness equal or superior to CABOT

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they replaced. 125 H Q h Street Boslon Massachusetts 02110 Tel (617) 423-6000 CBI ~ O O R


Society meetin~s

Baltimore April 20 "SOLID WASTE DISPOSAL" was the

top~c of a presentation by represen- tat~ves of the Maryland State Depart- ment of Health, who d~scussed the van- ous classes of regulat~ons governing the d~sposal of hazardous substances. The three classes, they sa~d. are dependent on the degree of r ~ s k to human health, I e. , great. major. or a substant~al threat

HARRY s ~ H ~ ~ ~ ~ ~ . secretary Executive Committee of the Montreal Society for Coatings Technology for the year 1977-78. Seated (left to right): R. Snyder; A. Hagopian; R.L. Sheppard; P. Ruiz; and R.A. Fraser. Standing: D. Connor; G. Bernicky; A.J. Parent; H. Philipp; R. Rauch; B. Papen-

burg; V. Pedersen; W. Kolanitch; and A. Marchetti

Chicago April 3 During the business meeting the

membership voted to adopt a proposed By-Laws change allowing Associate members to occupy positions on the So- ciety's Executive Committee.

The following slate of officers was elected for the year 1978-79: President-Walter J. Krason. Jr., of Enterprise Paint Mfg. Co.; Vice- President-W. Bud Bartelt. of Rust- Oleum Corp.; Secretary-Richard M. Hille. of United Coatings. Inc.; and Treasurer-John Petty, of Sherwin- Williams Co. John T. Vandeberg will remain as Council Representative.

W.B. BARTELT. S~rretary

C-PI-C March 13

J.P. McDonald. of Reichhold Chemi- cal, Inc.. spoke on "AIR DRY INDUS- TRIAL PRIMER LATEX SURVEY."

Mr. McDonald began by stating the obiective of the studv. which was to evaluate and compare water-borne industrial primers for performance properties using the following types of latex vehicles: acrylics, styrenelacrylics. and butadienelstyrenc. Divided into two sections, the survey compares the individual latices in a latex primer. and the effect that various modifiers have on the latex primer. he said.

In the first part. the primers were formulated with different types of latices. Acrylics. styrenelacrylics, and styreneibutadiene, all with and without functional groups. were evaluated for performance properties. A total of 18 different polymers were tested with vilr- ious monomers.

Of the various primers surveyed. a combination of styrene butylacrylate polymer and the combination of

butadiene styrene methylcrylate acid performed best.

The second part examined the effect of two resinous modifiers: epoxy ester and maleinized oil. Test results indicate that an excellent product can be made by blending the epoxy ester and the latex with the major criteria being cost.

Q. What film thickness was used when making the test?

A. Draw downs were made with a Bird applicator and held to I and 1.2 mils in the first set of testing. In the second set of testing 2 coat ( I .25 mils) and 4 coat (2.25 mils) dry film were used.

Q. What is separation? A. Separation is phasing or the clear

liquid on top.

After the business meeting Fran Alves. of Ohio Bell Telephone Co., spoke on "COMMUNICATIONS YEAR 2001."

ROBERT A. BROERMAN. Surretary

Detroit April 25 Among the honored guests in atten-

dance were Federation President-Elect James McCormick; Executive Vice- President Frank Borrelle; and Field Di- rector Thomas Kocis.

During the business meeting, the following slate of society officers was elected for the year 1978-79: Presi- dent-Mackenzie K. Endo, of Ford Motor Co.; President-Elect-Walter Stuecken, of Grow Chemical Co.; Treasurer-G.M. Sastry. of Chrysler Corp.; and Secretary-Gary Van de Streek. of Wyandotte Paint Products. Inc.

Mr. McCormick discussed current activities of the Federation. including its reorganization, to be voted on at the next Council meeting. Mr. Borrelle said that the 1978 Paint Show. to be held in Chicago. will be the largest ever. and discussed Federation officers travel to Societies. Mr. Kocis announced that the "PaintICoatings Dictionary" will be

Officers of the New York Society for Coatings Technology for the year 1977-78. Left to right: Vice-President-Saul Spindel; President-George J. Dippold; Secretary-Sidney

J. Rubin; and Treasurer-Mawin J. Schnall

Vol. 50, No. 641, June 1978 81

Constituent Society Meetings and Secretaries

BALTIMORE (Third Thursday-Eudowood Gardens, Towson). HARRY SCHWARTZ, Baltimore Paint &Chemical Corp., 2325 Hollins Ferry Rd., Balti- more, Md. 21230.

BIRMINGHAM (First Thursday-Warwickshire County Cricket Ground). R.G. SMITH. Arthur Holden & Sons Ltd., Bordesley Green Rd., Birmingham, England.

CHICAGO (First Monday-meeting sites in various suburban locations) WILBERT B. BARTLET, Rust-Oleum Corp.. 2301 Oakton St.. Evanston, Ill. 60204.

C-DI-C(SecondMonday-Sept. ,Nov. ,Jan. ,Mar. .MayinColumbus;Oct., Dec. ,Feb., Apr.inCincinnati,KingsIslandInn). ROBERTA. B R O E R M A N . T ~ ~ ~ ~ C O Chemicals, Inc., 620 Shepard Dr., Lockland, Ohio 45215.

CLEVELAND (Second Tuesday-meeting sites vary). PAUL HOUCK, Morgan Adhesives Co., 4560 Darrow Rd., Stow. Ohio 44242.

DALLAS (Thursday following second Tuesday-Vic's Gallery Restau- rant). WILLIAM F. HOLMES. DeSoto, Inc.. P.O. BOX 10, Garland, Texas 75040.

DETROIT (Fourth Tuesday-Rackham Memorial Bldg.). G.M. SASTRY, Chrysler Corp.. 5437 W. Jefferson, Trenton, Mich. 48183.

GOLDEN GATE (Monday before third Wednesday-Sabella's Resmu- rant. San Francisco). JOHN C. DICKMAN, Drew Chemical Corp., 2051 Pioneer Ct., San Mateo, Calif. 94403.

HOUSTON (Second Tuesday-Sonny Look's Sir-Loin Inn). WILLIAM A. WENTWORTH, Napko Corp., P.O. Box 14509, Houston, Tex. 77021.

KANSAS CITY (Second Thursday-Washington Street Station). WILLIAM FITZPATRICK, Cook Paint and Varnish Co., P.O. Box 389, Kansas City, Mo. 64141.

LOS ANGELES (Second Wednesday-Steven's Steak House). DONALD I. JORDAN, Cargill, Inc., 2801 Lynwood Rd., Lynwood, Calif. 90262.

LOUISVILLE (Third Wednesday-Essex House). J.K. MENEFEE, Hy- Klas Paint Co., 1401 S. 12th St., Louisville, Ky. 40210.

MEXICO (Fourth Thursday-meeting sites vary). EMILIO SANTILLAN. In- dustrias Resistol. S.A.. Apartado Postal 44-977. Mexico 12. D.F.

MONTREAL (First Wednesday-Bill Wong's Restaurant). ARTHUR T. PARENT, Monsanto Canada Ltd., 425 St. Patrick St., Quebec, P.Q.

NEW ENGLAND (Third Thursday-Fantasia Restaurant, Cambridge). JOHN GIUFFRIDA, Cabot Corp., Concord Rd., Billerica, Mass. 01821.

NEW YORK (Second Tuesday-varies between New York and New Jersey locations). SIDNEY J. RUBIN, Greepoint Paint & VarnishCorp., P.O. Box 14, Pratt Station, Brooklyn, N.Y. 11205.

NORTHWESTERN (Tuesday after first Monday-Jax Cafe). AL HEIT. KAMP, Cargill, Inc., P.O. Box 9300, Minneapolis, Minn. 55649.

PACIFIC NORTHWEST (Portland Section-Tuesday following second Wednesday; Seattle Section-the day after Portland; British Columbia Section-the day after Seattle). WALTER B. CLYDE, Glidden Chemical Coat- ings, Div. of SCM Corp., 2800 N.W. 31 St., Portland, Ore. 97210.

PHILADELPHIA (Second Thursday-VaUe's Steak House). CARL W. F u ~ ~ ~ ~ , R e i c h a r d Coulston, Inc., 300 Daleview Dr., Monisville, Pa. 19067.

