ENGINEERING RESEARCH INSTITUTE UNIVERSITY OF MICHIGAN ANN ARBOR Final Report DEVELOPMENT OF A DRY POLYVINYL ACETATE LATEX FOR USE IN WATER PAINTS September 14, 1953, to June 30, 1955 L'. L. Carrick F. L, Keck Project 2195 THE REARDON COMPANY ST. LOUIS, MISSOURI June 1955

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r- ENGINEERING RESEARCH INSTITUTE UNIVERSITY OF MICHIGAN TABLE OF CONTENTS Page LIST OF TABLES LIST OF FIGURES ABSTRACT OBJECTIVE DEVELOPMENT OF A DRY POLYVINYL ACETATE LATEX INTRODUCTION METHOD OF DRYING DESCRIPTION OF FREEZE-DRY PROCESS AND EQUIPMENT DISCUSSION OF EXPERIMENTAL RESULTS USING A PROTECTIVE COLLOID ELIMINATION OF PROTECTIVE 'COLLOID 1. By Washing and Use of Centrifuge 2* By Dialysis in Visking Dialysis Membrane EFFECT OF DRY POLYVINYL ACETATE ON BONDEX AND CEMENT CONCLUSIONS SURFACE TREATMENT OF BONDEX SUPPLEMENT ON THE DEVELOPMENT.OF A LIQUID POLYVINYL ACETATE PAINT SUPPLEMENT ON PAINT AND VARNISH REMOVERS APPENDIX GLOSSARY iii iv v. vi 1 1 1 1 2 2 3 3 4 6 7 8 12 13 17 45 ii

L - ENGINEERING RESEARCH INSTITUTE * UNIVERSITY OF MICHIGAN LIST OF TABLES Page 1. EFFECT OF DRY POLYVINYL ACETATE ON BONDEX AND CEMENT 6 2* WASHABILITY OF SURFACE-TREATED BONDEX 9 3* EXTERNAL EXPOSURE RESULTS OF WATER BASE PAINTS 12 4. EXPERIMENTAL FREEZE-DRIED MODIFIED POLYVINYL ACETATE 18 SYSTEMS iii

ENGINEERING RESEARCH INSTITUTE * UNIVERSITY OF MICHIGAN LIST OF FIGURES Page 1. Bondex surface sprayed with water. 10 2. Bondex surface sprayed with ammonium carbonate. 11 3. Bondex surface sprayed with ammonium sulfate, 11 4. Comparison of laboratory paint and varnish formulations. 15 5. Comparison of commercial and laboratOry-compounded paint 16 and varnish removers. i iv

ENGINEERING RESEARCH INSTITUTE * UNIVERSITY OF MICHIGAN ABSTRACT This report, together with the previous reports on the development of a polyvinyl acetate paint and the development of paint and varnish removers, constitutes a final report of the Reardon Company's contract, September, 1953 to June 30, 1955. The work was directed toward the development of a dry polyvinyl acetate latex which could be used either as an additive to Bondex and similar materials or as a base for a dry polyvinyl acetate paint. The paint would have the characteristic of being nonre-emulsifiable when dispersed in water and applied. Work had been done previously along these lines before Reardon Company's Product Development Department requested the development of a liquid polyvinyl acetate masonry paint and, subsequently, a paint and varnish remover suitable for trade sales. The reports covering the development of a liquid polyvinyl acetate paint and the development of a paint and varnish remover were issued in October, 1954. Further information on the external exposure results relative to the liquid polyvinyl acetate paint is summarized later on page 12, and on page 13 is a brief summary on paint and varnish removers, including pictures of the test panels which were not available at the time of our previous report. In addition to the three major phases of development work done for the Reardon Company, comparative tests were run on two texture paints for Mr, Ben Zmuda, the results of which were reported by letter and in the April, 1955 report. Photographs of the washing tests were sent to Mr. Zmuda later. The work done on the development of a dry polyvinyl acetate latex and polyvinyl acetate paint is discussed on the following pages. v

- ENGINEERING RESEARCH INSTITUTE * UNIVERSITY OF MICHIGAN OBJECTIVE The objectives of this project are as follows: a. The development and testing of vinyl acetate latex paints. liquid poly b. The formulation of paint and varnish removers. c. The testing of texture paints submitted by the Reardon Company. d. Development of a dry polyvinyl acetate latex which could be used either as an additive to Bondex and similar materials or as a base for a dry polyvinyl acetate paint. vi

- ENGINEERING RESEARCH INSTITUTE UNIVERSITY OF MICHIGAN DEVELOPMENT OF A DRY POLYVINYL ACETATE LATEX Introduction METHOD OF DRYING Polyvinyl acetate latex dries by evaporation to form a hard, tough, insoluble film. The problem was to make a dry polyvinyl acetate latex that, once redispersed, would form a film having similar properties. Two methods for drying the latex were considered: (1) spray drying and (2) freeze drying. Spray drying utilizes heat, which might lead to serious blocking problems of any dried polyvinyl acetate latex. Since laboratory equipment for freeze drying was available at the University of Michigan, this method was investigated first. The results were most gratifying; therefore, a freeze-dry unit was constructed in the laboratory. DESCRIPTION OF FREEZE-DRY PROCESS AND EQUIPMENT A brief sketch of the freeze-dry unit employed in our laboratory follows: EXHAUST FUMES I METHANOL I I. BATH I I I!l......../ DOTTED AREA-INSIDE DEEP FREEZE

ENGINEERING RESEARCH INSTITUTE * UNIVERSITY OF MICHIGAN Briefly, material is dried in our laboratory freeze-dry unit as follows. The material (polyvinyl acetate, etc.) is shell frozen in a flask by placing it inside the deep freeze, which has a temperature of -25 C. When frozen, the flask is connected to the freeze-dry unit and a vacuum applied. The ice is sublimed, leaving a network of polyvinyl acetate. The vacuum, which is about 100 microns, as noted from the closed-end mercury manometer, is applied for about four hours to ensure thorough drying of the sample. The sublimed water condenses in the condenser, which is at -25~C. When the sample is dried, the flask is removed from the unit and the material is removed from the flask with a spatula. The dried sample is powdered in a mortar. It is then suitable for redispersion and film casting. Discussion of Experimental Results All the experimental results on freeze drying various polyvinyl acetate latex samples are summarized in Table 4,pages 18 through 44. The components used in each sample run and the observations on the resultant films cast from the freeze-dried materials are listed. USING A PROTECTIVE COLLOID Initially, a protective colloid such as X-810, X-820 or Polymer C-3, all of which are alkali soluble, was added to the polyvinyl acetate sample before drying. Presumably, the protective colloid would be left surrounding the individual latex particles after the ice has been sublimed, thereby preventing the particles from fusing together as happens with straight polyvinyl acetate (see Sample 1). Also, the protective colloid would aid redispersion because of its solubility in water. All the sample runs from 1 through 59 were so treated. For the most part, the films cast from the early sample runs had fair-to-good adhesion to glass. All were hard and brittle. Generally, the film surface was rough because of poor dispersion. Some of the samples had small quantities of 20% acetic acid added prior to drying. This method was soon discontinued since materials so dried deteriorated on storage and as a result their films were unsatisfactory. Other samples after drying had (NH4)2CO3 added so that the redispersed system would be alkaline. Films from these systems (Samples 6, 7, 8, and 9) were very poor on all counts. Because the films with good adhesion to glass were brittle, and the plasticizer (film conditioning agent) could not be present during the drying operation (Samples 11, 12, 33, and 34), dry blending a plasticizer into the 2

- ENGINEERING RESEARCH INSTITUTE * UNIVERSITY OF MICHIGAN - dried modified polyvinyl acetate was attempted. Neither Carbitol or dibutyl phthalate could be added directly to the dry powder (Samples 23 and 24) be-. cause they solvated the polyvinyl acetate so rapidly that an insoluble, gummy mass resulted. An attempt was made to dry blend the dibutyl phthalate into the extender pigments and to this add the dried polyvinyl acetate sample, dispersing agents, etc. A film from this system had no adhesion, cohesion, etc. However, the addition of a film conditioning agent to a previously dispersed polyvinyl acetate sample gives a film of excellent flexibility, adhesion, and water resistance. Early attempts to add pigments and extenders to the modified latex gave films of unexpected results. Films from Samples 14 and 15 (both containing extender pigments) were excellent, while films from Samples 15, 16, and 18 (titanium dioxide pigment) were very poor. Samples of WC-130 having higher and lower molecular weights than the standard material were investigated to see if molecular weight is a factor in obtaining a satisfactory dry polyvinyl acetate (see Samples 39, 40, 48, and 49). Both the low- and high-molecular-weight material gave similar films; however, the WC-130 having higher molecular weight seemed to be better than the material having low molecular weight. The question of aging the material to insure distribution of all ingredients before drying was investigated (see Samples 41, 42, 53, and 54). In general, the results were the same as when the materials were not aged before drying. Drying under basic conditions (Samples 45 and 46) was investigated to see if better water resistance and other film properties could be achieved. It was found that the films had good adhesion but were very water-sensitive. Dispersion was more difficult because the basic materials were harder to wet. Latices other than WC-130 were investigated. Everflex G (Samples 33 and 34) and Rhoplex AC-33 (Samples 51 and 52) dried to a gummy, insoluble mass unsuitable for redispersion. Polymer Y (Samples 55, 36, and 38) dried and granulated easily; however, dispersion was unsatisfactory. Elvacet 81-900, which contains polyvinyl alcohol as a protective colloid, was dried (Sample 43). Results were satisfactory except that water resistance was poor. As a result, most of our work was done with WC-130, which gave us satisfactory results. ELIMINATION OF PROTECTIVE COLLOID 1. By Washing and Use of Centrifuge.-Since the main function of a film conditioning agent is to solvate the resin particles, it was decided to

