353-1208-5111 TEXAS AGRICULTURAL EXPERIMENT STATIONS. BULLETIN NO. m 114 NOVEMBER, 1908. Composition oi White Load and Points. BY G. S. FRAPS, PH. D., Chemist. POSTOFFICEZ COLLEGE STATION, BRAZOS COUNTY, TEXAS. AUSTIN, TEXAS: von BOECKMANN-JONES COMPANY, PRINTERS GOVERNING BOARD. (Board of Directors A. and M. College.) K. K. LEGETT, President . . . . . . . . . _ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. T. 1). RoWELL, Vice-President; . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..J A. HAIDUSEK . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..La t] J. M. GREEN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . WALTON PETEET... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. E. R. KONE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . L. L. MoINNIS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . W. B. SEBASTIAN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . “Breed STATION OFFICERS. H. H. HARRINGTON . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . W. ‘C. WELBORN . . . . . . . . . . . . . . . . . . . . . . . . . ..Vice-Director and Agric J. W. CARSON . . . . . . . . . . . . . ..Assistant to Director, and State Feed M. FRANoIs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..Vet 0. M. BALL . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . G.S.FRAPS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . H. J. o. BURNS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..Animal'H C. E. SANBORN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..Co-operative Ento H. NESS...~. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..Horti N. o. HAMNER . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..Assistant s. E. ASBURY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Assistant - E. o. CARLYLE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Assistant A R. P. MAR-sTELLER . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..Assistant Vete: o. W. oRIsLER . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..Chi ‘F. _R. NAVAILLE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..Sten A. s. WARE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..Sten STATE SUB-STATIONS. H. H. HARRINGTON . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. _ WV. S. HOTCHKISS, Superintendent . . . . . . . . . . . . . . . . . . ..Troupe, Smithi s. A. WAsoHKA, Superintendent . . . . . . . . . . . . . . . . . . . . . ..Beeville, Bee}? NoTE.—~The main station is located on the grounds of the Agricul t‘ Mechanical College, in Brazos county. The postofilcte address is College5 Texas. Reports and bulletins are sent free upon application to the Dir” TABLE 0F CONTENTS. Paint Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 Standard Pigments and Oils . . . . . . . . . . . . . _ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 5 iMaterials of Disputed Value, and Adulterants. .; . . . . . . . . . . . . . . . . . . . . . . . .. 6 Composition of White Lead Sold in Texas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 7 Composition of Outside White Paints . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 8 Other Paints . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 9 Other Texas Analyses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 9 Discussion of Results . . . . . . . . . . . . . . . . . . . . . . . . . . . i . . . . . . . . . . . . . . . . . . . . . . .. 9 Paint Laws . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 Suggestions Concerning Paint Laws . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 10 Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 Summary and Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 11 [Blank Page in Original Bulletin] COMPOSITION OF WHITE LEAD AND PAINTS. G. S. FRAPS, PH. D., CHEMIST. It is estimated that about 70,000,000 gallons of mixed paints are sold in the United States each year. If this estimate is correct, Texas would use mixed paints t0 the value of about $3,000,000 annually. Add to this the White lead and other unmixed paint materials which are used in the State, and we see that the annual expenditure for paint and paint materials is a very large sum. On account of the magnitude of the interests involved, and for the further reasons that paints are sometimes very inferior mixtures and the purchaser has no means of ascertaining‘ the nature of the material purchased Without an expensive analysis, a number of States have passed laws governing the composition of paints offered