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.
In the meantime, the chemical factories of Continental Europe, principally in Germany, Austria and Belgium, had taken hold of the novelty and under the collective name of lithopone or lithophone, by numerous processes, produced various grades of the pigment, branding the respective qualities as red seal, green seal, yellow seal, blue seal, etc., or selling them under some fancy name. Of this we shall speak later on. The crusade against the use of white lead in the various countries of Continental Europe, assisted the manufacturers, to a very great extent, in marketing their products, not only to industrial concerns, as has been the case in this country, until recently, but to the general painting trade. Up to 1889 the imports into this country were comparatively small. At that time one of the largest concerns manufacturing oilcloth and linoleum in the State of New Jersey began to import and use Charlton white. Shortly after that other oilcloth manufacturers followed suit, replacing zinc white with lithopone in the making of white tablecloth, etc., and later on abandoning the use of white lead in floor cloth and linoleum. This gave an impetus to several chemical concerns, that erected plants and began to manufacture the pigment. Competition among the manufacturers and the activity of the importers induced other industries to experiment with lithopone, and the shade cloth makers, who formerly used white lead chiefly, are now among the largest consumers. Makers of India rubber goods, implement makers and paint manufacturers are also consumers of great quantities, and the demand is very much on the increase, as the nature of the pigment is becoming better understood and its defects brought under control. Large quantities find their way into floor paints, machinery paints, implement paints and enamel paints, while the flat wall paints that have of late come into such extensive use owe their existence to the use of lithopone in their makeup.
The major applications studied in the report include paints & coatings, plastics, printing inks, paper & pulps, rubber, leather, linoleum, and others. Region-wise, the market is studied across North America, Europe, Asia-Pacific, and LAMEA. Presently, Asia-Pacific accounts for the largest share of the market, followed by North America and Europe.
As mentioned above, these oxide NPs are harmful in part because both anatase and rutile forms are semiconductors and produce ROS. Particularly, P25 kind has band-gap energies estimated of 3.2 and 3.0 eV, equivalent to radiation wavelengths of approximately 388 and 414 nm, respectively. Irradiation at these wavelengths or below produces a separation of charge, resulting in a hole in the valence band and a free electron in the conduction band, due to the electron movement from the valence to conduction bands. These hole–electron pairs generate ROS when they interact with H2O or O2 [43,44]. It was described that they can cause an increase in ROS levels after exposure to UV-visible light [45]. The NBT assay in the studied samples showed that bare P25TiO2NPs produce a large amount of ROS, which is drastically reduced by functionalization with vitamin B2 (Fig. 5). This vitamin, also known as riboflavin, was discovered in 1872 as a yellow fluorescent pigment, [46] but its function as an essential vitamin for humans was established more than sixty years later, and its antioxidant capacity was not studied until the end of the XX century [47,48]. This antioxidant role in cells is partially explained because the glutathione reductase enzyme (GR) requires it for good functionality. This enzyme is the one in charge of the conversion of oxidized glutathione to its reduced form which acts as a powerful inner antioxidant and can quench the ROS [49,50]. The cost of this action is that the glutathione is converted to the oxidized form and needs to be recovered by the GR. Consequently, the cells need more vitamin B2. Another glutathione action is the protection against hydroperoxide. This activity is also mediated by riboflavin. Therefore, local delivery of this vitamin seems to significantly help the cells in their fight to keep the oxidative balance, once they are exposed to high levels of ROS.