-- ENGINEERING RESEARCH INSTITUTE ~ UNIVERSITY OF MICHIGAN investigate the effect of the addition and removal of a film conditioning agent from the polyvinyl acetate latex prior to drying, the idea being to swell the resin particles and remove the film conditioning agent and other water soluble components, leaving the resin particles in a swollen condition. Carbitol was chosen as the conditioning agent instead of dibutyl phthalate because of its water solubility. Initial attempts to dialyze this system were unsuccessful; therefore, the system was subjected to a centrifuge. The polyvinyl acetate system was washed and centrifuged repeatedly. Samples 62 and 64 (WC-130 plus 10% Carbitol based on the latex solids) and Sample 63 (WC-150) were treated this way prior to freeze drying. In each case the dried material powdered with very little effort and wet readily, even though the resultant dispersions contained agglomerated resin particles. The films had excellent water resistance and excellent adhesion to glass. The addition of a protective colloid (Sample 63) made the dried material more difficult to powder and lessened the degree of wetting. Increasing the protective colloid content (Samples 73 and 74) lowered film adhesion to glass and destroyed water resistance. These results suggest that a protective colloid is not required. 2. By Dialysis in Visking Dialysis Membrane. —Use of a Visking dialysis membrane resulted in successful dialysis of polyvinyl acetate systems. Sample 78 (WC-130 plus 10% Carbitol) was dialyzed for two days before freeze drying. The dried material was not gummy, as might be expected (see Sample 60), but could be powdered easily. It formed an excellent dispersion from which a very good film was made. The film was hard, clear, somewhat brittle, and had good adhesion to glass. Its surface was smooth because the resin particles, for all practical purposes, completely redispersed. Water resistance was good. The major difference between a polyvinyl acetate system which is dialyzed and one which has been washed and centrifuged is that the dialyzed material redisperses almost completely. As a result, a better or at least a smoother film can be made because agglomerated resin particles are not present. Water resistance of the dialyzed systems was lower, but this may have been caused by thinner films. High- and low-molecular-weight samples of WC-150 (Samples 81 and 82) were dialyzed and also washed and centrifuged (Samples 88 and 89). In the case of dialysis, the high-molecular-weight material gave a slightly rougher surface, better adhesion, and better water resistance than the low-molecularweight material. Washed and centrifuged high- and low-molecular-weight WC-130 gave similar films, with the low-molecular-weight material producing a somewhat smoother surface. Dialyzed Samples 84 and 85 were freeze dried to see what effect, if any, Carbitol had on a pigmented system. As reported in Table 4, both samples formed very good films on glass; however, the water resistance of Sample 85

7- ENGINEERING RESEARCH INSTITUTE * UNIVERSITY OF MICHIGAN was poor instead of good. It appears that Carbitol detracts from the water resistance when a pigmented system is dialyzed. The addition of glyoxal to the polyvinyl acetate system before and after dialysis was investigated to see if it would increase the water resistance by tying up any free hydroxyl groups on the Cellosize. Glyoxal increased the water resistance of Sample 98, although it also increased the difficulty in removing the dried material from the flask. Glyoxal added after dialysis (Sample 101) was detrimental to the resultant film. Three paint formulations mentioned in our report "The Development of a Liquid Polyvinyl Acetate Paint," October, 1954, were dialyzed and freeze dried (Samples 94, 95A, and 96B). These paints had been aged from six to ten months. They dried and powdered satisfactorily and formed very good dispersions from which films were cast on glass. In each case the films were tough and had good-to-excellent adhesion to glass. Water resistance is excellent, although the films soften in time when in contact with water. These same aged paints, washed and centrifuged six times, are not satisfactory for redispersion (formulas 95B and 96B). When dry, they are very hard, making powdering for redispersion impossible. Sample 104 is the same as Sample 96A except that the paint was fresh. No observable differences in properties were noted, although dialysis of the fresh paint caused it to thicken appreciably. It was expected that the dibutyl phthalate present in the aged polyvinyl acetate paints (Samples 94, 95A, and 96A) would cause the dialyzed material to dry into a gummy, insoluble mass as it does WC-130 (Samples 11 and 12). Since it did not, Sample 97 (WC-130 plus 0l dibutyl phthalate) was dialyzed three days to see if the dibutyl phthalate was removed. After drying, Sample 97 was tough and rubbery, indicating that at least part of the dibutyl phthalate did not dialyze. As a result, the effect of pigment on a polyvinyl acetate system containing dibutyl phthalate was investigated. In the case of Sample 110, where MetroNite BXXXX is incorporated into the system, the dibutyl phthalate imparts flexibility to the film and at the same time increases water resistance to a rating of excellent. Both samples powder satisfactorily and form dispersion from which films can be cast. Sample 111 is similar to 110 except that it is dialyzed as a unit. The properties are very similar. Both have flexibility and excellent water resistance and therefore are promising as starting points for compounding a "dry" polyvinyl acetate paint. Samples 116, 117, 118, and 119 all point to the fact that dibutyl phthalate can be present during dialysis, providing a pigment is present. Dibutyl phthalate cannot be added to dialyzed polyvinyl acetate (Sample 108) and obtain a film having flexibility and water resistance. Possibly the pigments absorb the excess dibutyl phthalate not used in solvating the latex. Various dispersing agents were added to polyvinyl acetate systems to 5

I- ENGINEERING RESEARCH INSTITUTE * UNIVERSITY OF MICHIGAN aid dispersion of the dry powder. In general, they had little effect on the dispersion or the resultant film. However, Tergitol NP-35 did impart flexibility to a film, as does dibutyl phthalate or any film conditioning agent (see Samples 102, 105, and 106). However, the Tergitol NP-35 detracted from the water resistance. This can be seen by comparing pigmented Samples 116 and 117 with 118 and 119, respectively. Either one of these would serve as excellent starting points from which to build a dry polyvinyl acetate paint. EFFECT OF DRY POLYVINYL ACETATE ON BONDEX AND CEMENT A check of the relative merits of dialyzed WC-130 (Sample 83) and washed and centrifuged WC-130 (Sample 77) was made with Bondex and cement applied to prewet cement blocks and asbestos shingles. Varying quantities of the dried material were added to the Bondex and cement. *From the results listed in Table 1, it appears that the quantity of lime present in the Bondex controls the amount of dry polyvinyl acetate needed to eliminate dusting of the coating. Straight cement required 10% of Sample 83 to prevent dusting, while 15% of the same material added to Bondex did not prevent dusting, Both the compounded polyvinyl acetate paint and the polyvinyl acetate formula No. 8 (both liquid and freeze dried) were included in the investigation and are shown in Table 1. TABLE 1 EFFECT OF DRY POLYVINYL ACETATE ON BONDEX AND CEMENT System Observations 1. 2. 3. 4. 5. 6. 7. 8. 9* 10. 11. 12. 13. Cement Cement Cement Bondex Bondex Bondex Bondex Cement Cement Cement plus plus plus plus plus plus plus plus 15% Sample 83 25% Sample 83 25% Sample 77 25% Sample 77 15% Sample 83 25% Sample 83 10% Sample 83 5% Sample 83 No dusting. Good adhesion and film No dusting. Good adhesion and film No dusting. Good adhesion and film No dusting. Good adhesion and film Slight dusting when rubbed. No dusting. Good adhesion and film Dusted when rubbed* Dusted when rubbed. No dusting. Good adhesion and film Dusted when rubbed. No dusting. Smooth, adherent film. No dusting. Smooth, adherent film. No dusting. Adherent film. cohesion. cohesion. cohesion. cohesion. cohesion. cohesion. Dry Paint No, 1 Formula No. 8 Sample No. 96 (Formula 8 Dry) 6

