The skin of an adult person is, in most places, covered with a relatively thick (∼10 μm) barrier of keratinised dead cells. One of the main questions is still whether TiO2 NPs are able to penetrate into the deeper layers of the skin. The majority of studies suggest that TiO2 NPs, neither uncoated nor coated (SiO2, Al2O3 and SiO2/Al2O3) of different crystalline structures, penetrate normal animal or human skin. However, in most of these studies the exposures were short term (up to 48 h); only few long-term or repeated exposure studies have been published. Wu et al.83 have shown that dermal application of nano-TiO2 of different crystal structures and sizes (4–90 nm) to pig ears for 30 days did not result in penetration of NPs beyond deep epidermis. On the other hand, in the same study the authors reported dermal penetration of TiO2 NPs with subsequent appearance of lesions in multiple organs in hairless mice, that were dermal exposed to nano-TiO2 for 60 days. However, the relevance of this study for human exposure is not conclusive because hairless mice skin has abnormal hair follicles, and mice stratum corneum has higher lipid content than human stratum corneum, which may contribute to different penetration. Recently Sadrieh et al. performed a 4 week dermal exposure to three different TiO2 particles (uncoated submicron-sized, uncoated nano-sized and coated nano-sized) in 5 % sunscreen formulation with minipigs. They found elevated titanium levels in epidermis, dermis and in inguinal lymph nodes, but not in precapsular and submandibular lymph nodes and in liver. With the energy dispersive X-ray spectrometry and transmission electron microscopy (TEM) analysis the authors confirmed presence of few TiO2 particles in dermis and calculated that uncoated nano-sized TiO2 particles observed in dermis represented only 0.00008 % of the total applied amount of TiO2 particles. Based on the same assumptions used by the authors in their calculations it can be calculated that the total number of particles applied was 1.8 × 1013 /cm2 and of these 1.4 x107/cm2 penetrated. The surface area of skin in humans is around 1.8 m2 and for sun protection the cream is applied over whole body, which would mean that 4 week usage of such cream with 5 % TiO2 would result in penetration of totally 2.6 × 1010 particles. Although Sadrieh et al.concluded that there was no significant penetration of TiO2 NPs through intact normal epidermis, the results are not completely confirmative.
As early as sixty years ago, zinc sulphide was first thought of as a pigment for coloring India rubber and a patent for the process of its manufacture was issued in England. But it was not until twenty years later that zinc sulphide and its manufacture was seriously considered as a pigment for paint, and in 1874 a patent was issued for a process of manufacturing a white pigment, composed of zinc sulphide and barium sulphate, known as Charlton white, also as Orr's white enamel. This was followed in 1876 by a patent issued to a manufacturer named Griffith and the product, which was similar in character to Charlton white, was known as Griffith's patent zinc white. In 1879 another patent for a more novel process was obtained by Griffith & Cawley, the product made under this process proving the best of the series placed upon the market up to that date. After that time many new processes were patented, all, however, tending to the same object, that of producing a white pigment, composed of zinc sulphide and barium carbonate, the results, however, in many cases ending with failure.
The North American region suffered from the excess influx of material in the market, especially from the Asian countries, in the first half of the third quarter. The quarter, however, showed signs of significant improvement with a rise in the number of offtakes. Further, the lack of labor in the US challenged the rates of production of titanium dioxide and resulted in the depletion in the level of existing inventories, pushing the titanium dioxide price graph in an upward direction.