PIEDMONT (Third Wednesday-Howard Johnson's Coliseum, Greensboro, N.C.). JOHN V. H~~~os ,Ash land Chemical Co., 3652 Stokes Ave., Charlotte, N.C. 28210.

PITTSBURGH (First Monday-Skibo Hall, Carnegie-Mellon University Campus). ROBERTT. MARCUS, PPGIndustries, Inc., 151 Colfax St., Springdale, Pa. 15144.

ROCKY MOUNTAIN (Monday prior to second Wednesday--Ciasthaus Ridgeview, Wheatridge, Colo.). GLENN A. SORENSEN, Bennett's, P.O. Box 1320, Salt Lake City, Utah 84110.

ST. LOUIS (Third Tuesday-Salad Bowl Restaurant). HERBERT ROSENBLATT, Steelcote Mfg. Corp., 3418 Gratiot St., St. Louis, Mo. 63103.

SOUTHERN (Gulf Coast Section-Second Tuesday; Central Florida Section-Thursday after third Monday; Atlanta Section-Third Thursday). THAD T. BROOME, Precision Paint Corp., 5275 Peachtree Ind. Blvd., Atlanta, Ga. 3034 1.

TORONTO (Second Monday-Town and Country Restaurant). J . GROD ZINSKI, Reed - Pigments Div., 199 New Toronto St., Toronto, Ont. M8V 2E9. Canada.

WESTERN NEW YORK (Second Tuesday-Holiday Inn. Cheektowaga. N.Y.). THOMAS E. POPOVEC, National Gypsum Co., 1650 Military Rd.. Buffalo. N.Y. 14217.

available in September, and described the Manufacturing and Education Committees activities.

Al Keay, of Harmon Colors, Inc., spoke on "How DID You MAKE THAT COLOR."

Mr. Keay described the various methods of identification of pigments in mixtures using spectrophotometry in matching colors.

G.M. SASTRY, Secretary

Kansas City April 13 Robert Baker, of Witco Chemical

Co., presented "CORROSION RE- SISTANCE-A NEW APPROACH." which explained the possibility of using raw materials in coatings that, up until now, have been used in grease and asphalt-type coatings.

WILLIAM J. FITZPATRICK. Secretary

Los Angeles April 12 Honored guests in attendance in-

cluded the following Past-Presidents of the Society: Ted Hawlish (1939); John R. Warner (1945); Alan U. Hershey (1%1); Allan R. Yerby (1%6); Duke G. Cromwell (1970); John A. Gordon, Jr. (1973); Robert A. McNeill (1974); and Ken J . O'Morrow (1975).

Dr. Friso Willeboordse, of Union Carbide Corp., discussed "EVAPORA- TION OF ORGANIC CO-SOLVENTS FROM WATER-BORNE FORMULATIONS."

In a very interesting slide illustrated talk, Dr. Willeboordse presented the concept of Critical Relative Humidity and its effect, in conjunction with ambient relative humidity, on waterlco- solvent mixtures. If the ambient relative humidity is higher than the Critical Rel- a t ive Humidity (CRH) of a given waterlco-solvent mixture, the organic co-solvent will b e deple ted in the "tails" as the mixtureevaporates. If, on the other hand, the ambient relative humidity is lower than the CHR. the water will be depleted in the "tails". Finally, if the ambient relative humidity and the CRH are equal, the composition of the mixture will remain unchanged as it evaporates.

This concept, said Dr. Willeboordse, can be used to maintaia agivenflash-off time for a coating at differing ambient relative humidities, assure that the water-co-solvent mixture enriches in the co-solvent as the mixture evaporates in order to give high gloss, etc. It can also be used to adjust for other variables in the curing of water-borne coatings, such as ambient temperature and airvelocity over thedryingfilm, he said.

DONALD I. JORDAN. Serrctary


Montreal April 5 Messrs. W. Mills, N. Ray, and M.

Berube were presented with Federation 25-Year Service pins in recognition of their years of service to the Federation and the Society.

J. Joudry, of N L Industries. Inc.. presented "FORMULATING AND TEST- ING LEAD-FREE CORROSION INH~B~T~VE COATINGS."

A.J. PARENT. Recording Secretary

New York March 14

A moment of silence was observed in memory of Melvin M. Gerson, of Daniel Products Co.. who died recently.

The meeting was divided into four workshop sessions. A report ofeachfol- lows: r

Material Flow And Handling In the Paint Plant Gabriel Malkin, Consultant, dis-

cussed the advantages and disadvantages of various methods of handling raw materials. Dry materials are more simply handled in bulk. with the advantages being lower initial cost, freight. and break cost, he said. He added that a dry bulk handling system must be designed and built properly and should not be used unless one million pounds per year of an item is used.

Pigments. he said. can be handled in slurries because thereis nodispersing of Ti02 or other inerts and it is easier to design a slurry system than a dry system, although much labor is saved in both systems.

The best way to handle liquids is in tank cars. he said. Caution should be used when moving solvent-based vehicles; use of air pressure is a fire hazard and cleanliness is of prime importance.

Q. What are the hazards ($handling lorex?

A. Latex is initially stored by the manufacturer in large tanks which are subject to changes in temperature and bacteria; poor pumping practices at the receiving point may cause shearing action on the latex; storage tanks and tankwagons may not be clean.

Coatings Technology For the Beginner

Donald E. Brody. of Skeist Laboratories. Inc.. discussed. in basic terms, the various aspects of coatings technology. Topics included in the presentation were drying methods. mcthods of polymerization. crosslinking methods. coatings classifications. formulation ingredients. and quality vs. cost.

Q. Does the oxidation of the double bonds in the vehicle aflect color retention in the paint?

A. Sometimes chromophores are formed, adding color to the paint as it dries and ages.

Costing and Pricing Of Coatings

Murray Guttenplan, of Pur-All Paint Products Co., Inc., discussed the factors contributing to the final selling price of the manufactured product.

Raw material cost is simply a weighted cost of all the raw materials in the product, he said. However, determining the individual costs may not be that simple. Different companies use different approaches, including: last actual price and freight paid; first in, first out;

weighted average of stock on hand; and future market, etc.

The actual calculations are rather simple, he said, but should bedone at all levels from the benchman to management, when the final selling price is finally determined.

Certain factors are easily obtained, such as the cost of packaging, freight, sales commission, discount, and any others which may be a percentage of final price, he said.

The more difficult items are the various labor costs, overhead, total mer- chandising, etc. These, however, may be grouped together by the simple method of total expenses divided by the total production to obtain the cost per item-or each item may be laborious taken individually, he added.

. HYDROUS AND ANHY- DROUS ALUMINUM 5111. 1 CATE PIGMENTS . KAOLIN CLAYS 1

Vol. 50. No. 641. June 1978 83

Society meeting (hntinumtl

Another factor mentioned by Mr. Guttenplan is the "degree of difficulty" of manufacturing. This is a plus or minus factor determined from the batch size, how difficult or time consuming it is to produce, exceptional high price of raw material, very high loss, long tank- age time, and many or special laboratory procedures, he explained.

Finally, after all these and any other expenses that may be particular to any one coating, the final and most important item of profit must be added, he

isocyanate terminated urethane polymer, and two-component non- yellowing urethane coatings, which use a non-yellowing urethane adduct (or prepolymer), a curative, plus a catalyst and any necessary additives to obtain the coatings characteristics required.

SIDNEY J. RUBIN. Secretary

Pacific Northwest, Mar. 16 Vancouver Section

said. A presentation on "COLOR-

APPEARANCE EVALUATION" was given SalesmanlPurchasing Agent by Thomas Keane, of Gardner Labora-

Interface tory, Inc. Mr. Keane's talk centered around a

Edward Czaplicki, of International series of slides illustrating various ap- Paint Co., Inc., presented an interesting pearance phenomena He then de- talk on the general functions of the pur- scribed the processes ind equipment chasing agent and what he expectsfrom necessary for measuring these a salesman.

Mr. Czaplicki described the particu- phenomena' R.P. STEWART. Secretary

lar areas of dislike regarding salesman. including lack of motkation; communication, and information. He em- phasized that the ingredients for suc- Mar. 9 cess between salesman and the purchas- ing agent are communication, respect, and an understanding of one another's responsibilities.