- ENGINEERING RESEARCH INSTITUTE * UNIVERSITY OF MICHIGAN - TABLE 1 (continued) The formulation of the dry paint used in system 11 follows: System Grams TiPure R-510 2.5 ASP 400 0.94 BXXXX (MetroNite) 1.0 WP-300 (Cellosize) 0.025 Daxad 11 0.025 Daxad 23 0.0125 Dry PVA (Sample 83) 2.0 Water 5.0 When applied to glass the paint (dry) showed good adhesion although it was somewhat brittle. The surface was rough because of occluded air. The water resistance of the film was fair. CONCLUSIONS Our experimental work has shown that a polyvinyl acetate properly treated can be transformed into a useful powder by freeze drying. However, dry polyvinyl acetate has an affinity for water; therefore, the material must be protected to prevent possible blocking. Freeze-dried polyvinyl acetate systems like Samples 116 or 117 offer excellent starting points from which to build a dry polyvinyl acetate paint. These systems which incorporate dialysis of a preplasticized polyvinyl acetate with an extender pigment give a film having excellent adhesion to glass, toughness, flexibility, surface smoothness, and excellent water resistance. In addition, dry polyvinyl acetate latex can be used as an additive to materials like Bondex, cement, etc. The coating is improved, although fair percentages of the dry polyvinyl acetate are necessary. Since straight cement required less dried polyvinyl acetate to prevent dusting than Bondex (see Table 1), it appears that the large quantity of lime in the Bondex is responsible for the dusting of the coating. As a result, means of counteracting this lime were inestigated and are rateported under the following section, "Surface Treatment of Bondex." Based upon the promising results and the potential market for a dry polyvinyl acetate latex and paint, further work, particularly formulation and testing of a dry polyvinyl acetate paint, appears to be justified. 7

- ENGINEERING RESEARCH INSTITUTE * UNIVERSITY OF MICHIGAN - SURFACE TREATMENT OF BONDEX While working with Bondex we found that the surface dusted regardless of whether a one- or two-coat system was applied. However, spraying water on the Bondex surface eliminated this dusting phenomenon. Because water was beneficial, it seemed advisable to observe the effect various salt solutions might have on Bondex. Two salts were used: ammonium carbonate and ammonium sulfate. The general idea was that the ammonium carbonate would react with the lime in the Bondex to form crystals of calcium carbonate, which would harden the surface. The equation for this reaction follows: Ca(OH)2 + (NH4)2CO3 - CaCOs + 2NH3 + 2H20 Limestone, CaCO3, is inert and therefore does not undergo any further reaction with the Bondex. However, when ammonium sulfate is used, it reacts with the lime to form gypsum. Some of the gypsum, either in the calcined or uncalcined form, acts by combining with the tricalcium aluminate in the Portland cement to form a complex sulfoaluminate. This sulfoaluminate is very insoluble and precipitates, thus taking the 3CaO*Al203 out of solution and rendering it unavailable for crystal formation. The equations for these reactions follow: Ca(OH)2 + (NH4)2S04-* CaS04 + 2NH3 + 2H20 or CaSO4*2H20 + 2NH3 3CaS04 + 3CaO*A120s + XH20 -- 3CaOA1l203.3CaS04-31H20 Six weathered asbestos shingles (three sandblasted and three washed) were coated with two coats of Bondex one hour apart. Before applying the Bondex each shingle was thoroughly wet. Before the second coat of Bondex was applied, each shingle was again moistened to facilitate ease of application. Each shingle was allowed to dry four hours and then sprayed with water, ammonium carbonate, or ammonium sulfate. Sufficient spray was given each shingle so that the Bondex surface was thoroughly wet, The shingles were allowed to age ten days before they were scrubbed on the scrubb t Gardner Model 105 Straight Line Washability and Abrasion Machine. Water was used for the scrubbing test to 8

t - ENGINEERING RESEARCH INSTITUTE * UNIVERSITY OF MICHIGAN provide moderate lubrication for the bristle brush. Results of the washability tests are listed below. TABLE 2 WASHABILITY OF SURFACE-TREATED BONDEX Sample No. Description Results 1 Two coats of Bondex applied: to washed asbestos shingle, followed by water spray. Scrubbed 25 cycles. Coating completely removed. Most of the damage was done during the first 10 cycles. 2 3 Two coats of Bondex applied to sandblasted asbestos shingle, followed by a water spray. Two coats of Bondex applied to washed asbestos shingle, followed by a spray of concentrated ammonium carbonate. Two coats of Bondex applied to sandblasted asbestos shingle, followed by a spray of concentrated ammonium carbonate. Two coats of Bondex applied to washed asbestos shingle, followed by a spray of concentrated ammonium sulfate: Two coats of Bondex applied to sandblasted asbestos shingle, followed by a spray of concentrated ammonium sulfate. Scrubbed 45 cycles. Coating began to break down after 20 cycles. Coating 50* destroyed after scrubbing 100 cycles. Breakdown began after 50 cycles. Scrubbed 500 cycles. Surface of coating barely broke down except for one end. This end wore away before 200 cycles, but further scrubbing was not detrimental to the coating. Scrubbed 1000 cycles. Coating did not break downs Scrubbed 2500 cycles. Coating did not break down. 5 6 - - -- - ----- - -- -- -- — — -~ -- - - ------ -- ------ --- 9

ENGINEERING RESEARCH INSTITUTE * UNIVERSITY OF MICHIGAN Photographs of the above shingles after being scrubbed are found on this and the following page. From these data it is evident that the water resistance and abrasion resistance of a Bcndex coating can be increased manyfold by spraying the coating with a compound such as ammonium sulfate, which will react with the lime. Some of the gypsum formed renders insoluble complexes while the rest forms crystalline gypsum which hardens the Bondex and also acts as a binding agent. Therefors, by utilizing a common practice of the cement industry, it has been possible to pioduce a moro dense Bondex film which has better cohesive and adhesive properties. A comnarisoi of formulas 1 and 2 with 5 and 6 in the experimental work bears this out. Panel 1 Scrubbed 25 cycles Panel 2 Scrubbed 45 cycles L Figure 1. Bondex surface sprayed with water. 10 - - - --- - -- --

ENGINEERING RESEARCH INSTITUTE UNIVERSITY OF MICHIGAN r'..-^i~~Panel 5 Scrubbed 100 cycles Panel 4....:Scrubbed 500 cycles j ~ ~ ~ ~ " _m ssl~~~~~~~~ " i _~~~~~~~~~~~~~__.4, I;;I "I — ~~~~~~~~~~~~~~~~~~~~~~~~~..1 -- Figure 2. Bondex surface sprayed with ammonium carbonate. Panel 5 Scrubbed 1000 cycles Panel 6 Scrubbed 2500 cycles Figure 3. Bondex surface sprayed with ammonium sulfate. 11

ENGINEERING RESEARCH INSTITUTE * UNIVERSITY OF MICHIGAN SUPPLEMENT ON THE DEVELOPMENT OF A LIQUID POLYVINYL ACETATE PAINT Supplementing the report on the Development of a Liquid Polyvinyl Acetate Paint, dated October 1954, we have listed below the external exposure results as of June 30, 1955 of the polyvinyl acetate paints exposed on the roof of the East Engineering Building, University of Michigan. These paints were applied in one- and two-coat systems on asbestos shingles which had been weathered for five years. The asbestos shingles were prewet before the polyvinyl acetate paints were applied in order to prevent pinholing. The panels were held in a test rack at an angle of 450 facing toward the south, The formulation of formulas 5, 6A, and 8 are listed in the glossary; the other formulations may be found in the report on the Development of a Liquid Polyvinyl Acetate Paint. TABLE 3 EXTERNAL EXPOSURE RESULTS OF WATER BASE PAINTS Formulation Blistering Chalking 9 Months Exposure 12 Months Exposure 1 coat 2 coats 1 coat 2 coats 1 badly slightly severely badly yes 2 badly slightly badly badly yes 3 some none badly none yes 4 none none none none 5 severely some severely badly yes 6a none none slightly none yes 6b none none slightly none yes 6c none none slightly none yes 7 Months Exposure 10 Months Exposure 6d some none slightly slightly yes 7 none none none none yes 8 none slightly none badly yes III L _ - L! I l _ l _ ~IiI. ~] l I I............ -. '.... 1: e - 1.: 12

