Having thus described the origin and uses of the pigment, we now come to the question, what is lithopone? It is, in short, a chemical compound usually consisting of 30.5 per cent zinc sulphide, 1.5 per cent zinc oxide and 68 per cent barium sulphate, but these proportions vary slightly in the different makes. Lithopone of this composition is sold as the highest grade, either as red seal or green seal, as it best suits the idea of the manufacturer. Many manufacturers, especially in Europe, sell and also export other brands under other seals, containing 24, 20, 18 and as little as 12 per cent of zinc sulphide with very small percentages of zinc oxide, the balance being usually barium sulphate, but sometimes certain portions of China clay or gypsum (calcium sulphate) or whiting (calcium carbonate). Such brands are not a chemical compound, but mechanical mixtures of the chemically compounded lithopone and the admixtures referred to.
It’s true that titanium dioxide does not rank as high for UVA protection as zinc oxide, it ends up being a small difference (think about it like being 10 years old versus 10 years and 3 months old). This is not easily understood in terms of other factors affecting how sunscreen actives perform (such as the base formula), so many, including some dermatologists, assume that zinc oxide is superior to titanium dioxide for UVA protection. When carefully formulated, titanium dioxide provides excellent UVA protection. Its UVA protection peak is lower than that of zinc oxide, but both continue to provide protection throughout the UVA range for the same amount of time.
Although barium sulfate is almost completely inert, zinc sulfide degrades upon exposure to UV light, leading to darkening of the pigment. The severity of this UV reaction is dependent on a combination of two factors; how much zinc sulfide makes up the pigments formulation, and its total accumulated UV exposure. Depending on these factors the pigment itself can vary in shade over time, ranging from pure white all the way to grey or even black. To suppress this effect, a dopant may be used, such as a small amount of cobalt salts, which would be added to the formulation. This process creates cobalt-doped zinc sulfide. The cobalt salts help to stabilize zinc sulfide so it will not have as severe a reaction to UV exposure.
The produced barium sulfide enters the leacher, and the temperature is controlled above 65°C to obtain a barium sulfide content of 70%, and then enters the clarification barrel, add zinc sulfate for reaction after clarification, control the zinc sulfate content to be greater than 28%, pH=8~9, and obtain a mixture of barium sulfate and zinc sulfide with a density of 1.296~1.357 g/cm3.
, 2. The herein-described process for manufacturing lithopone of various grades and a by-product of sodium hydrosulfid, which consists in preparing separate solutions of zinc sulfate and barium sulfid, which solutions are mixed with each other and with that of sodium bisulfate, all in equivalent and calculated amounts to produce and precipitate the desired grade of lithopone and leave the so dium hydrosulfid in solution, substantially as described.
A great number of other brands with fancy names have gone out of the German market, because of some defects in the processes of manufacture. The English exporters, as a rule, offer three or four grades of lithopone, the lowest priced consisting of about 12 per cent zinc sulphide, the best varying between 30 and 32 per cent zinc sulphide. A white pigment of this composition containing more than 32 per cent zinc sulphide does not work well in oil as a paint, although in the oilcloth and shade cloth industries an article containing as high as 45 per cent zinc sulphide has been used apparently with success. Carefully prepared lithopone, containing 30 to 32 per cent sulphide of zinc with not over 1.5 per cent zinc oxide, the balance being barium sulphate, is a white powder almost equal to the best grades of French process zinc oxide in whiteness and holds a medium position in specific gravity between white lead and zinc oxide. Its oil absorption is also fairly well in the middle between the two white pigments mentioned, lead carbonate requiring 9 per cent of oil, zinc oxide on an average 17 per cent and lithopone 13 per cent to form a stiff paste. There is one advantage in the manipulation of lithopone in oil over both white lead and zinc oxide, it is more readily mis-cible than either of these, for some purposes requiring no mill grinding at all, simply thorough mixing with the oil. However, when lithopone has not been furnaced up to the required time, it will require a much greater percentage of oil for grinding and more thinners for spreading than the normal pigment. Pigment of that character is not well adapted for use in the manufacture of paints, as it lacks in body and color resisting properties and does not work well under the brush. In those industries, where the paint can be applied with machinery, as in shade cloth making, etc., it appears to be preferred, because of these very defects. As this sort of lithopone, ground in linseed oil in paste form, is thinned for application to the cloth with benzine only, and on account of its greater tendency to thicken, requires more of this comparatively cheap thinning medium, it is preferred by most of the manufacturers of machine painted shade cloth. Another point considered by them is that it does not require as much coloring matter to tint the white paste to the required standard depth as would be the case if the lithopone were of the standard required for the making of paint or enamels. On the other hand, the lithopone preferred by the shade cloth trade would prove a failure in the manufacture of oil paints and much more so, when used as a pigment in the so-called enamel or varnish paints. Every paint manufacturer knows, or should know, that a pigment containing hygroscopic moisture does not work well with oil and driers in a paint and that with varnish especially it is very susceptible to livering on standing and to becoming puffed to such an extent as to make it unworkable under the brush. While the process of making lithopone is not very difficult or complicated, the success of obtaining a first class product depends to a great extent on the purity of the material used. Foreign substances in these are readily eliminated by careful manipulation, which, however, requires thorough knowledge and great care, as otherwise the result will be a failure, rendering a product of bad color and lack of covering power.