SIDNEY J. RUBIN. Secretary

New York April 11

Honored guests attending the meeting included the following Past- Presidents of the Society: Moe Bauman, Herman Singer, Marvin Wexler, John Toscano, William Singer, Al Sarnotsky, John Oates, Sidney Levinson, John Congelton, William Greco, Ben Chatzinoff, Herbert Hill- man, Herman Singer, Richard Schmidt. Moe Coffino, and John Biskup. In addition to Mr. Oates, who is Federation President, the meeting was also at- tended by Frank Borrelle, Federation Executive Vice-President, and Tom Kocis, Editor of the JCT.

Society President George Dippold presented a contribution of $500 to Mr. Oates for the Paint Research Institute.

Harold Garey. of K.J. Quinn & Co., Inc., spoke on "NoN-Y ELLOWING URETHANE COATINGS."

Following a brief introduction of the eight non-yellowing types of urethane coatings. Mr. Garey focused his attention on two of these: non-yellowing moisture curing, which cure by the action of atmospheric moisture with an

Highlighting the meeting was the presentation of 25-year membership pins to those Society members who have been actively involved in Society affairs for the past 25 years. The recipi- ents include: R.G. Alexander, Umberto Ancona, Kalman Azarchi, Dean Berg- er, Bill Clark, Robert Cox, Horace Ether, W. Grantham, Chris Hannevig, Pat Hunt, Bill Johnson, Dick Kiefer, J.J. McAnally, M.J. McDowell, E. Merkle, Walter Mock, H.A. Pfeiffer, Lothar Sander, E.R. Smalley. L.P. Spencer, W.H. Toole, E.J. Welch, George Woodward, David S. Young. and H. Zimmerman.

Fred Falk, of Precision Colors, Inc.. spoke on " ~ I M ~ L A R ~ T I E S A N D DIFFER- ENCES BETWEEN INKS AND PAINTS."

CARL W. FULLER. Secretary

Piedmont April 19

Among the honored guests in attendance was Tom Kocis, Federation Field Service Director, who spoke briefly about the 1978 Annual Meeting and Paint Show in Chicago, and announced that the "PaintiCoatings Dictionary" will be available this September.

"MICROBIOLOGICAL PROBLEMS AS- SOCIATED WITH WATER-REDUCIBLE COATINGS" was the topic of a presentation by William Machemer. of Troy Chemical Corp.

Mr. Machemer stated that industrial finishes and maintenance paints have been based, in the past, on resins designed for reduction with organic solvents. However, today the formulator must use water-reducible resins to a greater extent as the base for these industrial products. It is extremely important. he said. to recognize that the presence of water introduces the possibility of microbial problems in the production. storage, and application of these newer coating systems. Mr. Machemer talked in depth about an approach aimed at providing total microbial control in storage, during application, and on exposure.

CHARLES B. WILSON. Vice-President

Pittsburgh April 3 "HYDR~PHOBIC WETTING I N AQUE-

OUS SYSTEMS" was discussed by Rob- ert W. Vash. of Byk-Mallinckrodt.

Mr. Vash said wettingagents work by replacing air and moisture at the pigment surface with themselves and are classified by five distinct types: anionic, cationic, electro-neutral, amphoteric. and nonionic. Use of a wetting agent, he added. may help tint acceptance, improve hiding. help remove entrapped air, improve gloss, and reduce flooding and flocculation.

However. post adding wetting agents. which are highly concentration dependent, may result in only part of the surfactant adhering to the pigment surface with the remainder possibly causing an adverse effect on the package stability, he said.

In solvent systems, said Mr. Vash. the vehicle forms a more or less continuous medium with wetting agents forming a double layer around the pigment particles where the outer layer repels the outer layers of other particles. However, in a water-based system. the vehicle exists more as discreet particles to the extent of almost being in a colloidal state and water serves as the continuous medium.

Mr. Vash explained that one part of the molecule attaches to the pigment surface. and the other part of the molecule reachcs out towards the water and repels the molecules. The effec- tiveness of hydrophobic wetting agents depends upon their concentration. and evidence points to !he fact that they are best added at the beginning of a grind. he concluded.

R~HI.:K'I ' T. MARCUS. Src.wton.


Elections

MENDEZ, CALLOS DORANTES - Metno Associate - - Quimica Mexicans, S.A., Mexico.

Active MONEDERO, ROSA MARIA ROJAS- ~ h i l P m ~ R ~ ~ . DANA J.-Union Carbide Gorp..

las, S.A.. DE C.V.. Mexico, D.F. Needham Heights, Mass. SHARP, LOUIS J. - L~lly Industrial Coatings, PEREZ, A G U S ~ N HERRARA - Alcan ~ l ~ m i -

Inc., Indianapolis, Ind. nio, S.A., Tulpetlac, Edo De Mex. Retired SANTILLAN, EMILIO R. - Industrias Resis- PARKER CHARLES ~ . - ~ t ~ b b i ~ ~ ~ ~ ~ , j ,

MEXICO tol, S.A., Estado De Mexico. RFD X I , Monson, Mass.

TREVINO, JOSE LUIS - Pigmentos y Oxidos,

Active

ALMAGUER. GILBERTO - Pigmentos y Oxidos, S.A., Monterrey, N.L., Mexico.

ALVAREZ, JOSE LUIS GARCIA- Pigmentos y Oxidos, S.A., Nuevo Leon. Mexico.

ARCE~GERARW SANCHEZ-Pinturas Do-AI. S.A., Monterrey.

BREMER. BERNARDO M. - Monquimica, S.A., Monterrey.

CABRERA. REBECA-Cfa. Sherwin Wi lk~m~, S.A. de C.V.. Monterrey.

FLORES, OCTAVIO MIRANDA - PKV Quimica. S.A.. Mexico 20 D.F.

GALINDO, MIGUEL~ARDENAS- Pigmentos y Oxidos, S.A., Mexico. D.F.

IBARROLA. HILARIO E. - El Nervion S.A.. Mexico, D.F.

LARA, JESUS- Hexaquimia, S.A.. Mexico, D.F.

LOZADA, ENRIQUE F. - Pinturas Azieca, S A M e v i r n n F

S.A. Nuevo Leon, Mexico.

NEW ENGLAND

Active

NORTHWESTERN

L?IHAK, F . JACK-Warners Industrial Supplies. Minneapolis. Minn.

ADAMS. JAY W.-The Dampney Co., Associate Everett, Mass.

ALVAREZ. FREDERICK w., ~ r . - ~ ~ ~ t ~ ~ ~ WHITING. JAMES F.-N L Industries. Inc.. Lacquer Corn., Malen. Mass. Bensenville, Ill.

A R C H A M B A U L ~ . J. PAUL C.-Markem Corp., Keene, N.H.

BISCAN. WILLIAM A.-Kyanize Paints, Inc.. Everett. ROCKY MOUNTAIN

BRAKKE. N. B R A D F O R ~ L ~ ~ ~ ~ Chemical Prod., Templeton, Mass. Associate

KIRSCH. SEYMOUR D.-Linatex Corp. of SCHWEIGER. CRAIG S.-Thompson- America, Peabody, Mass. Hayward Chemical Co., Denver, Colo.

NETEZCHLEBA. FRANK S.-Eastern Chem- SMITH. WILLIAM L.-Dresser Minerals, Lac Corp., Malden, Mass. Houston, Tex.

1 High Spocd Shot Mills

iCHOL0 MACHINE CORPORATION

Val. 50, No. 641, June 1978 85

Technic01 Rrticles in Other Publications Compiled by the Technical Information Systems Committee-H. Skowronska, Chairman

Double Liaison - Chimie Des'Peintures (in French)

Published by Les Presses Continentales, Rue de Cherch-M~di. F-75006. Paris, France

Vol. 25 No. 271 March 1978

Toussaint. A.. Piens, M.. Padina, E., and Scimar, R. - "Wash- Primers; Their Use;" 23-27.

Pepin, B. - "Zinc Phosphate - Strontium Chromate in Water-Based Anti-Corrosive Primer"; 29-38.

Grimm. M. - "Influence of Chlorinated Aliphatic Hydrocarbons on the Characteristics of Alkyd Resin Films;" 41-43.

Faidutti, M. - "Solvent Toxicity and YL (Ysam) System;" 44-47.

Farbe und Lack (In German)

Published by Curt R. Vincentz Verlag, 3 Hannover. Postfach 6247. Schiffgraben 43. Germany

Vol. 84 No. 4 April 1978

Schmelzer, H. - "Color-Matching for Letterpress and Offset Printing Inks:" 208-212.