for sale in their borders. The first of these was North Dakota. Minnesota, South Dakota, and Iowa have followed suit. The object of this bulletin is to present the composition of certain Texas paints which have been subjected to analysis and to discuss paints and paint laws. "hese laws require the composition of the paint to be stated upon the package. PAINT MATERIALS. Paint materials may be divided intotwo classes: First, those which are gen- erally’ recognized as standard paint materials; second, those which are of dis- puted value or which can be considered only as adulterants. The first class includes white lead, zinc oxide, pure linseed oil, turpentine, and pure colors. In the second class belongs carbonate of lime, silicates, bary'tes, petroleum products, water, etc. - STANDARD PIGMENTS AND OILS. IWzife Lead.—\Vlifte lead is probably the oldest and most important of all our pigments. It is used in a white paint for color and body. In other paints it is used to give body. It possesses good color, body, covering power, and per- manency. It mixes easily with oil and forms a paint that flows easily from the brush, Whereas, most other pigments do not work well. It appears to enter into combination with linseed oil, and form a coating of great permanency. Zinc Weider-This is also called zinc white and "Chinese white.” It is some- what variable in composition. It forms a very permanent pigment and has bet- ter coloring power than white lead. Its chief fault is want of body, that is to say, it does not hide the surface over which it is spread. " Zinc oxide is at present recognized as a standard paint material, but is ilsually mixed with more or less white lead. The proportion in which the zinc should be mixed is a subject of considerable difference of opinion among paint men. Some desire no zinc oxide, preferring only pure white lead. Others use 50 per cent or more of zinc oxide. Iiiizsced Oil-Linseed oil is recognized as the most suitable oil for paints. For example, Jenkins, in “Paint Color Mixing,” says: “It is quite necessary that pure linseed oil should be used in the manufacture of all paints, although there are one or two substances on the market which may be employed in very cheap work. No attempt should be made to execute a really good jo-b unless 6 TEXAS AGRICULTURAL EXPERIMENT STATIONS. pure linseed oil is used." Manufacturers of mixed paints, as a general rule, advise their customers t0 use nothing but pure linseed oil as a thinner. Linseed oil has a property 0t drying or hardening in a suitable length of time, forming a varnish-like mass, which cements the particles of the pigment to one another and to the surface t0 which they are applied. If an oil is used which does not have this property of hardening and cementing, the paint is liable t0 become chalky and rub off. Turpentmm-A small amount of turpentine is considered necessary in paint. Paint authorities, as a whole, recommend the use of pure turpentine and no substitute, and paint manufacturers also advise the use of pure turpentine to thin their paints. A dryer is usually added to make the linseed oil harden more rapidly. Dryers usually consist of resinates or linoleates of lead or manganese, or borate of manganese. The terms “dryer” and “Japan” are used interchangeably. The dryers are usually made by heating litharge, red lead, oxide of manganese, or borate of manganese, with li11seed oil or resin, and dissolving the melted mass in turpentine or benzine or both. Dryers are carriers of oxygen, causing the linseed oil to oxidize and harden. MATERIALS OF DISPUTED VALUE AND ADULTERANTS. The materials described below are considered as having comparatively low value in paints. When used in large quantities they may usually be consid- ered as adulterants, or the paint may be considered as an inferior paint made of cheap materials. It is quite possible, however, that under certain circum- stances a small amount of some .of these materials may be of value. Some paint manufacturers claim that a small quantity of car-bonate of lime is of ad- vantage in paints. Others, however, say such an addition is only a disadvantage except as it serves to lower the cost of the paint. Carbonate of Limel.