ENGINEERING RESEARCH INSTITUTE * UNIVERSITY OF MICHIGAN The film integrity of formulas 4 and 7 is good. Formula 4 is very white in color and appears to be the best paint applied to the asbestos shingles. No explanation is offered for the blistering of the two coats of formula 8. The single coat of formula 8 does not show this type of failure. It is interesting to note that the paint rack itself, coated with different systems of polyvinyl acetate and white lead, has stood up very well. Those sections painted with white lead, both primer and top coat, are considerably darker than the others. All the wood regardless of the system used showed checking. The whitest system was the polyvinyl acetate primer acrylic top coat. SUPPLEMENT ON PAINT AND VARNISH REMOVERS The report on the Development of Paint and Varnish Removers issued October) 1954 compared the performance characteristics of 25 commercial paint and varnish removers and 39 laboratory formulations. The differences in the performance of these paint and varnish removers were observed after they were applied to panels finished with clear alkyd urea furniture varnishes. At the time of the report, pictures of the test panels, particularly panels A and D, were not available. Pictures of these two panels are included in this report on pages 15 and 16. Almost all the laboratory paint and varnish removers were applied to panel A for comparison purposes. Panel D gives a comparison of the eight best commercial paint and varnish removers with the better laboratory-compounded paint and varnish removers. Of the better commercial removers applied to panel D, only formulas C, T, and V, represented by J. B. Day Company's KutKote Remover, Universal Technical Products' Universal Remover, and Dux Paint and Chemical Company's Atomic Remover, respectively, gave satisfactory results. On the other hand, many of the laboratory formulations such as formulas 23, 27, 28, 29, 35, 36, 37, and 39 were equivalent to or better than the best of the commercial paint and varnish removers tested. It should be noted that a clear alkyd urea furniture varnish such as used on the test panels provides an excellent finish for comparing paint and varnish removers. Oleoresinous-type finishes were unsatisfactory because all the paint and varnish removers, commercial and laboratory, gave satisfactory results. Most of the commercial paint and varnish removers tested had little or no effect on the alkyd urea furniture finish (see picture of panel D, page 16), while almost all the laboratory formulations gave satisfactory results. A general laboratory formulation found to be very satisfactory follows: 13

- ENGINEERING RESEARCH INSTITUTE * UNIVERSITY OF MICHIGAN - Parts by Weight Methylene chloride Paraffin Methocel 4000 HG Methanol Active solvent Water 177 to 172 2 3 to 4 12 6 4 to 6 The solvent may be Carbitol, Cellosolve acetate, Tetralin, cyclohexanol, furfural, or combination of same. More detailed results may be found in the report on the Development of Paint and Varnish Removers. 14

ENGINEERING RESEARCH INSTITUTE * UNIVERSITY OF MICHIGAN -- Row 1 0 L w r. f.e..0 L s: Row 2 Row 3 Panel A Figure 4. Comparison of laboratory formulations (left to right). Row 1 Row 2 *Formula 10 *Formula 20 9 19 8 18 7 17 6 16 5 15 4 14 5 15 2 12 1 11 paint and varnish Row 3 *Formula 30 29 28 27 26 25 24 23 22 21 *Formulations may be found on pages report on Development of Paint and issued October 1954. 9 and 10 in the Varnish Removers, 15

ENGINEERING RESEARCH INSTITUTE * UNIVERSITY OF MICHIGAN \ Row 2 ^^^^lR0y^^K^^^^^^m_^Ml,:- MMWRow 2i Panel D F iure 5. Comparison of commercial and laboratorycompounde(d paint and varnish removers (left to right). Row 1 Row 2 Row 3 *Formula C *Formula 36 *Formula 5 E 37 6 Q 5 15 S 15 28 T 23 29 U 17 33 V 35 14 W 27 38 (multiple coats) 39 9 -- *For formulations see Tables I and III in report on Development of Paint and Varnish Removers, issued October 1954. 16

APPENDIX

I TABLE 4 EXPERIMENTAL FREEZE-DRIED MODIFIED POLYVINYL ACETATE SYSTEMS Sample Run No. Components pH Observations ~~~~~~~~~~~ 1 -, 1.. -j l,,, -, -. ~-,,..., s' OD 1 WC-130 2 WC-130 x-810 10% NI40H 3 WC-150 x-81o 10% NI40H 20% acetic acid 4 WC-130 X-810 10% NaOH 5 WC-130 X-810 10% NaOH 20% acetic acid 6 WC-150 X-820 10% NH40H 35.0 gm 3.2 gm 43.5 gm 4.2 gm 10,0 cc 42.9 gm 4.2 gm 42.0 gm 4.6 gm 8,0 cc 32.1 gm 3.3 gm 7 3 5 3.2 5 A hard and brittle film with good adhesion to glass was formed. Material powdered easily. Films made with and without the addition of (NH4)2C03 had an orangepeel effect. Cause was poor dispersion. Film was very rough because of agglomerated resin particles. It had good adhesion to glass. Material powdered easily. Film,which was hard and brittle, had good adhesion to glass. Very poor film formed. Poor adhesion to glass. Making system alkaline with ammonium carbonate resulted in the same kind of poor film. Material dried into an insoluble, unpowderable mass. m z m z m m -4 C G) 70 m 70 n m z -( C 4 C) m iZ "n J

I TABLE 4 (continued) Sample Run No. Components pH Observations 7 WC-130 x-820 10% NH40H 20% acetic acid 30.2 gm 3.0 gm 4.0 cc 3.4 A hard but brittle film with fair adhesion to glass formed. Making system alkaline with ammonium carbonate resulted in a film with poor adhesion, etc. m z z m m 70 m z -I -) rA m:0 z en m *) 8 WC-130 x-820 10% NH40H NPX 24.7 gmr 2.5 gm 5.5 A hard but brittle film with fair adhesion to glass formed. Film is white rather than translucent. Surface of film is severely checked. Making system alkaline with ammonium carbonate resulted in a film with poor adhesion, no cohesion, and no checking. H 9 WC-130 X-820 10% NH40H NPX 20% acetic acid 27.1 gmn 2.7 gm 4.0 cc 3.3 A hard but brittle film with fair adhesion to glass formed. Film is not smooth but is translucent. Making system alkaline with ammonium carbonate resulted in a film with poor adhesion, etc. 10 WC-130 X-820 10% NI40H NPX Water 27.1 gm 2.7 gm 4,0 cc 5.5 A hard but brittle film with good adhesion to glass formed. Film slightly more translucent than Sample No. 9. z Z m S0 0 zn z >. ZI 11 WC-5510 X-820 10%f NH40H NPX 12 WC-5510 X-820 10 NH40H NPX 20% acetic acid 26.6 gn 2.5 gm 3.9 On drying, the system fused into an insoluble, unpowderable mass. On drying, the system fused into an insoluble, unpowderable mass. 21.4 gm 2.0 gm 3.0 cc i

I TABLE 4 (continued) Sample Run No. Components pH Observations Run. N............. 13 TiPure R-510 WC-130 x-81o 10% NH40H 20% acetic acid 14 MetroNite BXXXX WC-130 x-81o 10% NH40H 15 ASP 400 WC-130 X-81o 10% NH40H 13.8 gm 26.2 gm 2.7 gm 10.0 cc 9.4 gm 10.5 gm 1.2 gm 9.4 gm 15.8 gm 1.7 gi 10.4 gm 11.2 gm 1.3 gm 1.0 cc 27.8 gm 2.8 gm 5.0 cc 10.3 gm 12.0 gm 1.2 gm 2.5 cc 3.0 6 6 Very poor film formed. No adhesion to glass. Considerable evidence of checking. A hard but brittle film with good adhesion to glass formed. Resultant film was smooth and somewhat porous, like that of commercial polyvinyl acetate paints. A hard but brittle film with good adhesion to glass formed. Film is porous, as was No. 14. m z i m m r1 m C) m I: 90 n >1 m z m I -C) f 16 TiPure R-510 WC-130 x-81o 10% NH40H Water 17 WC-130 x-81o 10% NH40H 20% acetic acid 18 TiPure R-510 WC-130 X-820 10% NH40H NPX Water Very poor film formed. No adhesion or cohesion. 5 Film mud-cracked, as did Sample No. 13. 3.3 5 A hard but somewhat brittle film with good adhesion to glass was formed. Film was translucent and quite porous. Very poor film formed. No adhesion to glass. Severe mud-cracking resulted. I

I TABLE 4 (continued) Sample Components pH Observations 19 MetroNite BXXXX TiPure R-510 WC-1350 x-810o 10% N4OH 20 Nytal 300 WC-130 x-81o 10% H4o0H Water 21 'WC-150 x-810o 10% NH40H 22 WC-150 x-81o 10% NH40H 25 WC-150 x-81o 10% NH4OH 24 WC-150 x-81o 10% NH40H 25 WC-150 X-810 10% NH40H 7.4 gin 10.0 gm 18.5 gm 1.8 gmin 8.6 gm 20.0 gm 2.0 gmi 1.0 cc 19.5 gm 2.0 gm 21.5 gm 2.1 gm 15.8 gm 1.4 gm 28.5 gmi 2.8 gm 16.8 gm 5.0 gm 5.2 5.5 5.5 Film that resulted had much poorer adhesion to glass than anticipated. Mud-cracking still prevalent. Addition of ammonium carbonate to the system resulted in a poor film. Mud-cracking did not occur, however. Film formed on glass was rough and contained air bubbles. Had fair-to good-adhesion to glass. For ultimate dry blending. m z Z m m 70 m m 70 rn Vm hi V0 m Z v> 0 WS x V) Used in experiments with Bondex.and compounded cement paints. Used for dry blending with Carbitol. Used for dry blending with dibutyl phthalate. 5.5 Film is rough because of excessive foaming. Has fair-to-good adhesion to glass, although brittle. 5 26 wc-150 10% c-3 18.1 gm 1.8 gm Film had good adhesion to glass in addition to having fair cohesion. Film was not hard and brittle as with the other samples. I