Bagda, E. - "The Connection between Surface Tension and Solu- bility Parameter in Fluids;" 212-215.

Hosp. E. - "Problems of Adhesion Testing with the Tear Method (2): Holographic Determination of the Distribution of Stress in Plane Models of the Test Punch;" 216-220.

Reisch, B. and Rosenberg. A. - "Modem Alkyd and Epoxy Resins. Their Curing by Radiation and Their Suitability as Binders for Offset Printing Inks;" 220-225.

Brushwell. W. - "Coatings Based on Polymer Resins" (literature review); 226-227.

German Standard Draft DIN 6164 Part I: DIN Colour Chart; System Based on the 2"-Standard Colorimetric Observer; 234-236.

German Standard Draft DIN 6164 Part 2: DIN Colour Chart; Specifi- cation of Colour Specimens; 237.

German Standard Draft DIN 617 1 Part 1: Surface Colours for Traffic Signs; Colours and Colour Limits for Illumination by Daylight; 238-242.

Skandinavisk Tidsskrift f6r Farg och Lack Published by Dansk Bladforlag KIS, Holbersgade 20, 1057

Copenhagen. Denmark

Vol. 24 No. 2 February 1978

Eikers. E.-"Cathodic Protection is not a 'Sort o f Science;" 35-41. Hansen. W.-"Use and Abuse of Ink Standardization;" 42-56

(9 pages).

Vol. 24 No. 3 March 1978

Igetoft, L. - "Pretreatment and Painting of Galvanized Steel - An Investigation by Laboratory and Field Tests;" 69-87 (in Swedish).

IndustrieLackier-Betrieb (In German)

Published by Curt R. Vincentz Verlag. Postfach 6247.3000 Hanover I . Schiffgraben 43. Germany

Vol. 45 No. 9 September 1977

Ziegweid. J.E. - "The Problem of Static in Electrostatic Spraying;" 339-342.

Weigel. K. - "Powder Coating Layering on Heaters;" 343-346. Golibrzuch, W. - "Thermal Purification ofout-going Airand Coating

Techniques;" 347-350.

Vol. 45 No. 10 October 1977

Gork. W. - "Furniture Coatings and Universal Protection;" 377-379. Ziegweid. J.E. - "The Problem of Static in Electrostatic Spraying.

Pan 11;" 380-384.

Vol. 45 No. 12 December 1977

Miiller, 0. - "New Ideas for Planningand ConstructionIBuilding with LayeredlStratified DesignlArrangement;" 447-448.

Bahlmann. W. - "Mechanical Surface Preparation. Part 11;"453-457. Trepels. M. - "Removal of Coating Residues in Spray Booths;"

458-460.

Vol. 46 No. I January 1978

Van Eijnsbergen. J.F.H. - "Duplex System - Twenty Years of Expe- rience;" 5-6.

Franzoni. A.M. - "Quality Powder Coatings as a Result of Correct Curing Conditions;" 7-10.

Wilde. H. -"The State ofsafety Techniquesfor Dryingof Coatings;" 11-16,

Paint Manufacture Published by Wheatland Journals Ltd.. 157 Hagden Lane. Watford

WD I . 8 LW. England

Vol. 48 No. 3 March I978

Walton, A.J. - "Interactionsin Non-Aqueous Paint Systems. Part I:" 29-32.

Plaste und Kautschuk mit Fachteil Anstrichstoffe (In German)

Published by VEB Deutscher Verlag fiir Grundstoffindustrie. 27 Karl-Heine-Strasse. 7031 Leipzig. E. Germany DDR


Jeremejewa. T.W.. Jewereinow. W.W.. Dawydowa. J.W.. Kar- jakina. M.I.. Sarynina. L.I.. and Entelis. S.G. - "Studies on De- termination of Molecular Weight and Functionality Distribution of Oligoesters by Adsorption Chromatography:" 192- 194.

Journal of Coat ings Technology

Verfkroniek (in Dutch)

Published by Groot Haesebroekseweg I . Postbus 71. Wassenaar. Netherlands

Vol. 51 No. 2 February 1978

Riberi. B.-"Combinations of Coal Tar and Polyurethanes;" 39-43.


Daniel. F.K. and Pineiro. R. - "Economic and Technical Parameters of Pigment Dispersions;" 66-7 1.

Coatings and Plastics Preprints

1 Now theresa 1 fast, economical

alternative to field exposure

studies.

Preprints of Papers Presented before the ACS Division of Organic Coatings and Plastics Chemistry

Anaheim. Calif. March 1978 Vol. 38 No. I I Fracture Mechanics of Polymers (30 papers); 1-23. 81-105. 152-184.

236-256, 306-327. 394-4 17. Additives for Plastics and Coatings (I8 papers); 24-60. 106-132, 185-

218. Computer Applications in Coatings and Plastics (8 papers); 61-80.

133-151. Dynamic Mechanical Studies of Polymers (Borden Award Sym-

posium honoring J.K. Gillham) (I4 papers); 219-235.284-305.355- 391. - .

Electrical Properties of Polymers (30 papers); 257-283.328-354,4 18- 449. 516-549. 61 1-633.

New Concepts in Coatings and Plastics (9 papers); 450-476.694-7 15. High Performance Composites (17 papers); 477-515. 576-610, 662-

693. Polymeric Thin Films (I5 papers); 550-575. 634-661.716-742, Inquiries regarding price and availability of this preprint book should be sent to Dr. S.S. Labana. Scientific Research Labs. Ford Motor Co.. P.O. Box 2053. Dearborn. Mich. 48121.

Polymer Preprints Preprints of Papers Presented before the ACS Division of Polymer

Chemistry

Anaheim. Calif. March 1978 Vol. 19 No. I

Witco Award Symposium Honoring J . Furukawa (Abstracts of 9 papers); 1-4.

Multicomponent Polymer Systems (40 papers); 5-215. Sequence Distribution in Polymers as a Function of Reaction Condi-

tions (I2 papers); 2 16-285. Stress-Induced Crystallization-Part 11 ( 2 2 papers): 286-368. Polymeric Drag Reducers (I2 papers); 369-435. Special Topics in Polymer Chemistry ( 5 ! papers): 436-704. Electrical Properties of Polymers (abstrilcts of 30 papers): 705-713.

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Vol. 50, No. 641, June 1978

.lTleetin~)s / Educcrtion

PNW Spring Symposium Draws Over 300 An attendance of 312 was recorded at

the 1978 annual symposium of the Pa- cific Northwest Society for Coatings Technology, May 4-6, in Seattle. The Puget Sound Section was host.

The Program Chairman was Curt Bailey, of Parker Paint Co. He was as- sisted by Robert Hogg, Bill Clary, Don McKenzie, George McKee, Bob Ro- denberg, Lou Waldron, Miki Na- kamuia, Fred Schmucker, Jim Roberts, Morris Moen, Bill Shackelford, and Mrs. Bailey (Lynne).

The Federation was represented by President John Oates and Executive Vice-President Frank J. Borrelle.

Technical Program

The program sessions included the following presentations:

t "Use of Straight Chain Ketones in Formulating Air Pollution Exempt Coatingsw-James Dickert, of Eastman Chemical Co.

"New Concept of Pigment Wetting in

Aqueous Coating Systems5'-Wolfgang Zinnert, of Byk-Mallinkrodt.

"Technical Features and Attributes of the Micro-Element Media Millsm- Myron Segal, of Premier Mill Corp.

"Fire Protection-Your Workers and YourPlant"-Melvin V. Harris, of Ver- Ian Ltd.

"Paint Industry: Hazardous Chem- icals"-Peter Breysse, of University of Washington.

"Innovations in Water-Reducible Coatings"--George H. Wilhelm, of Ashland Chemical Co.

"The Paint Research Institute-An UpdateM-Mr. Oates.

"Future Economics of Latexes for Coatingsw-Lowell R. Comstock, of Union Carbide Corp.

Business Session

During the annual business meeting, Society President, Bill Shackelford, presented a check for $425 to the Paint Research Institute. President Walt Bal-

linger, of the Golden Gate Society, presented a check of $500 to PRI. Both were accepted by Mr. Oates.

The traditional competition between the three sections (Portland, Puget Sound, British Columbia) of the Society transferred to the stage this year in the form of an "International Skits Compe- tition." Each group presented its comi- cal version of a typical Society meeting.