—Carbonate of lime is also known as Paris white, Spanish white, English white, whiting, and marble dust. These materials, however, are not all the same thing, but are different qualities of carbonate of lime. Whiting is chalk which has been ground to a very fine powder and settled in powder to free it from coarse particles. Paris white is a finer quality of whiting. Marble dust is a very cheap form of carbonate of lime, obtained by grinding marble. Whiting when mixed xvith oil loses its white color and becomes a dirty gray color. It costs about one-tenth as much as zinc oxide, or white lead. SiZica.——This is prepared by grinding quartz to a very fine powder. It has very little body, but possesses considerable covering power when very finely ground. It costs about one-fourth as much as white lead. Chin/I Olay.—-China clay is widely distributed in nature and requires purifi- cation only before it is ready to be used. It costs about one-tenth as much as white lead. Barytesr-Barytes is barium sulphate. It is also called Blane Fixe. Barytes is a very important white pigment, ranking next to white lead and zinc oxide in the extent of its use. It has little body, and does not work well in oil. It has a high specific gravity, and this is one reason why it is used to adulterate white lead, which also has a high specific gravity. Barytes is found as such and is prepared for use by grinding. Precipitated barytes is also used. Barytes costs about one-seventh as much white lead. Sabin, in “Technology of Paint and Resin,” says: “These barium compounds COMPOSITION or WHITE LEAD AND PAINTS. _ 7 are the least objectionable, being in fact subjects chemically inert, and 0f stable composition; but they are practically without coloring power, being nearly transparent in oil, and while they probably help to protect the wood, they are really used to cheapen the paint and commonly to increase the profits to the maker and no benefit at all to the dealer or consumer.” As We shall see in the following pages, “White lead” sometimes consists en- tirely of barytes. This is a fraud, pure and simple. Linseed Oil Substitutes.—Linseed oil, as we have stated, is the best oil for use in mixing paints. Resin oils and other substitutes are sometimes used. The disadvantage of other oils is that they do not harden sufficiently to hold the pigment thoroughly on the surface painted, and so the covering does not resist the action of disintegrating influences as Well as it should. We have stated that paint manufacturers, as a rule, advise the use of pure linseed oil to thin their paints. In view of such recommendation, they ca11 hardly defend the use of linseed oil substitutes in their paints. Be1zzine.-—Benzine is sometimes used in place of turpentine. The intent of its use appears to be to cheapen the paint. . As paint manufacturers advise the use of pure turpentine only, little can be said in defense of the use of a benzine thinner. Wate~r.—Water is added to some paints, the object being to cheapen the paint and make it look thicker. The thick appearance causes people to believe that they are getting more for their money. Prof. E. F. Ladd found the vehicle of one sample of paint t0 contain as much as 24 per cent Water, and another sample to contain as much as 22 per cent. A small amount of water may occur naturally in paints. Since the passage of the North Dakota law water is no longer present in brands which formerly contained water when sold in North Dakota. COMPOSITION OF WHITE LEAD SOLD IN TEXAS. Eleven samples of white lead in original packages were collected by us and subjected t_o analysis. The following four samples were found of high purity: C0llier’s, Carter’s, Harrison’s, and Houston Paint Company’s. The analyses of the other seven samples are shown in Table I. Five of the seven samples contained 75 per cent 0r more of barium sulphate. Two of these five did not contain any white lead at all, and the remaining three did not contain over 5 per cent. The other two white leads, so called, contained about 30 to 45 per cent white lead; the remainder of the pigment consisted mostly of zinc oxide and carbonate of lime. Four of the samples of White lead referred to above were sold in small pack- ages, but they were sold as white lead, and nothing else. The other three were sold in larger packages and undoubtedly represent adulterated white lead which has been sold in quantity for painting purposes. It is evident that, while pure white lead can be purchased in the State, there are a number of pigments sold under this name which either are not white lead at all, or are highly adulterated. TABLE lL-“PERCENTAGIJ COMPOSITION OF ADULTERATED WHITE LEAD (_ PIGMENT) . 