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Tin-glazing

Tin-glazing is the process of giving tin-glazed pottery items a ceramic glaze that is white, glossy and opaque, which is normally applied to red or buff earthenware. Tin-glaze is plain lead glaze with a small amount of tin oxide added. The opacity and whiteness of tin glaze encourage its frequent decoration. Historically this has mostly been done before the single firing, when the colours blend into the glaze, but since the 17th century also using overglaze enamels, with a light second firing, allowing a wider range of colours. Majolica, maiolica, delftware and faience are among the terms used for common types of tin-glazed pottery.

History
white ware bowl, not tin-glazed (left), found in Iran, and Iraqi tin-glazed earthenware bowl (right) found in Iraq, both 9th–10th century. British Museum. The earliest tin-glazed pottery appears to have been made in Abbasid Iraq (750–1258) in the 8th century, fragments having been excavated during the First World War from the palace of Samarra about fifty miles north of Baghdad. The history of tin glazes in the Islamic world is disputed. One possible reason for the earlier production of tin-glazed wares could be attributed to the trade between the Abbasid Empire and ancient China from the 8th to 9th century onwards, resulting in imitation of white Chinese stoneware by local Islamic potters. Another might be local glaze-making rather than foreign influence, supported by the similarity between the chemical and microstructural features of pre-Islamic white opaque glazes and that on the first tin-opacified wares resulting in the emergence of Italian Maiolica. Amongst others, Luca della Robbia, born in Florence about 1400, used tin oxide as an opacifier in glazes. Potters began to draw polychrome paintings on the white opaque surface with metallic oxides such as cobalt oxide and to produce lustreware. The off-white fired body of Delftware and English Majolica was made to appear white, and hence mimic the appearance of Chinese porcelain, by the application of a glaze opacified and coloured white by the addition of tin oxide. By the late 18th century the reduction in the price of porcelain, and the new English creamwares and related types, stronger, lighter and often cheaper than traditional earthenwares, hit the production of tin-glazed wares very hard, and production of "useful" rather than decorative wares almost ceased, so that "by 1850 the industry was almost extinct" in France. In 1947 Arthur Lane wrote it was "now only [made in Europe] in a few places to provide the tourist with souvenirs" Manufacturing process and colours Though the recipe of tin glazes may differ in different sites and periods, the process of the production of tin glazes is similar. Generally speaking, the first step of the production of tin glazes is to mix tin and lead in order to form oxides, which was then added to a glaze matrix (alkali-silicate glaze, for example) and heated. After the mixture cooled, the tin oxide crystallises as what has been mentioned above, therefore generates the so-called white tin-opacified glazes. Besides, the body of tin-opacified wares is generally calcareous clays containing 15-25% CaO, of which the thermal expansion coefficient is close to that of tin glazes, thus avoid crazing during the firing process. On the other hand, the calcareous clay fired in an oxidising atmosphere results in a buff colour, thus lower the concentration of tin oxide used The white opaque surface makes tin glaze a good base for painted decoration. The decoration is applied as metallic oxides, most commonly cobalt oxide for blue, copper oxide for green, iron oxide for brown, manganese dioxide for purple-brown and antimony for yellow. Late Italian maiolica blended oxides to produce detailed and realistic polychrome paintings, called istoriato. To these oxides modern potters are able to add powdered ceramic colours made from combinations of oxide, sometimes fritted. In the sixteenth century, the use of subtle and blended colours which were not strong enough to penetrate the opaque glaze made the delicate control of tonal values possible, and the painting therefore had to be done on the glaze surface, which then becomes a common manner of painting on tin-glazed wares. The disadvantage was that only a narrow group of pigments produced good colours after firing at the relatively high temperatures of up to . These included cobalt blue, manganese dark purple, copper green, antimony yellow, and the very tricky iron reds and brown, which only some potters were able to make as a good red. In the 18th century overglaze enamels began to be used in the same way as on porcelain; this technique is often called petit feu in English when talking about faience (the Italian name is piccolo fuoco). A much wider range of colours was possible, but after the fired and glazed wares were painted a third firing was required, at a lower temperature of perhaps . In modern versions, the pottery vessels are biscuit fired, usually between . The fired vessel is dipped in a liquid glaze suspension which sticks to it, leaving a smooth and absorbent surface when dry. On this surface colours are applied by brush, the colours made from powered oxides mixed with water to a consistency of water-colour paint, sometimes with the addition of a binding agent such as gum arabic. The unfired glaze absorbs the pigment like fresco, making errors difficult to correct but preserving the brilliant colors of the oxides when fired. The glazed and