I TABLE 4 (continued) Sample uSaple Components pH Observations Run No.! i _ i, 1,j, _ 1 _. 1_ _r _ -....,,, _ 1 i,,,.,,, ~ J.,, -,_.... 27 WC-150 x-81o 10% NH40H NPX 22.6 gm 2.3 gm A hard but brittle glass formed. film with good adhesion to 5 28 WC-150 x-810 10% NH40H NPX 20% acetic acid 15.0 gm 1.5 gm 5.0 cc Film shows good to excellent adhesion to glass. 5.4 m z C) z m m 7Q 0 7-I m m n m 29 WC-150 x-810 10% NH40H NPX 20% acetic acid 20.5 gm 2.1 gm 4.0 cc Same as Sample No. ing. 28. For ultimate dry blend 50 WC-130 x-810 10% NH40H NPX 20% acetic acid 31 WC-130 x-810 10% NH40H 28.6 gm 2.9 gm 7.0 cc Same as Sample No. 28. For ultimate dry blending. 5.5 19.1 gm o.5 gm A hard but brittle film with fair adhesion to glass was formed. Film was white instead of translucent. 32 WC-150 10% C-3 19.0 gm 1.9 gm 4.1-4.2 Same material as Sample No. 26. z m 90 0 n 1 z 33 Everflex G 4 5 Material dried to a gummy, insoluble, unpowderable mass. Material dried to a gummy, insoluble, unpowderable mass. 34 Everflex G x-82o 10% NH40H NPX 26.1 gm 2.6 gm I

I TABLE 4 (continued) Sample Ru Nol Components pH Observations Run No. ~ ~!, i i i I l i I i I l i I i,.l, i, I j 11 I, i I, _ i i i j - - i - j_!...... 35 Darex Polymer Y 10% C-3 36 Darex Polymer Y 10% C-3 K-707 37 WC-150 x-810 10% NH40H NPX K-707 35.0 gm 3.5 gm 35.0 gm 3.5 gm 14.7 gm 0.7 gm 0.7 gm 6 Material could not be dispersed satisfactorily; hence, a very poor film having a granular appearance and no adhesion to glass was formed. The addition of ammonium carbonate made a slurry possible; however, the film results were the same. A film with a rough surface and fair adhesion to glass was formed. Film was granular in appearance. Addition of ammonium carbonate aided dispersion of the material. Resultant film was the same except that its adhesion to glass was slightly better. m z -i m z m 7e 70 m tA PC n z A) m -n I -n 0 1 z tA G);c 38 Polymer Y 5.5 5.9 3.6 A hard film, white in color, with fair-to-good adhesion to glass was formed. The K-707 caused the dispersion to foam. Film is water soluble, Material granulates readily and is difficult to wet. Satisfactory slurry not obtained. Film formed on glass is granular and has very poor adhesion to glass. Addition of ammonium carbonate makes wetting of the material easier; however, foaming occurs. Film results are identical to original results. Film very white in color; fair adhesion to glass. It developed very noticeable mud cracks. 59 WC-130 H.M.W. x-81o 10% NH40H 20% acetic acid 15.1 gm 1.3 gm 2.2 cc

1. TABLE 4 (continued) Sample Run No Components pH Observations Ru n~ No. — --- -- -- 40 WC-130 L.M.W. x-81o 10% N540H 20% acetic acid 41 WC-150 x-8o 10% N40HO 42 WC-130 x-810 o10 NH40H 20% acetic acid 43 Elvacet 81-900 X-820 10% NH40H NPX 2248 gm 2.3 gm 4.2 cc 47.5 gm 4.7 gm 33.1 gm 35.53 gm 7.0 cc 33.0 gm 3.3 gm 3.5 5.5 Surface of film having a white appearance was severely mud-cracked. Film had fair adhesion to glass. Sample aged 3 days before drying. Dried material is very difficult to powder; hence, dispersion of material is poor. A fairly hard and brittle film with good adhesion to glass was formed. Film, translucent in color, has a rough aurface caused by poor dispersion. Water is detrimental to the film even though it has some cohesive properties. Sample aged 3 days before drying. Dried material powdered with minimum difficulty. Film formed on glass had a smooth surface, translucent appearance, good adhesion, but no cohesive properties. Film is very water sensitive. Dried material is extremely difficult to powder; hence, dispersion is poor. Film formed on glass is rough, translucent, and shows good adhesion. It is also tough, i.e., not as brittle as WC-130. Film is affected by water, but not to the extent anticipated. Unable to redisperse the material and cast a film because the dried material could not be powdered. m z m C}' z m m -4 m 70 en m C TV1 c >1 z Gb 44 Elvacet 81-900 16.3 gm 10% polyvinyl alcohol 72-60 1.6 gm i

I TABLE 4 (continued) Sample Run No, Components pH Observations ro 3I 45 WC-150 x-81o 10o NH40H Conc. NH40H 46 wc-130 x-81o 10% NH40H 20% conc. NH40H 47 wc-130 10% polyvinyl alcohol 72-60 48 WC-150 H.M.W. x-8o10 1 NH40H 49 WC-130 L.M.W. x-81o 10% NH40H 17.7 gn 1.8 gm 0.8 cc 25.4 gm 2.3 gm 1.0 cc 10.5 Dried material powders satisfactorily but lumps 8.1 remain and are present in the film. Film, with good adhesion to glass, is hard and quite brittle. It is very water sensitive. Dried material powders satisfactorily but does not wet readily, making dispersion very difficult. Film formed on glass has good adhesion and a rough surface. Film brittleness is less than an acidic film. Film is more water sensitive than an acidic film. m z Cb m m rn z 0 730 -I m 70 n m -4 1 m m -4 C. z 28.8 gm 5.0 gm Dried material wets easily but disperses poorly. Film formed on glass had good-to-excellent adhesion although it was not continuous. Film was slightly white, hard, and rather brittle. Water softens the film rather than dissolves it. 29.1 gm 2.9 gm 24.6 gm 2.5 gm 5.2 5.2 Powdered material wets but does not disperse well. Film is very tough and has good adhesion to glass. Its surface is translucent and quite rough. Water resistance is better than average although water softens the film. Powdered material wets but does not disperse well. Film is fairly tough and has good adhesion to glass. Surface is translucent and quite rough. Water resistance is fair. Film softens in contact with water. I

TABLE 4 (continued) Sample Run No. Components pH Observations - - - --- - - ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ 50 WC-150 x-820 10% NH40H NPX 10% polyvinyl alcohol 72-60 51 Rhoplex AC-33 52 Rhoplex AC-33 x-810 10% NH4OH o 53 WC-150 c' X-x-81o 10% NH40H 54 WC-130 x-8l0 10% NH4OH 20% acetic acid 55 Elvacet 81-900 x-810 10o NH40H Daxad 11 52.9 gm 1.5 gm 1.5 gm 4.5 A hard and brittle film with good adhesion to glass is formed. Surface is translucent and rough. Water resistance is above average, although film softens when in contact with water. re z Z m m 70 z rr Cb m Wn -4 -4 m 7.8 Material, in drying, formed a partial film, making redispersion impossible. 21.7 gm 2.2 gm 47.5 gm 4.7 gm 33.1 gn 3.3 gn 7.0 cc 28.4 gm 5.7 gm 0.2 gm 7.4 Material dried to a gummy, insoluble mass unsuitable for redispersion. This sample aged 7 days before drying. Dried 5.3 material difficult to powder. It wets fairly well, but lumps of resin remain in the poor dispersion. Film formed is hard and brittle with good-to-excellent adhesion to glass. Surface is rough. Film is water sensitive. Material after aging 7 days is partially coagulated. Material did not dry satisfactorily. No film cast from this material. z m 70 -4 '1 0 z 6.2 Dried material powders quite easily but wets poorly. Resultant dispersion contained resin particles and was foamy. Film formed on glass was tough (not brittle) and very rough. It has fair-to-good adhesion to glass. Water dissolves the film. I