New Officers

Oflicers for the coming year will be: President-Michael Griffin, of Reichhold Chemicals Ltd.; Presi- dent-Elect-Walter Clyde, of Glidden- Durkee Div.; Secretary-Curt Bailey, of Parker Paint Co.; Treasurer-Dick Stewart, of Mills Paint Sales Ltd.; Council Representative-John A.J. Fil- chak, of General Services Administra- tion; and Administrative Secretary- Charles Bededeard, of Gaco Western, Inc. The 1979 symposium will be held in Vancouver. May 3-5.

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The NiPar S-30 finish has superior film integrity. No cotton-like pre- cipitate or milky discoloration.

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NiPar S-30 (nitropropane solvents). It solves your problems.. . without creating new ones.


Dallas and Houston Societies Host 300 at Paint Convention Three hundred and one persons at-

tended the 1978 Southwestern Paint Convention of the Dallas and Houston Societies, April 13-15, in Dallas.

Ollis Walker, of Standard T Chemical Co., was General Chairman and Steve Prodromo, of N L Industries, sewed as Vice-Chairman. The Program Chair- man was Sam Biffle, of Sherwin- Williams Co. Others on the Dallas Host Committee were: Don J. Webb, William F. Holmes, Levell L. Stephens, Carlos E. Doms, Ray C. Pierrehumbert, JoeL. Broome, Noel L. Hamson, and Duane & Lisa Smith.

The Federation was represented by President John J. Oates and Executive Vice-hesident Frank J. Borrelle. At the Saturday luncheon, Mr. Oates was presented the President's " 10-gallon hat," a tradition of the SW Paint Con- vention.

The two-day program consisted of the following presentations:

"Design Experiments for Research and Productionm-Ralph DeBusk, of

Eastman Chemical Products, Inc. "Fundamentals in Color Pigment

Selections"-Ralph Edelman, of E.I. du Pont de Nemours & Co., Inc.

"Particle Size and Shape and Effect on Water-Based Coatings7'-George P. Larson, of Georgia Kaolin Co.

"Acrylic Latex Maintenance Paintsw-Martin 1. Grourke, of Rohm and Haas Co.

"Microbiological Problems Associ- ated with Water-Reducible Industrial Coatings"-William E. Machemer, of Troy Chemical Corp.

"Heavy Metal Additives for Coat- ings-A Prospectivew-Samuel Bel- letiere, of Tenneco Chemicals, Inc.

"Fifty Years of Optical Properties in the Paint and Coatings Industry"- Richard S. Hunter, of Hunter Associ- ates Laboratory, Inc.

A report on the 1978 Water-Borne and High Solids Conference--Dr. Rob- ert Burke, of the Department of Polymer Science, University of South- em Mississippi.

The 1979 Southwestern Paint Con- vention will be held at the Shamrock Hilton Hotel, Houston, April 5-7.

OCCA-30 Hosts Visitors From 53 Countries at Exhibition

The Oil and Colour Chemists' Asso- ciation held its 30th annual technical exhibition, OCCA-30, at Alexandra Palace in London, April 18-21.

The very successful event was at- tended by visitors from 53 countries, who viewed the exhibits of 147 organizations featuring raw materials, plant, and equipment for the paint, printing ink, color, and allied industries.

The Association has announced that OCCA-31 is scheduled to be held April 3-6, 1979. Again, the site will be the Alexandra Palace. Details regarding exhibiting in or attending the exhibition are available from R.H. Hamblin, Di- rector and Secretary, Priory House, %7 Harrow Rd., Wembley, Middlesex, HA0 2SF, England.

Vol. 50, No. 641, June 1978

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89

J. Roger Garland, of Gulf and West- em Industries, Inc., has received the 1978 Liberty Bell Award of the Philadelphia Society for Coatings Technology. Mr. Garland, who is a Past-President and former Technical Committee Chairman of the Society, is the 41 st person so honored for outstanding contributions to the advancement of the protective coatings industry and the Philadelphia Society.

Air Products & Chemicals, Inc., Al- lentown, Pa., has named F.J. Ryan to the newly-created position of Group Vice-President for Chemicals, Poly- mers, and Plastics. Formerly Vice- President of the Industrial Chemicals Div., he has been with the company since 1957.

The company, in a re-organization of management, has named Edward Don- ley Chairman and Chief Executive Of- ficer; Dexter F. Baker has succeeded him as President and Chief Operating Officer; Leon C. Holt, Jr. is Vice- Chairman and Chief Administrative Of- ficer; and Richard Fleming has been named Executive Vice-President.

Hilton-Davis Chemical Co., in a major reorganization of its Pigments and Chemicals Divisions' sales and marketing efforts, has appointed Robert L. Dittmar General Manager of the Pig- ments Div., while Douglas H. Threader was named General Manager of the company's Chemicals Div.

Reporting to Mr. Dittmar will be Rob- ert F. Sharrock, Director of Marketing, and Gustav Gurska, National Sales Manager for pigments. In the Chemicals Div., Mr. Threader has reporting to him Richard L. Humbert, Director of Mar- keting, and Edward J. Britton, National Sales Manager of the division.

In two divisional appointments, Con- chemco Coatings has named Charles W. Barnes Ill Vice-President and General Manager of the company's Western Div. R.E. Whiting has been named to the same positionsfor the Southwestern Div. of the company.

Dana J. Peterka has been promoted to District Sales Manager for the Coatings Materials Sales Force of Union Carbide Corp. Operating in the company's New England Region, Mr. Peterka will be based in the Needham Heights (Bos- ton), Mass. office.

J.R. Garland G. Malkin

Gabriel Malkin was chosen as the re- cipient of the New York Society for Coatings Technology's PaVaC Award for 1978. This honor is bestowed on members of the Society "for their outstanding contributions to the advancement of the coatings industry and the New York Society."

Mr. Malkin retired March I as Chief Engineer of Benjamin Moore & Co. after 28 years with the company. He has served as Mission Manager of the NPCA Water Quality Task Force and as a member of the Air Quality Task Force and continues to serve on these task forces. He has also served as Chairman and member of numerous committees for the Society and the Federation, and continues to serve the Federation as Delegate to NPCA and Governmental Agencies (Environmental Control).

Paul G. Tietze has been appointed Laboratory Group Leader for Witco Chemical C o p . at its Technical Center in Oakland, N.J.

Robert P. Marshall has been appointed District Sales Manager for Ameron, Inc., Protective Coatings Di- vision, in the newly-formed Mid-States District. The district, headquartered in Detroit, will encompass the marketing areas of Michigan, Ohio, West Virginia. and Kentucky.

Applied Color Systems, Inc.. Devon, Pa., has appointed JamesT. DeGroff to its corporate staff as Manager of Busi- ness Development.

William E. Younger has retired as President of C.M. Athey Paint Co., Bal- timore, Md. He has been associated with Athey Paint since 1939. Mr. Younger will retain his position on the Board of Directors and will remain Pres- ident of the Burch Paint and Glass Co. and McPhail Paints. Inc.

D.J. Fritz R.F. Wilkinson

Donald J. Frib has joined the Supe- rior Varnish & Drier Co., Mer- chantville, N.J., as Technical Director. His responsibilities include planning, directing, and coordinating the technical and quality control activities of the company. Mr. Fritz, previously employed by NL Industries, Inc., Dutch Boy Paint Div. and Synres Chemical Cop. , is a member of the Board of Di- rectors of the Federation and is a Past- President of the Philadelphia Society.

Robert F. Wilkinson has been appointed to the newly-created post of Di- rector, Manufacturing Services, of PPG Industries' Coatingsand Resins Div. He will be responsible for coatings and resins processing and materials management for the division. Succeeding him as Divisional Director of Planning and Development is Malcolm Hay, Jr.

Eastman Chemical Products, Inc. has made two marketing appointments: Bruce E. Moore has been named Assist- ant Director of Marketing of the company's Coatings Chemicals Div., and will be headquartered in Kingsport. Tenn.; Fred W. Voigt has been named Senior Marketing Representative for the division in New Jersey.

James C. Fitzpatrick has been named Eastern Sales Representative for Hodag Chemical Corp. Mr. Fitzpatrick will be based in Woodbridge. N.J.

Anthony P. Bianciella has been promoted to Manager, Corporate Engineer- ing for Drew Chemical Corp., Boonton, N.J. In his new position, he will super- vise the areas of project engineering. engineering services. and process engineering.

