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Staining of a sanitaryware glaze after years of use

This problem typically happens after some years of use. Here are some questions to answer:
A glaze may look smooth visually, but is it really? If the surface has micro-cavities and surface disruptions this could give organics a place to attach and build up. Firing curves need to take into account the LOI of glaze materials (which can affect the microsurface), materials like calcium and barium carbonate, dolomite, talc and even clay.
Has the mirco-surface of the glaze changed? Many labs offer surface analysis services so it is possible to have a surface compared with one known to be good.
Is the glaze subject to leaching? This could happen if the fired matrix has excessive phase changes, possibly due to poor mixing, frit quality issues or materials of excessive particle size (e.g. use 400 mesh silica instead of 200 or 300). A change in the flow of a routine melt fluidity test can alert you to changes in materials or slurry preparation.
Zircon is implicated in cutlery marking, if your glaze is marking this puts suspicion on the zircon as at least part of the problem. What grade of zircon do you use? It should be 5 micron. Are you using high-energy mixing to separate the zircon agglomerates?
Is your glaze fired at the temperature to produce optimum hardness and durability? Fire it higher and lower than the production temperature and test surface properties and melt flow. If you determine, for example, that it is under-firing, then add flux to melt it a little more. If it is under-fired, add SiO2 or Al2O3 or reduce flux (KNaO, MgO or CaO).

Staining of sanitaryware glazes

Related Pictures

Adding an opacifier can produce cutlery marking


Opacified glaze is cutlery marking

This is G2934 cone 6 matte (left) with 10% zircon (center), 4% tin oxide (right). Although the base unopacified recipe does not cutlery mark the other two do. Although the marks clean off all of the two on the right, the zircon version (in this case Zircopax) version has the worst and is difficult to clean. Thus, a small change is all that is likely needed. One solution is to reduce the matteness of this glaze, moving to more toward a satin surface. A way to do this is to line-blend in a glossy glaze to create a compromise between the most matteness possible yet a surface that does not mark or stain. Another option is to switch to 400 mesh silica in the recipe, that will enable many more of the particles to go into solution in the melt, thus increasing the gloss a little (an improving the firing surface in other ways).

Links

Troubles Staining of Fired Ceramic Glazes
Ceramic glazes are glass. That means they are always easy to clean, right? Wrong - because the surface is not always glassy.
Glossary Sanitary ware
A type of porcelain zircon-glazed ceramic that includes bathtubs, sinks, toilets, etc.

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