7 TABLE 4 (continued) Sample Run No. Components pH Observations Run No. 56 Elvacet 81-900 X-820 10% NH40H NPX Conc. ammonium hydroxide 57 WC-130 x-810 10% NH40I 58 MetroNite BXXXX WC-130 Water x-81o 10% NH40H 59A WC-130 5% Cellosize WP-300 27.0 gm 2.7 gn 1.0 cc 29.2 gm 2.9 gm 10.2 5.5 Dried material is hard, powders with difficulty, but wets well. A hard and brittle film with good adhesion to glass was formed. Film was very rough (caused by resin particles) and translucent. Water dissolves the film. Material to be used for dry blending. m z m z m >1 m 30 3: -I m1 -4 m 20.7 gm 21.0 gm 2.0 cc 2.1 gm Dried material powders satisfactorily. used for ultimate dry blending. To be ro -4 0 47.8 gm 11.0 gm 4.1 Material aged two days before drying. Dried material powders satisfactorily, wets readily, but dispersion contains resin lumps. A brittle film with fair adhesion to glass was formed. Film was slightly rough and translucent. Water softens the film. z T1 Z m I z -ib -( f% 59B Sample 59A X-820 10% Ho40H NPX 20.9 gm 2.1 gm 5.1 Material aged five days before drying. Dried material powders easily, wets readily, disperses well, but foams. A brittle film, white in color, was formed on glass. It had no adhesion to glass. Surface of the film was white. I

I TABLE 4 (continued) Sample Run No.Components pH Observations Run No. i i,..~ l I I I, I l I, I I -- ~ ~ - _ l -... '-.I I I. IIl. I. I. I,, I........ I " 60 WC-130 Carbitol 78.2 gm 4.7 gm 3.8 Method used to dialyze sample was unsatisfactory. Material dried to a gummy, insoluble mass. 61 Sample 60 x-81o 10% NH40H 28.1 gm 2.8 gm 5.5 Material dried to a gummy, insoluble mass. m z z m m 70 m z -70 n -4 m ro 62 WC-150 plus Carbitol (10% based on latex solids), (System washed and centrifuged 6 times.) To this X-820 10% NH40H NPX was added. 63 WC-150 (System washed and centrifuged 6 times). 64 WC-130 plus Carbitol (10% based on latex solids). (System washed and centrifuged 6 times). Basic screening test. See on a controlled sample. Basic screening test. See on a controlled sample. Basic screening test. See on a controlled sample. Sample 68 for results Sample 65 for results. Sample 67 for results 65 WC-130 (system washed and centrifuged 6 times). Water added to the washed system to reconstitute the material to a solids content approximating the original. Dried material powders satisfactorily into fine granules. These wet readily. Film is clear in color. Surface of film is rough because of agglomerated resin particles. Film is tough and has excellent adhesion to glass. Water resistance is excellent. C z m (0 on z I

I TABLE 4 (continued) Sample Run No. Components pH Observations Run No. 66 Sample 65 X-820 10% NH40H NPX 9.5 gm 0.95 gm 67 WC-130 plus Carbitol (10% on the latex solids). (System washed and centrifuged 6 times.) Water added to the washed system to reconstitute the material to a solids content approximating the original. ro %0 Material powders easily and wets satisfactorily. It requires agitation to obtain any degree of dispersion. Film is partially white in color. Surface is rough because of the resin agglomerates. Film has excellent adhesion to glass, is hard and slightly brittle. Water resistance is excellent. Material powders easily and has the appearance of powdered sugar. It wets readily. Film is clear in color. Surface is rough. Film is check-free, hard, slightly brittle, and has excellent adhesion to glass. Water resistance is excellent. Material:powders satisfactorily but is not like powdered sugar (see Sample 67). It wets satisfactorily. Film is partially white in color. Surface is somewhat rough. Film, which is hard but not brittle, has excellent adhesion to glass. Water resistance is excellent. Material powders easily into fine granules (not like powdered sugar). It wets satisfactorily and disperses very well. Film is clear in color. Surface is rough, caused by air bubbles instead of agglomerated resin particles. Film, which is hard and quite brittle, has excellent adhesion to m z m m 70 G m en t/ m:0 -n m m 68 Sample 67 x-82o 10% HN40H NPX 10.9 gm 1.1 gm C z Z m!f 0 n z 69 Elvacet 81-900 (system washed and centrifuged 6 times). Water added to the washed system to reconstitute the materials to a solids content approximating the original.

TABLE 4 (continued) Sample Run No. Components pH Observations! ~ ~ ~.. i i i. i i _..1..l t glass. Water resistance is fair-to-good, although water tends to dissolve the film. 70 Sample 69 X-820 10% NH40H NPX 10.0 gm 1.0 gm w% 71 Elvacet 81-900 plus Carbitol 0 (10% on latex solids). (System washed and centrifuged 6 times). Water added to reconstitute material to 60% solids. Material powders easily but does not produce fine granules (Sample 69). It wets slowly. Film is white in color. Surface is very rough because of agglomerated resin particles. Film is partly checked. It has good adhesion even though it is brittle and hard. Water resistance is poor. Material powders easily into fine granules. It wets satisfactorily, forming an excellent dispersion containing entrapped air. Film is clear in color. Surface is very smooth except for occluded air bubbles. Film, which is quite hard and brittle, has excellent adhesion to glass. It has poor water resistance, dissolving when in contact with water. Material powders easily into fine granules resembling powdered sugar. It wets readily although resin agglomerates are present in the dispersion. Film is almost clear in color. Surface is rough because of the agglomerated resin particles. Film, which is hard and quite brittle, has excellent adhesion to glass. Water softens the film. m z m z m m 70 -I C( m ein In 3) m 70 S I.-4 C 4 m 0 z m -- 0 I G~ z 72 Sample 71 X-820 10% NH40H NPX 10.0 gm 1.0 gm

7 TABLE 4 (continued) Sample Components pH Observations Run No. 73 WC-130 plus Carbitol (10% on latex solids). X-820 10% NH40H NPX (System washed and centrifuged 6 times). Water added to reconstitute material to 47.5% solids. 19,0 gm 1.5 gm 12,0 gm 3.0 gm Material powders easily into fine granules. It wets readily; however, dispersion contains resin agglomerates. Film is white in color. Surface is rough because of the agglomerated resin particles. Film, which is hard and brittle, has good adhesion to glass. Water resistance is poor. Material powders easily into fine granules. It wets much slower than Sample 73, Dispersion is very poor. Film is white. Film has no adhesion to glass and is severely checked throughout. Dried material adhered together and developed a yellow color on standing. m z z m m 70 z 7 -m m 3> 73 n I -I m 74 Sample 73 x-82o 10% NE40H NPX H 75 WC-130 plus 10% Carbitol Unsuccessful dialysis attempt (not using a dialysis membrane). 76 MetroNite BXXXX WC-130 plus 10% Carbitol based on resin solids. (Washed and centrifuged 8 times.) 25.8 gm 39.0 gm Material easily removed from flask after drying. Powders with some difficulty but wets readily. Type of Film Formed on Glass Color - white; surface - very rough. Film has excellent adhesion to glass and is very hard and tough. Water resistance is excellent. Material same as Sample 65 used as an additive to Bondex. Z z m 50 -( I C} n z 77 WC-130 (Washed and centrifuged 8 times.) I

71 TABLE 4 (continued) Sample Run No. Components pH Observations Run No. I I I I I 78 WC-130 plus 10% Carbitol based on resin solids. (Material dialyzed two days in Visking membrane.) 79 WC-130 plus 10% Carbitol based on resin solids. (Material dialyzed four days in Visking membrane.) 80 WC-130 (Dialyzed for two days in Visking membrane. ) 81 WC-130, high molecular weight. (Dialyzed for two days in Visking membrane.) ro Material powders easily and wets satisfactorily. Forms an excellent dispersion with very few resin particles present. Type of Film Formed on Glass Color - clear; surface - very smooth. Film, which is hard and brittle, has good adhesion to glass. Water resistance is fair to good. Material powders easily into very fine granules similar to powdered sugar. It wets satisfactorily but foams somewhat, Type of Film Formed on Glass Color - clear; surface - very smooth. Film is tough and has excellent adhesion to glass. Water resistance is fair to good. Similar to Sample 78 used as an additive to Bondex. Dried material more difficult to remove from flask than Sample 80. Material powders into fine granules which wet satisfactorily. Dispersion has some foam but is almost free of resin particles. Type of Film Formed on Glass Color - clear; surface - slightly rough. Film, which is hard and brittle, has excellent adhesion to glass. Water resistance is fair to good. m z m z m m -I rn -g 70 m Vn n S z -- m 0 w -1 z m 0 >m Zb j

I TABLE 4 (continued) Sample Run No. Components pH Observations 82 WC-130, low molecular weight. (Dialyzed two days in Visking membrane ) Material powders easily into fine granules which in turn wet satisfactorily, Type of Film Formed on Glass Color - clear; surface - smooth. Film, which is hard and brittle, has good adhesion to glass. Water resistance is poor. m z z m m r0 m m -g -m m rn J4w k~I 83 WC-130 (Dialyzed five days in Visking membrane ) 84 MetroNite BXXXX 36.8 gm WC-130 29.2 gm Water 5.0 cc (Dialyzed two days in Visking membrane. ) Similar to Sample 80. Will be used as an additive to Bondex. Material powders satisfactorily. It wets fairly well and forms a foamy dispersion. Type of Film Formed on Glass. Color - white; surface - fairly Adhesion to glass is excellent. sistance is good. smooth. Water re 85 MetroNite BXXXX 36.8 gm WC-130 plus 10% Carbitol Based on resin solids 29.2 gm Water 5.0 cc (Dialyzed two days in Visking membrane.) Material powders satisfactorily, somewhat easier than Sample 84. It wets well and forms a foamy dispersion. Type of Film Formed on Glass Color - white; surface - smooth. Adhesion is excellent. Water resistance is poor. z m 0 n I m z I