Ted Grobelny has been named Mar- keting Program Manager for Thiokoll Chemical Division. Trenton. N.J.


Reichard-Coulston, Inc. has announced the retirement of Morton Treade after42 years of service with the company. Mr. Treade, who was the company's Technical Service Manager, is a Charter Member of the New York Pigment Club, a Paint Pioneer of the New York Paint Varnish and Lacquer Association, a member of the New York Society for Coatings Technology, and a Patron Member of the Steel Structures Painting Council. Mr. Treade was a re- cipient of the Roy H. Kienle Award in 1971 for "technical achievement and outstanding services rendered to the Technical Committee of the New York Society". He is a graduate of Brooklyn Polytechnic Institute, class of 1924.

Edward J. Brislin has been named Manager of the West Coast Dept. of R.T. Vanderbilt Co., Inc.

Wallace A. Stede has been appointed General Manager of the Chemical Coat- ings Div. of Pratt & Lambert, Buffalo, N.Y.

Glidden Coatings & Resins has named James D. Russell Eastern Region Trade Sales Manager, headquartered in Reading, Pa. Succeeding Mr. Russell as Manager-Product Planning at Glidden headquarters in Cleveland is James Sainsbury.

du Pont Co.'s Polymer Product Div. has established a new profit center for coating resins and chemicals, which consolidates marketing, manufacturing, research and product development activities. Heading the profit centerwill be William A. Lewing, formerly National Sales Manager for the division.

The Board of Directors of Sherwin- Williams Co. recently re-elected William C. Fine President and elected Geoffrey L. Tickner Group Vice- President of the newly-formed General Products Group.

Dr. Marco Wimer, Vice-President of Research Development, Coatings and Resins Div., PPG Industries, Inc., presented a talk on "Progress in Elec- tropainting" at the Conference on "The New Technologies for Industrial Finishing," in London, England, May 23-25. The conference was sponsored by the Paint Research Association of England. Speakers from seven countries participated.

Conchemco Chemicals. Inc. has ao- pointed James 8. simpson Technical 6- rector of its Resin Laboratorvin Kansas City, Mo. Mr. Simpson has 24 years experience in the formulation and production of resins.

John E. Fikwater, Jr. has been appointed Technical Service Supervisor for coating products by Polyvinyl Chemical Industries, Wilmington, Mass. He will be responsible for the coatings applications and technical service laboratory.

Manreen P. Thorn and Warren Davis have been appointed Technical Sales Representatives for ThiokollChemical Div., Trenton, N.J. Ms. Thorn will be responsible for the area of northern New Jersey and Pennsylvania and southeastern New York, including Long Island. Mr. Davis will cover the southeastern United States.

Richard Fleming, of Air Products & Chemicals, Inc., has been re-elected Chairman of the Chemical Industry In- stitute of Toxicology.

atural armor plate longer lasting paint

e lmpervlous plates of armor, the tiny mica flakes dis-

netration, heat, light, and chemicals. Muscovite of significant importance as a secondary pigment in

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Vol. 50, No. 641, June 1978

People (Continued,

The new officers of the Society of Plastics Engineers were installed at the 36th annual technical conference in Washington, D.C., April 24-27. Assum- ing office were: President-Jack L. Isaacs, of General Electric Co., Louis- ville, Ky.; President-Elect-Joseph Magliolo, Jr., of Southwest Chemical and Plastics Co., Seabrook, Tex.; First Vice-President-George P. Schmitt, of IBM Corp., Endicott, N.Y.; Second Vice-Resident-Howard T. Ysteboe, of Berg Electronics Div., du Pont Co., New Cumberland, Pa.; Secretary- James E. Chinners, Jr., of Diamond Shamrock Corp., Cleveland, Ohio; and Treasurer-Reed H. Belden, of Allied Chemical Corp., Momstown, N.J.

Southern Protective Products Co., Atlanta, Ga., has appointed Norman Stephens Director of Sales and Market- ing.

Bill Dillman has been named Sales Coordinator for Penn Color, Doyles- town, Pa. He succeeds Tom Niehaus, who is retiring.

Paul J. Lesniewski has joined Armstrong Products Co. as Field Sales Engineer and will be responsible for the temtory in the northeast U.S. He will be based in Branford, Conn.

In recently announced staff changes at the National Paint and Coatings As- sociation, Royal A. Brown was named Vice-President, Technical and John M. Montgomery was named Vice- President, Law. Raymond J. Connor, formerly Assistant Director, succeeds Mr. Brown as Director of the Technical Division. Larry Thomas, formerly As- sociate General Counsel, succeeds Mr. Montgomery as General Counsel.

Obituary Homer C. Reed, retired Vice-

President of Kerr-McGee Corp., died March 21 in Laguna Beach, Calif. He was 69 years old.

Ray Eastman, retired from Frost Paint and Oil Co., Minneapolis, Minn. and a Past-President of the Northwest- em Society (1959). died in March.

Julius Shugar, co-founder of the Bal- timore Paint and Color Works Co., died in Pompano Beach, Fla., March 27, while vacationing. He was 73 years old.

William L. Minarik, 53. of H.B. Ful- ler Co., St. Paul, Minn. and a Past- President of the Northwestern Society for Coatings Technology (l974), died in March.

Automated Weathering

- Accelerated QmUmV - Weathering Tester

.Unique Condensation rnechan~sm simulates raln and dew. Fluorescent UV lamps simulate sunlight.

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Low initial cost, plus yearly operating savings of thousands of dollars over carbon arc and xenon arc. Plugs in anywhere and uses ordinary tap water. Service required just once a month.

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CALL FOR PAPERS - CORROSION/79

National Association of Corrosion Engineers March 12-16, 1979 - Atlanta, Ga.

Corrosion Research Conference

Five technical sessions are planned for the 1979 international corrosion forum:

Environmentally Induced Brittle Fracture Processes Under Static and Dynamic Loadings

Mechanisms of Breakdown of Passivity

Surface Chemistry and Its Influence on Atmospheric Weathering Behavior of Metals and Alloys

Inhibition of Corrosion Process

General Sessions

Persons with fundamental corrosion research in progress on the above topics wishing to make a presentation at the NACE Corrosion Research Conference should send a title and brief abstract, priortoJuly 1,1978, to Chairman Dr. Ellis D. Verink, Jr., Dept. of Materials Science and Engineering, University of Florida, Gainesville. Fla. 3261 1.


Literature

Auto Sampler A two-page data sheet presenting a

new auto sampler, Model AS-50 for flame atomic absorption is now available. The brochure describes the instrument keyboard functions and the automatic analysis features. For further information, write for bulletin L-534, Perkin-Elmer Corp., Instrument Div., Main Ave.. Mail Station 12, Norwalk. Conn. 06856.

Liquid Flooring A four-page color brochure is avail-

able which describes a new nonporous flooring of colored ceramic quartz granules fused during application into a seamless topping with specially formulated 100% thermosetting epoxy resins. For further information, write Dur-A- Flex. Inc., 100 Meadow St., Hartford, Conn. 061 14

Dust Collection Literature describing a new energy

efficient concept for controlling air- borne dust at belt conveyor junction points is now available. The installation of a continuous action insertable dust collector without long runs of duct work is shown. Forfurther information, write DCE Vokes Inc., Suite 900A, Plainview Plaza, 10101 Linn Station Rd., Jeffer- sontown, Ky. 40223

Precision Balance Literature describing a new elec-

tronic balance designed for the paint industry is now available. The device features three displays, making it easy to mix two or more ingredients, weigh- out portions, or compare actual with desired values. Further information on Model RS 25 may be obtained by writing to August Sauter of America, Inc., 80 Fifth Ave., New York, N.Y. 10011.

Work-Handling Equipment A new eight-page bulletin offers in-

formation about a redesigned line of OSHA-quiet, on-line, automated spraying equipment which handles all flame- spray applications. For copies of the literature, "Metco Flame Spray Handling Equipment," write Metco, Inc., Dept. 937, 1101 Prospect Ave., Westbury, N.Y. 11590.

Analyzing System Literature is available which intro-

duces an instrument that analyzes the volume fraction of liquidiliquid, solid1 liquid, liquidlgas, and solidlgas flows. The system's patented rotated field sen- sor permits measurements over 100% of the cross-section of a circular pipe. For more information, contact Auburn International, Inc., Charles C. Snell, Product Manager, One Southside Rd., Danvers, Mass. 01923

We're helping Ford with a bright new look. At a recent Coating Society Symposium in manufacturing excellence.