1286 1291 1292 1572 1574 1604 1664 White lead . . . . . . ..None None 3.31 5.04 1.75 45.16 31.79 Zinc oxide . . . . . . ..16.67 8.73 10.70 10.35 12.63 26.94 27.85 Barium sulphate . .80.68 80.52 76.93 81.71 81.02 15.28 27.66 8 TEXAS AGRICULTURAL EXPERIMENT STATIONS. 1286 1291 1292 1572 1574 1604 1664 Oxide of iron and alumina . . . . . . . . . . . .. .. .. 1.46 1.13 .73 .55 Carbonate of 1ime.. 0.20 4.12 5.30 1.84 1.51 8.47 10.58 Clay . . . . . . . . . . . . . . . . . . 6.30 3.05 ... .. 2.50 2.51 Magnesiumcarbonate.... 1.50 .26 Silica . . . . . . . . . . . .. 1.35 .. 6.01 _ COMPOSITION OF OUTSIDE WVHITE PAINTS. Eleven samples of ready mixed paints, outside White in color, were subjected to analysis. rOne of these paints carried a label showing its composition. As two samples of ‘these were made by the same manufacturer, ten manufacturers are represented. Three of these samples appear to be pure lead and zinc paints, so far as the pigment is concerned, and their composition is approximately as follows: 1.794 contains 42 per cent white lead to 57 per cent zinc oxide. 1573 contains 25 per cent White lead to 75 per cent zinc oxide. 1575 contains 30 per cent white lead “and 70 per cent zinc oxide.‘ It will be noted that these samples contain relatively largfe amounts of zinc oxide. Five of the remaining seven paints contain 10 to 15 per cent carbonate of lime and the other two contain 36 to 51 per cent barium sulphate. The analyses of the paints are given in Table II. It is claimed by some paint men that car- bonate of lime is of advantage in a paint. The only claim which can be made for barium sulphate is its cheapness. TABLE II.—COMPOSITIOX OF PIGM’EXT——ADL'LTERATED OUTSIDE WHITE. 1418 1421 1492 1493 1576 1603 1665 1667 White lead. . . . . .3596 39.51 14.66 41.81 43.91 44.64 10.95 38.02 Lead sulphate......... Zinc OXidQ . . . . . . 41.35 49.10 36.58 42.97 39.58 34.12 32.1 6 21.02 Barium sulphate. . 3.93 .. 15.65 .. 4.68 .. 51.71 36.73 Oxide of iron and alumina . . . . .. 1.19 .49 .67 .61 .31 1.48 1.38 Clay . . . . . . . . . . .. .69 .94 .. .80 .. .85 Carbonate of 1ime.14.82 11.32 13.58 14.55 10.33 14.30 1.47 2.03 Carbonate of mag- nesia . . . . .. .30 .10 1.86 .60 Silica . . . . . . . . . . . . . . . .. 4.70 .87 Insoluble . . . . . . . . . . .. .17 .19 The Vehicle.—The character of the vehicle of some of these paints is shown in Table III. Two of the paints contain a large excess of volatile oils. Four of the paints contain benzine with the turpentine. One contains mineral oil, and some. appear to contain some resin oil mixed with the linseed oil. Corrrosrrron 0F WHITE LEAD AND PAINTS. 9 TABLE III.—CHARACTER OF VEHICLE. Laboratory Percentage of N0. Volatile. N on-Volatile. Remarks. 1421 11.11 89.89 1492 14.95 85.05 1493' 13.59 86.42 1532 15.61 84.39 1576 8.53 91.47 1603 7.58 92.42 Benzine and mineral oilpresent. 1665 27.13 72.87 Benzine. 1667 10.10 i 89.89 Benzine present. 1573 11.49 88.51 Benzine present. 1575 9.59 91.41 1287 20.71 79.29 OTH ER PAINTS. Three other paints were examined, as described below. All three Were adul- terated: Sample 1288 is a brown paint, adulterated with 15 per cent carbonate 0f lime and 15 per cent clay. Sample 1294 is a lead chromate paste, adulterated with 58 per cent barytes. Sample 1532 is a light green paint, containing 13.55 per cent carbonate of lime. OTHER TEXAS ANALYSES. Bulletin No. 44 of this station by H. H. Harrington and P. S. Tilson (1897), discusses paints and painting materials, and presents the analyses of three white leads and eight mixed paints. One of the three white leads was found to be pure; the other two contained 67 to 74 per cent barium sulphate, and only 1.6 and 9.8 per cent white lead. They were thus shown to be highly adulterated. _ Of the eight mixed paints, one might be called pure. The pigment contained 82 per cent zinc oxide. Of the remaining seven paints, three contain over 37 per cent limestone; one contains 56 per cent barium sulphate; two contain 14 per cent barium sulphate, and one contains 13.5 per cent lime and clay. These paints must be regzrrrled as of inferior quality, or adulterated, according to the claims made for them by the manufacturer. However, every mixed paint is usually claimed to be the “best made." DISCUSSION OF RESULTS. We did not examine these paints for all possible adulterants. For example, water, which was found in a number of paints tested in North Dakota, Was not estimated. a It appears that “white lead” is sold in Texas that does not contain any white lead at all, and that adulterated