I TABLE 4 (continued) Sample Run mp Components pH Observations Run No. 86 Elvacet 81-900 (Dialyzed two days in Visking membrane. ) 87 Elvacet 81-900 plus 10O Carbitol based on resin solids (Dialyzed two days in Visking membrane. ) 88 WC-130, high molecular weight, (Washed and centrifuged 6 times-) Material does not powder well and does not wet. In order to make a dispersion satisfactory for casting a film the material was ground in a mortar. Film that resulted was clear, had a rough surface, good adhesion to glass, and very poor water resistance. Material was more difficult to powder than Sample 86 and did not wet. In order to make a satisfactory dispersion, material was ground in a mortar. Film that resulted was clear, had a fairly rough surface and good adhesion to glass but very poor water resistance. Material powders easily and wets readily. However, dispersion contains agglomerated resin particles. Type of Film Formed on Glass Color - clear; surface - very rough. Film,which is hard and tough,has excellent adhesion to glass. Water resistance is excellent. m z m m m I Z C m m m C) rn m m C z m en 0 z 89 WC-130, low molecular weight. (Washed and centrifuged 6 times,) Material powders easily and wets readily. However, dispersion contains agglomerated resin particles Type of Film Formed on Glass Color - clear; surface - rough Film, which is hard and tough, has excellent adhesion to glass. Water resistance is excellent. I

I TABLE 4 (continued) Sample Run No. Components pH Observations Run No.* 90 WC-130 (Dialyzed two days in Visking membrane. ) 91 WC-130 (Washed and centrifuged 7 times.) 92 Vinac WR-20 (Dialyzed two days in Visking membrane. ) 93 TS-22 (Dialyzed two days in Visking membrane ) 94 Formula No. 5 (formulation appears on page 19 of the final report on Development of a Liquid Polyvinyl Acetate Paint and also appears in glossary of this report.) (Material dialyzed 3 days in Visking membrane.) Same as Sample 80; to use for blending with other materials. Material used as an additive for Bondex. Material powders with some difficulty. It wets satisfactorily. Typeo fFilm Formed on Glass Color - clear; surface - smooth. Adhesion is fair. Water resistance is very poor. Material powders easily but does not wet, although dispersion is possible. Type of Film Formed on Glass Color - clear; surface - rough. Adhesion is excellent. Water resistance is fairly good. Material thickened appreciably on dialysis. Dried material powdered and wet satisfactorily. Dispersion contained a few agglomerated resin particles. Type of Film Formed on Glass Color - white; surface - relatively smooth. Film is tough and has good adhesion. Water resistance is excellent. m z m z m m z n m 70 C) I =i.-4 -1 Z m 0 Z< m 3C -< 0 *m z I

I TABLE 4 (continued) Sample Run No. Components pH Observations i...l......., j l j,, 95A Formula No. 6A (formulation appears on page 2 of the final report on Development of a Liquid Polyvinyl Acetate paint and also in glossary of this report). (Material dialyzed 3 days in Visking membrane.) 95B Same as 95A (Washed and centrifuged 6 times.) 96A Formula No. 8 (formulation appears on page 8 of the final report on Development of a Liquid Polyvinyl Acetate Paint and also in the glossary of this report). (Material dialyzed 3 days in Visking membrane.) 96B Same as 96A (Washed and centrifuged 6 times.) Material did not thicken on dialysis. Dried material powdered and wet satisfactorily. Dispersion contained a few agglomerated resin particles. Type of Film Formed.on Glass Color - white; surface - some roughness. Film is tough and has fair-to-good adhesion to glass. Water resistance is excellent. The solids when centrifuged packed so tightly together in the bottom of the centrifuge tube that they could not be separated. As a result, no redispersed polyvinyl acetate film was cast from this product. Material powdered satisfactorily, but wet with considerable difficulty. Agglomerated resin particles are present in the dispersion. Type of Film Formed on Glass Color - white; surface - fairly rough. Film is very tough and has excellent adhesion to glass. Water resistance is excellent. Material dried satisfactorily but could not be powdered, making the casting of a film impossible. m z m Z m m 7> z - 73 m -n C) m 70 n z I -- m < m -4 0 "n T'I (> Z I

I TABLE 4 (continued) Sample Run No. Components pH Observations 97 WC-130 plus dibutyl phthalate to the extent of 10% based on latex solids. (Material dialyzed 3 days in Visking menibrane ) 98 WC-130 plus a small quantity of glyoxal (Material dialyzed 3 days in Visking membrane.) Material was difficult to remove from the flask because it is slightly rubbery. Material, which is hard and tough, could not be powdered. Material dried satisfactorily but was difficult to remove from flask. It powders easily into fine granules which wet satisfactorily. Dispersion is foamy and contains a few scattered resin particles. Type of Film Formed on Glass Color - clear; surface - smooth. Adhesion is excellent. Water resistance is good. m z 0 z Z m m m -I -- -I m ze T, IS m( 99 WC-150 (Material dialyzed 3 days in Visking membrane.) 100 WC-150 (washed and centrifuged 6 times) plus a small quantity of Daxad 11. Material dried for eventual use in dry paints. Material powders easily and wets well. Dispersion contains some flocculated resin particles. Type of Film Formed on Glass Color - clear; surface - slightly rough. Film is slightly brittle but has excellent adhesion to glass. Water resistance is good. The dispersing agent detracts from the water resistance. z m 70 = -( -E 0 I

I TABLE 4 (continued) Sample Run No. Components pH Observations Run No.. 101 WC-130 (dialyzed) plus a small quantity of glyoxal. Material dried satisfactorily. It powders easily and wets well. The addition of glyoxal results in a dispersion that tends to settle out. Type of Film Formed on Glass Color - white; surface - rough because film is discontinuous. Film is brittle and has good adhesion to glass. Water resistance is fair because the film formed is discontinuous. m z z m m 79 z n 70 m n m I V) -I m *.102 WC-130 (dialyzed) plus Tergitol ws~ NPX. Dried material is somewhat rubbery. Material wets well but makes a dispersion which is discontinuous. Type of Film Formed on Glass Color - almost clear; surface - very rough. Film, which is flexible, has fair adhesion to glass. Water softens the film, 103 WC-130 (dialyzed) plus X-820 10% NH40H NPX to the extend of 10% based on latex solids. Material powders and wets satisfactorily. Disperses very well. Type of Film Formed on Glass Color - opaque; surface - fairly smooth. Film,which is hard and brittle, has good adhesion to glass. Water softens but does not whiten the film. z rm 0 TI I 0 l

I TABLE 4 (continued) Sample Run No. Components pH Observations Run No. Formula No. 8 (see Sample 96A). (Dialyzed for 2 days after paint had been freshly made.) Dialysis thickens paint appreciably. It is easily removed from the flask. It powders easily and wets satisfactorily. Disperses well, although a few agglomerated resin particles are present. Type of Film Formed on Glass Color - white; surface - fairly smooth. Film is not brittle and has excellent adhesion to glass. Water resistance is excellent. m z m m Z m m 7Q z m 73 m m n I -4 cr * 105 WC-130 (dialyzed) Tergitol NPX 7.5 gm 4 drops Dried material satisfactorily removed from flask. It powders with difficulty but wets readily. Flocculated resin particles cause dispersion to be lumpy. Type of Film Formed on Glass Color - clear; surface - rough. Film does not have the flexibility of Sample 103. Adhesion is good-to-excellent. Water softens the film. 106 WC-130 (dialyzed) Tergitol NPX 7.5 gm 10 drops Dried material very difficult to remove from flask. It is very hard and rubbery, making powdering impractical. No film was cast from this material because of the dispersion difficulties. z - -< m 0 Cn -, z z I

I TABLE 4 (continued) Sample Run No. Components pH Observations Run No. 107 WC-130 (dialyzed) Tergitol NPX Daxad 11 7.5 gm 2 drops trace Dried material powders satisfactorily. It wets readily but the dispersion contains some flocculated resin particles. Type of Film Formed on Glass Color - clear; surface - rough. Film, which is hard and brittle, has good adhesion to glass. Water resistance is poor to fair. m z z m m z C6 m m I -I m 108 WC-150 (dialyzed) Dibutyl phthalate 7.5 gm 3 drops 0 Material dried satisfactorily. It powders very well and wets readily. Dispersion contains agglomerated resin particles. Type of Film Formed on Glass Color - clear; surface - rough. Film, which is hard and brittle, has good adhesion to glass. Water resistance is poor to fair. 109 WC-130 (dialyzed) Tergitol NP-35 7 gm 2 drops Dried material powders into fine granules which tend to block on standing. Material wets very fast. Dispersion is relatively free of agglomerated resin particles, but the film appears to be discontinuous. Type of Film Formed on Glass Color - clear; surface - fairly rough. Film, which is very flexible, has good adhesion to - glass. Water resistance is excellent. Aging of film results in some loss of flexibility. c. z m 70 -Z I z >L i