decorated vessels are returned to the kiln for a second firing, usually between 1000 and 1120 °C (the higher temperatures used by modern potters). Lustered wares have a third firing at a lower temperature, necessitating a delicate control of the amount of oxygen in the kiln atmosphere and therefore a flame-burning kiln. Traditional kilns were wood firing, which required the pots to be protected in the glaze and luster firings by saggars or to be fired in a muffle kiln. Except for those making luster ware, modern tin-glaze potters use electric kilns. The recrystallisation of tin oxide during the firing provides evidence of the slightly different methods of different production sites, as the crystal size, the distribution and the concentration may be influenced. For instance, the analysis of the 14th century Islamic tin glazes from eastern Spain indicates that these samples may be produced by non-fritting methods, as the heterogeneous distribution of tin oxides may be the remains of original grains of tin oxides. In this application, additions of up to 6% are reported to be used. The cost of tin oxide rose considerably during World War I (1914-1918), and resulted in a search for cheaper alternatives. Whilst zirconium compounds are not as effective, their low price led to a gradual increase in popularity with an associated reduction in use of tin oxide. Today, tin oxide finds limited use in glazes, generally its use is restricted to specialist low temperature applications, and by artisanal studio potters. The whiteness resulting from the use of zirconia has been described as more clinical than that from tin oxide, and is consequently preferred in some applications. The Koninklijke Tichelaar Makkum factory, or Royal Tichelaar Makkum, based in Makkum, Friesland continue the production Delftware using tin-glazed earthenware. ==Properties==
Properties
, the raw ingredient in Tin-glazing. Only one tin compound, tin(IV) oxide (SnO2), also called stannic acid, is commercially exploited for tin glaze. After firing, tin oxide remains in suspension in the vitreous matrix of the glaze. Because tin's high refractive index is different from the vitreous matrix, light is scattered: hence the opacity of tin glaze. Generally speaking, the more different the refractive index between the particles and the glaze matrix, the larger the opacity. Similarly, the closer the particle size to the light wavelength (100–1000 nm for visible light) and the more irregular the surface, the larger the degree of opacification. The degree of dissolution increases with the firing temperature, and hence the extent of opacity diminishes. Although dependent on the other constituents the solubility of tin oxide in glaze melts is generally low. Its solubility is increased by Na2O, K2O and B2O3, and reduced by CaO, BaO, ZnO, Al2O3, and to a limited extent PbO. In some cases, the tin oxide is presented not only as small crystals but also as aggregates of particles. These factors – the high refractive index, the low solubility in glazes and the particle size make tin oxide an excellent opacifier. In the beginning of the use of tin oxide, it is mainly viewed as a slip layer between the glaze and ceramic body. This could be seen from the SEM photomicrographs of some earlier Islamic glazed ceramics, of which the particles of tin oxide are concentrated at the interface, together with the existence of wollastonite, diopside and air bubble as other opacifiers. The microanalysis of later tin glazes reveals the distribution of tin oxide through the glazes rather than just at the interface, which indicates that tin oxide is really acting as an opacifier instead of only a surface coating layer. ==Composition==
Composition
Analyses and recipes The earliest Middle Eastern tin glazes used calcium, lead and sodium compounds as fluxes in combination with the silica in silica. An Islamic opaque white glaze has been analysed, and is quoted below as a Seger formula: ::*PbO=0.32 ::*CaO=0.32 ::*K2O=0.03 ::*Na2O=0.29 ::*MgO=0.04 ::*Al2O3=0.03 ::*SiO2=1.73 ::*SnO2=0.07 In this recipe, the addition of alkali helps to increase the hardness of the surface and clarify the colour of the glaze as well. With the development of tin glazes, the significant amount of tin oxide indicates its deliberate addition as an opacifier. A recipe involving the use of three ingredients was given in Abu’l-Qasim’s treatise from Persia in the 14th century: a glass-frit of quartz and potash, a lead-tin calx and a calcination of limestone and quartz. Afterwards, with the spread of tin glazes, lead gradually became the principal background in tin glazes, though a small proportion of alkali was still introduced in order to increase the fusibility. No specific recipes alluding to tin glazes in Spain have been found in ancient archives. However, recent research has shown that, at least since the 10th century AD, most Islamic white glazes in Spain were lead-silica glazes with tin oxide as an opacifier. That is, no alkaline glazes or lead-alkaline glazes have been found. Piccolpasso recorded several glazes used in Italy in the 1550s, all variations of lead, tin, lime, soda and potash glazes. It is believed early Spanish glazes were similar. ::*PbO=0.52 ::*CaO=0.16 ::*K2O=0.03 ::*Na2O=0.29 ::*Al2O3=0.15 ::*SiO2=2.77 ::*SnO2=0.23 A more recent recipe is: In conjunction with small additions of zinc oxide and titanium oxide, additions of tin oxide up to 18% to lead glazes can produce a satin or vellum surface finish. ==References==
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