leads are also sold. Pure lead can be purchased. v It appears that mixed paints containing materials of inferior value are sold and some of these paints mustbe considered as highly adulterated. It appears that in the majority of cases consumers of White lead, mixed paints, and other paint materials, have no means of knowing anything about the quality of the materials which they use. l0 TExAs AGRICULTURAL EXPERIMENT STATIONS. The remedy for this condition of affairs would be to require the composition of the white lead or paint to be stated on the label in unambiguous terms. The purchaser of paints would then be able to judge Whether or not he desired a paint of such character. Some of the more progressive paint manufacturers are already placing such a statement upon their products. This should be required of all, and paints and paint materials should be inspected to see that such statements are correct. PAINT LAl/VS. The object of paint laws are as follows: First. To place each purchaser of paint or paint materials in possession of exact information of its character and composition. Second. To see that such information is correct. Third. To secure and difiuse such information regarding paints as to aid the consumer to select the materials best suited to his purpose. The North Dakota paint law requires a statement of composition only When the paint is not composed of pure white lead and zinc oxide, pure color, linseed oil, turpentine and dryer. The Texas feeding stuff law requires exact information to be given regarding every feed stuff sold in the St-ate, whether the feed is pure or not. In the opinion of the writer, a paint law] should afford the purchaser exact informa- tion in regard to paint and paint materials ofiered for sale in. the State, no matter what ingredients the paint is composed of. The purchaser would then be able to select the character of paint desired. A paint composed of pure White lead and zinc oxide might not contain these two in the desired proportions. Some painters desire pure White lead, others wish only a small proportion. of zinc oxide, while others do not object to a large quantity. The purchaser should be given exact information in regard to his paint, and be allowed to make his own choice. SUGGESTIONS CONCERNING PAINT LAWS. In the opinion of the writer, the following suggestions should be incorporated in paint laws: 1. The exact composition of all paints or paint materials should be printed on a label or tag attached to the package. _ 2. The statement should be expressed in terms approved by the officer in charge of the law. 3. A penalty should be provided for any statement concerning the paint or paint material which is false or misleading, whether such statement is made on the tag or label, package, in advertisement, or elsewhere. 4. The oilieer in charge of the law should be authorized and required to pub- lish the analyses, and other information regarding the paints and paint materials in bulletins, reports or elsewhere. ACKNOWLEDGMENTS. Messrs. A. C. Deiler and J. T. Cruse are responsible for the analyses printed in this Bulletin. The author also derived some assistance from the reports and bulletins of the North Dakota Experiment Station. The methods of analysis used were for the most part those described in “Mixed Paints, Color, Pigments and Varnishes,” by Ladd and Holley. CoMroslrlon OF WHITE LEAD AND PAINTS. 11 SUMMARY AND CONCLUSIONS. 1. Eleven samples of so-called white lead were examined. Four were pure and seven adulterated or substitutes. Two did not contain any white lead and three did not contain over 5 per cent. A 2. Fourteen samples of mixed paints were examined. Four were pure lead and zine paints. Six samples contained 10 _t0 15 per cent carbonate of lime,» three contained 36 to 58 per cent barium sulphate, and one contained 15 per cent carbonate of lime and 15 per cent clay: 3. Two of these paints contained benzine a_s an inferior substitute for tur- pentine; some appeared to contain linseed oil adulterated with resin oil, and one contained l-inseed oil adulteratcd with a mineral oil. 4. Some paints and white lead examined by this station in 1897 were found to be highly adulterated or of inferior quality. 5. Paint laws should require a statement of the composition of every paint or paint material offered for sale, and a penalty should be fixed for any false or misleading statement concerning paints wherever made. 6. Suggestions are made regarding paint laws.