Cleveland. Ford Motor Company revealed that If yourstandardsdeserveourproducts,writeor they have improved paintappearance.Oneofthe call to find out howwe can improve your product. reasons: HunterLab's D47R-6F DORIGON Dis- tinctness-of-Image Abridged Goniophotometer.

The D47 allows Ford to monitor specific changes in application techniques, solvent blends, oven-bake temperatures and metal finishing~ to insure that each area conforms to Ford's standards. For the first time ever, our instrument provided Ford with accurate D of I correlation between assembly plants throughout the country. In addition to reducing supervisory requirements.

Our complete line of glossmeters, spectro- photometers and calorimeters are designed for companies like Ford who pride themselves on

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Vol. 50, No. 641, gune 1978 93

Letters to the Editor Accelerated Weathering Data Should Be Listed

TO THE EDITOR: In the article. "Accelerated Tests of

Weather-Resistant Natural Finishes for Pinus rudiaru." [Ser February JCT, pp 59-64-Ed.] the authors refer to a carbon arc Weather-Ometerm Model 600-WR operated according to ASTM Recommended Practice G 23-69.

The Atlas Model 600-WR Weather- Ometer employs a xenon arc. not a carbon arc. Since the New Zealand Forest Service does not have a Model XW carbon arc Weather-Ometer. I have confirmed though correspondance with the senior author, Alan Preston, that expo- sures were conducted in their Model 600-WR Weather-Ometer and the reference should be to G 26-70. "Recom- mended Practice for Operating Light- and Water-Exposure Apparatus (Xenon-Arc Type) for Exposure of Non-Metallic Materials."

The exposure conditions employed by the authors, xenon arc, 18 min light and water spray followed by 102 min of light only for 2500 hr, is quite different from those reported by Black and Mraz whom the authors reference in the USDA Forest Service Research Paper FPL 232 (1974). Black and Mraz report exposure in a Model XW carbon arc Weather-Ometer for 16-20 weeks. 5 cycles per week of 7 hr water spray followed by 17 hr light only.

As the spectral energy distribution contributes to the photodegradative effect [JCT. 49 No. 633. 37 (197711 it is important to describe correctly and in detail the conditions of exposure. Both ASTM Recommended Practice G 23 and G 26 already state that reference to them should not be made unless accom- panied by the information specified in the report section. If this is adhered to. there will be less confusion and readers mayjudge betterthe significance ofpub- lished results.

RAYMOND A. KINMONTH. JR. Atlas Electric Devices Co.

CLASSIFIED ADVERTISING

CONSULTANT European company requires resins and additives Consultant for paints and coatings. Experience in product formulation and application technology essential. Write Box 101, c/o Journal of Coatings Technology, 1315 Walnut St., Phila.. Pa. 19107.

ASTM Designation G 26 Report Form

Laboratory Forest Research -- Institute-

Material C l e ~ f i n i s h e s on pre-treated Pinus radirrta - - - -~ - - -

G 26 Test Method No. 2/77 - - -.

Reference Standard Used U n e x p s e d replicates - -

Other ASTM Test No. D 164 1-59 ~p - - --

Exposure Apparatus: ASTM Type AH- - - -

Mfr. Model -- 600-WR - . Weather-Ometer - - - ~ -

Light Source: Water Cooled 6000 W ~p .- -

Method Used to Regulate Wattage to Lamp Manual schedule - -

Optical Filters: Type Borosilicate, Age Outer - 0-2000 hr. Inner - 0-400 hr.

Spectral Irradiance: ! x W l m 2 a t 420 nm

lrradiance Units 50-60 pW/cm2/nm -- -

Elapsed Exposure Time -1500Jh - -- -

Exposure Conditions: Program 2 hr. Light 120 rnin - - -

Black Panel Temperature . . . . . . . . . .6I0C Air Temperature . . . . . . . . . . . . . . . . .20"C Dry Bulb Temperature . . . . . . . . . . . .48.S'C

. . . . . . . . . . . . . . . Relative Humidity .53% Specimen Water Spray . . . . . . . . . . . .I8 min cycle Specimen Nonspray ............. .I02 min cycle

Specimen Spray Water Type Distilled_ - --

Specimen Spray Nozzle Type: Mfg. Designation F-80--~ Specimen Relocation Procedure During Exposure Random

--

TO THE EDITOR: As Mr. Kinmonth correctly points

out. our Weather-Ometer is indeed an xenon arc model and we should have referred to the exposure practices as being carried out in accordance with ASTM G 26 and not G 23 as stated.

We consider it appropriate that this information (shown above) be made available to JCT readers. This should assist in making readers and authors aware of the different techniques possible in accelerated weathering studies.

ALAN F. PR~STON Forest Research Institute

More on Linseed Oil Article TO THE EDITOR:

I understand and applaud the effort5 of Dr. Rakoff s department. to help that segment of our farm communily represented by the Flaxseed Processors As- sociation, since anything which will assist our farm production is of great val-

ue. LSw Lettc~rs to thc Editor. May JCT. p 114 - Ed.] However. my entire point is that these important efforts have come too late. in this case, and represent mis-spent effort.

Tenneco. Mooney Chemical. and many others have run comprehensive tests on all types of drying oils (including, of course. linseed). substituting driers other than lead. The other branches of government. whose edicta we must ohserve, have ruled out lead in most forms. for most purposes in paints regardless of thc form in which i t is used. for domestic-type products.

If suggestions are in order from the field. may I offerthis'? Efforts should he spent pre.;erving the continued use of linseed oils through upgrading of thc few factors which have brought other and better product. to the market. such as improved col$ir retention, hC!ler chemical resistar~ic. etc.

E v ~ R ~ : I - ~ G. Corn President. Multi Coat Corp.


Coming events

FEDERATION MEETINGS (Nov. 1-3)-56th Annual Meeting and 43rd Paint Industries'

Show. Conrad Hilton Hotel. Chicago. Ill. (FSCT. Suite 830. 1315 Walnut St.. Philadelphia. Pa. 19107).

SPECIAL SOCIETY MEETINGS

(Feb. 28-Mar. 2)-Western Coatings Societies' Symposium and Show. Fairrnont Hotel. San Francisco, Calif. (Ed Kevin. The O'Brien Corp.. 450 E. Grand Ave., South San Francisco, Calif. 94080).

OTHER ORGANIZATIONS (July 10-13)-World Conference on Future Sources of Or-

ganic Raw Materials. Toronto. Canada. (Chemical Institute of Canada. 906-151 Slater St.. Ottawa, Ontario, Canada K IP 5H3).

(July 13-14)-2nd European Conference on Flammability and Fire Retardants. Sheraton Hotel. Copenhagen, Denmark. (Vijay Mohan Bhantagar, Editor, "Advances in Fire Retardants," 209 Dover Rd.. Cornwall. Ontario K6J 1T7. Canada).

(July 17-21)-Fourth International Conference in Organic Coatings ScienceandTechnology. Apollon Palace Hotel, Athens. Greece. (Prof.AngelosV. Patsis, CSB 209. StateUniversityof New York, New Paltz, N.Y. 12562).

(July 23-27bArchitectural Aluminum Manufacturers Asso- ciation Summer Committee Week. Hyatt Regency Chicago. Chicago, Ill. (Barbara Lewke. Meetings Coordinator. AAMA. 35 E. Wacker Dr., Chicago, 11. 60601).

(July 24-28)-"Coatings and Polymer Characterization" Conference. Kent State University, Kent. Ohio. (Carl J. Knauss, Chemistry Dept.. Kent State University, Kent. Ohio 44242).

(July 31-Aug. 4)-Gordon Research Conference on "Physics and Chemistry of Coatings and Films." Proctor Academy. An- dover, N.H. (Dr. Alexander M. Cruickshank. Director, Pastore Chemical Laboratory, University of Rhode Island, Kingston, R.I. 02881).

(Aug. 21-23)-First International Conference on Durability of Building Materials and Components. Ottawa, Canada. (K. Char- bonneau. Executive Secretary, National Research Council of Canada. Ottawa, Canada KIA OR6).