7 TABLE 4 (continued) Sample... SRa No. Components pH Observations Run No. 110 MetroNite BXXXX WC-150 (dialyzed) Dibutyl phthalate 10.0 gm 7.5 gm 5 drops Material is difficult to remove from flask. powders very easily into fine granules. It wets satisfactorily. Type of Film Formed on Glass Color - white; surface - smooth. Film is flexible and has excellent adhesion. Water resistance is excellent. It 111 MetroNite BXXXX WC-5510 Water (Dialyzed for 5 days.) 20 gm 15 gm 5 gm I-H 112 WC-130 (Basic with NH4OH) (Dialyzed) Dried material difficult to powder. It wets readily. Dispersion foams. Type of Film Formed on Glass Color - white; surface - smooth. Adhesion is excellent. Film is tough and flexible. Water resistance is excellent. Dried material was very easily removed from flask. Material, which powders easily, resembles powdered sugar. Wets slowly, but dispersion that results is excellent except for the foam. Type of Film Formed on Glass Color - clear; surface - smooth. Film has good adhesion to glass. Water resistance is very poor. Film dissolves rapidly. m z z m m 79 z m m 70 -I -I m Z m 0 -I( 0 zn 2 0 3) I

-1 TABLE 4 (continued) Sample Run No. Components pH Observations,~u n J,i.,. 11 _ ____11_,_11_....... _., " ' 113 WC-130 (dialyzed) (Basic with NH40OH) Tergitol NP-35 7T5 gm 2 drops Dried material is very hard and consequently powders with difficulty. It wets readily. Dispersion contains agglomerated resin particles and appears to need an emulsifying agent. Type of Film Formed on Glass Color - white; surface - discontinuous. Film lacks adhesion and flexibility. Water resistance is very poor. m z m Cb m m >0 m n z mm r) 114 MetroNite BXXXX WC-130 (dialyzed; basic with mN40H) Tergitol NP-35 Dibutyl phthalate Daxad 23 10 gm 7,5 gm 2 drops 2 drops trace Material powders with difficulty into granules which wet readily. Dispersion contains a few agglomerated resin particles and appears to need an emulsifying agent. Type of Film Formed on Glass Color - white; surface - discontinuous and rough. Film has no strength nor adhesion to glass. Water resistance is very poor. MetroNite BXXXX WC-5510 Water Tergitol NP-35 (Material dialyzed 4 days) 20 gm 15 gm 5 gm 5 drops Material is difficult to powder because of its tendency to be rubbery. Type of Film Formed on Glass Color - white; surface - rough, caused by a few scattered resin particles. Film is flexible and has good adhesion to glass. Water resistance is excellent. C z m u0 V) -( 0 "z n z I

I TABLE 4 (continued) Sample Run No. Components pH Observations i.. 1,.. i..,. _ l 116 MetroNite BXXXX WC-5505 Water (Material dialyzed 5 days) 117 MetroNite BXXXX wC-55025 Water (Material dialyzed 5 days) 118 MetroNite BXXXX WC-5505 Water Tergitol NP-35 (Material dialyzed 6 days) 20 gm 15 gm 5gm Material powders easily and wets satisfactorily. Dispersion is good although it does foam. Type of Film Formed on Glass Color - white; surface - smooth except for occasional air bubbles. Film is flexible and has excellent adhesion to glass. Water resistance is excellent. 20 gm 15 gm 5 gm Material powders easily and wets satisfactorily. Dispersion is better than Sample 116, although it does foam. Type of Film Formed on Glass Color - white; surface - some roughness caused by occasional resin agglomerates and air bubbles. Adhesion to glass is excellent. Film is flexible but not as much as Sample 116. Water resistance is excellent. m z m z m m z C-I 73 m tA C m 70 m z -( < -n m z 20 gm 15 gm 5 gm 2 drops Material, easily removed from flask, powders easily and wets readily. Dispersion contains air bubbles and agglomerated resin particles both of which tend to disappear on stirring. Type of Film Formed on Glass Color - white; surface - slight roughness caused by very fine resin agglomerates. Film is tough and flexible and has excellent adhesion to glass. Water resistance is good. I

I TABLE 4 (continued) Sample Run No. Components pH Observations --. --.. L....~..... _. _. 119 MetroNite BXXXX WC-55025 Water Tergitol NP-35 (Material dialyzed 6 days), 20 gm 15 gm 5 gm 2 drops Material, easily removed from flask, powders easily and wets satisfactorily. Dispersion is very good, although it does contain air bubbles. Type of Film Formed on Glass Color - white; surface - smooth. Film is flexible, tough,and has good adhesion to glass, Flexibility is less than Sample 118. Water resistance is good. m z Z z m m z 0 m m) m 70 n I z -4 i -4 m 0 z m 0o Vn =0 z

ENGINEERING RESEARCH INSTITUTE * UNIVERSITY OF MICHIGAN GLOSSARY Trade Name Description Supplier we-130 WC-130 L.M.W. WC-130 H.M.W. TS-22 Vinac WR-20 Elvacet 81-900 Darex Polymer Y Everflex G Rhoplex AC-33 WC-5510 WC-5505 WC-55025 Polyvinyl acetate latex Polyvinyl acetate latex, low molecular weight Polyvinyl acetate latex, high molecular weight Polyvinyl acetate latex Polyvinyl acetate latex Polyvinyl acetate latex Polyvinyl acetate latex copolymer Modified polyvinyl acetate latex Acrylic latex WC-130 plasticized with 10% dibutyl phthalate based on latex solids WC-130 plasticized with 5% dibutyl phthalate based on latex solids WC-130 plasticized with 2-1/2% dibutyl phthalate based on latex solids Bakelite Company Bakelite Company Bakelite Company Shawinigan Products Corp. Colton Chemical Co. Dupont Corp. Dewey and Almy Co. Dewey and Almy Co. Rohm and Haas Co. 45

7- ENGINEERING RESEARCH INSTITUTE * UNIVERSITY OF MICHIGAN - Trade Name Description Supplier 72-60 K-707 Cellosize WP-300 Tergitol NPX and NP-35 Daxad 11 and 23 X-810 X-820 Polymer C-3 x-810 10% NH40H X-820 10% NI40H ASP 400 TiPure R-510 Nytal 300 MetroNite BXXXX Polyvinyl alcohol Ammonium polyacrylate Hydroxyethyl cellulose Nonionic wetting agents Dupont Corp. Goodrich Chemical Co. Carbide and Carbon Chem. Carbide and Carbon Chem. Sodium salts of polymerized alkyl naphthalene sulfonic acids Alkali soluble copolymer Alkali soluble copolymer Modified vinyl acetate, alkali soluble 10% solution of X-810 in water made alkaline with NH40H 10% solution of X-820 in water made alkaline with NH40H Clay - aluminum silicate Titanium dioxide - rutile Talc Magnesium and calcium silicates and carbonates Dewey and Almy Co. Monsanto Chemical Co. Monsanto Chemical Co. Monsanto Chemical Co. Edgar Bros., Inc. Dupont Corp. R. T. Vanderbilt Co. MetroNite Company 46

- ENGINEERING RESEARCH INSTITUTE * UNIVERSITY OF MICHIGAN - Formula No. 5 Formula No. 6A TiPure R-510 Mica 325 mesh w.g. WC-10* Cellosize WPHS (5%) Ethylene glycol Glyoxal (30%) Daxad 11 Tergitol NPX Water Percent 25.2 2.8 23.3 9.3 2.3 0.5 0.2 0.1 36.3 100.0 Water Daxad 11 TiPure R-510 ASP 400 MetroNite BXXXX Ethylene glycol WC-5510 Cellosize WPHS (5%) Glyoxal 30% Tergitol NPX Percent 20.1 0.2 20.0 7.5 8.o 2.9 27.6 13.0 0.6 0.1 100.0 Composition of WC-10: WC-130 latex solids Dibutyl phthalate Water 13.0 lb 1.3 9.0 23.3 lb Formula No. 8 Percent TiPure R-510 ASP 400 MetroNite BXXXX Water Daxad 11 Ethylene glycol WC-5510 K-707 (15% T.S.) Carbitol Cellosize WP-300 (5%) Tergitol NPX Water 20.0 7.5 8.0 20.1 0.2 2.5 28.3 2.6 1.7 4.0 0.1 5.0 100.0 47

UNIVERSITY OF MICHIGAN 3 9015 02844 9232