(Sept. 10-15)-176th American Chemical Society National Meeting. Miami Beach, Fla. (A.T. Winstead, ACS, 1155 16th St., N.W., Washington. D.C. 20036).

(Sept. 12-15)-Scientific Colloquium on Corrosion in Water. Pecs. Hungary. (Scientific Societyof Mechanical Engineers. 1372 Budapest. P.O. Box 451, Hungary).

(Sept. 14)-NPCA Regional Seminar on "Fire Protection." New York. N.Y. (Georgene Savickas. Director, Meetings and Con- ventions. National Paint and Coatings Association, 1500 Rhode Island Ave.. N.W., Washington, D.C. 20005).

(Sept. 19)-NPCA Regional Seminar on "Energy Analysis and Conservation." Chicago, Ill. (Georgene Savickas, Director. Meetings and Conventions. National Paint and CoatingsAssocia- tion, 1500 Rhode Island Ave., N.W., Washington, D.C. 20005).

(Sept. 26-28)-AFPISME Conference on Radiation Curing. Holiday Inn O'HarelKennedy. Rosemont. IIi. (Association for Finishing Processes of SHE. Technical Div.. 20501 Ford Rd., P.O. Box 930. Dearborn. Mich. 48128).

(Sept. 27-29)-National Coil Coaters Association Fall Tech- nical Meeting. Hyatt Regency Hotel. Washington, D.C. (Don White. NCCA. 1900 Arch St.. Phila.. Pa. 19103).

(Oct. 4-5)-Society of Plastics Engineers RETEC, "Coloring of Plastics XII-Automotive Color." Saw Mill Creek Inn. Huron. Ohio. (Louis J. McDonald. W.R. Grace 8 Co., 880 Deepwoods Dr.. Medina. Ohio 44256).

Vol. 50, No. 641. June 1978

Cornin9 Events

(Oct. 10-11)-National Association of Corrosion Engineers North Central Meeting on "Coatings and the Law." Marriott Motor Inn. Cleveland, Ohio. (NACE, P.O. Box 986, Katy. Tex. 77450).

(Oct. 10-12)--Fifth Annual UMR-DNR Conference and Expo- sition on Energy. Conducted by the University of Missouri - Rolla and the Missouri Dept. of Natural Resources. (Dr. J. Derald Mor- gan, Conf. Dir., 108 Electrical Engineering Dept., University of Missouri - Rolla, Rolla, Missouri 65401).

(Oct. 15-19)-Architectural Aluminum Manufacturers Asso- ciation 42nd Annual Convention. The Contemporary, Walt Disney World, Fla. (Barbara Lewke, Meetings Coordinator, AAMA. 35 E. Wacker Dr., Chicago, 111. 60601).

(Oct. 28-Nov. 3)-Fifth Annual Meeting of Federation of Ana- lytical Chemistry and Spectroscopy Societies. Hynes Memorial Auditorium, Boston, Mass. (P. Lublin, GTE Labs, 40 Sylvan Rd.. Waltharn. Mass. 02154).

(Oct. 30-Nov. 1)-National Paint and Coatings Association Annual Meeting. Palmer House, Chicago, Ill. (GeorgeneSavickas, NPCA, 1500 Rhode Island Ave., N.W., Washington, D.C. 20005).

(Nov. 8-9)-Powder Coating Conference. Convention Center, Cincinnati. Ohio. (Association for Finishing Processes of SME, 20501 Ford Rd.. Dearborn. Mich. 48128).

(Nov. 13-15)-Society of Plastics Engineers National Techni- cal Conference, "Plastics in Packaging." Hyatt Regency O'Hare, Chicago. (Eugene E. Wilson, SPE, 656 W. Putnam Ave., Green- wich, Conn. 06830).

(Mar. 5-9)-30th Pittsburgh Conference on "Analytical Chemistry and Applied Spectroscopy." (Pittsburgh Section. Ana- lytical Group, et al., Convention Center, Cleveland, Ohio).

(Mar. 12-16)-National Association of Corrosion Engineers Annual Conference and Materials Performance and Corrosion Show, CORROSIONl79. Atlanta Hilton, Atlanta, Ga. (NACE. P.O. Box 986, Katy, Tex. 77450).

(Mar. 22-23bCoatings - 79: International Symposium on Coatings. Carillon Hotel, Miami Beach, Fla. (V.M. Bhatnagar, Alena Enterprises of Canada, P.O. Box 1779, Cornwall, Ont., K6H 5V7, Canada).

(Mar. 29-30)-International Conference on Spectroscopy. Konover Hotel, Miami Beach, Fla. (V.M. Bhatnagar, Alena Enter- prises of Canada. P.O. Box 1779. Cornwall, Ont. K6H 5V7. Canada).

(Apr. 1-6)-Pacific Chemical Conference: 1979. Honolulu. Hawaii. (A.T. Winstead, ACS. 1155 - 16th St.. N.W.. Washington, D.C. 20036).

(Apr. 3-6)-OCCA-31. Oil and Colour Chemists' Association 31st Annual Technical Exhibition. Alexandra Palace. London. England. (The Director & Secretary. Oil and Colour Chemists' Association. Priory House, 967 Harrow Rd.. Wembley, Middlesex, HA0 2SF, England).

(Apr. 19-20)-Second Canadian Chromatography Confer- ence. Hampton Court Hotel, Toronto, Canada. (V.M. Bhatnagar, Alena Enterprises of Canada, P.O. Box 1779. Cornwall, Ont. K6H 5V7. Canada).

(Apr. 25-May 3)-70th Annual Meeting of the American Oil Chemists' Society. Fairmont Hotel, San Francisco, Calif.

(May 18-19)-International Symposium on "Flammability and Fire Retardants." Maria Isabel Sheraton Hotel. Mexico City, Mexico. (V.M. Bhatnagar, Alena Enterprises of Canada, P.O. Box 1779. Cornwall. Ont. K6H 5V7. Canada).

(June 20-23)-Oil and Colour Chemists' Association Confer- ence. "The Challenge to Coatings in a Changing World." Strat- ford Hilton Hotel. Stratford-on-Avon, England. (The Director and Secretary. OCCA. Priory House. 967 Harrow Rd., Wembley. Middlesex HA0 2SF. England).

(June 25-26 and 28-29)-European Conference on Paints and Coatings, "Eurocoatings-79.' Excelsior Hotel, Rome, Italy. (V.M. Bhatnagar. Alena Enterprises of Canada, P.O. Box 1779. Cornwall, Ont. K6H 5V7, Canada).

(July 2-3)-World Spectroscopy Conference. Sheraton Hotel, Lisbon, Portugal. (V.M. Bhatnagar, Alena Enterprises of Canada, P.O. Box 1779, Cornwall, Ont. K6H 5V7, Canada).

(July 5-6)-World Chromatography Conference. Sheraton Hotel. Lisbon, Portugal. (V.M. Bhatnagar. Alena Enterprises of Canada, P.O. Box 1779, Cornwall, Ont., K6H 5V7, Canada).

(Aug. 30-31)--Japan Conference on Polymers and Plastics. Palace Hotel, Tokyo, Japan. (Vijay Mohan Bhatnagar, Alena En- terprises of Canada. P.O. Box 1779, Cornwall, Ontario K6H 5V7, Canada).

(Oct. 3-5)-9th Congress of the Federation of Scandanavian Paint and Varnish Technologists. Stockholm. Sweden.

Advertisers Index

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HUNTER ASSOCIATES LABORATORY, INC. ...................... .93 THIOKOUCHEMICAL DIV.. ....................................... .21

.................................... ........................... IMC CHEMICAL GROUP, INC, &Q, 79,88-89 TROY CHEMICAL CORP. Cover 3

...... ......................................... JOHNSMANVILLE PRODUCTS CORP., FILT. & MIN. DIV. Cover 2 UNlROYAL CHEMICAL.. .10

................................................ .......................................... NALCO CHEMICAL CO. .18 VEBA-CHEMIE AG 11 N L INDUSTRIES, INC., CHEMICALS DIV.. ........................ .4-5

WHITTAKER, CLARK & DANIELS, INC. ............................ 95 ORIEL CORP. ................................................... 8 7 WlTCO CHEMICAL CORP. ....................................... .26

Journal of Coat ings Technology

Eight solid reasons r liquid

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Journal of Coatings Technology 1978 Vol.50 No.641

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Transcript of Journal of Coatings Technology 1978 Vol.50 No.641