We are looking at two pairs of samples, they demonstrate why knowing about glaze chemistry can be so important. Both pairs are the same glazes: G2934 cone 6 matte and G2916F cone 6 glossy. The left pair has 5% maroon stain added, the right pair 5% purple stain. The red and purple develop correctly in the glossy but not the matte. Why? The Mason Colorworks reference guide has the same precaution for both stains: the host glaze must be zincless and have 6.7-8.4% CaO (this is a little unclear, it is actually expressing a minimum, the more the CaO the better). The left-most samples of each pair here have 11% CaO, the right-most have 9%. So there is enough CaO. The problem is MgO (it is the mechanism of the matteness in the left two), it impedes the development of both colors. When you talk to tech support at any stain company they need to know the chemistry of your glaze to help.
These are thermal expansion curves for body, engobe and glaze (from a dilatometer, a device that measures it against increasing temperature). The upper line is the body. The center line is the engobe. The lower line is the glaze. The ceramic tile industry is very conscious, not only of glaze-fit but also engobe-fit. Engobes (slips) are employed to cover brown or red burning bodies so they glaze like a porcelain. Typically technicians tune the formulation of the engobe to have an expansion between the body and glaze. The body is highest so that during cooling, as it contracts, it puts a squeeze on the engobe (the engobe thus never finds itself under tension). The glaze has the lowest expansion, it is under a state of compression by the engobe (and slightly more by the body). This equilibrium enables the tile to wear for many years without crazing or shivering. Chart courtesy of Mohamed Abdelmagid.
The glaze on the right is crawling at the inside corner. Why? Multiple factors contribute. The angle between the wall and base is sharper. A thicker layer of glaze has collected there (the thicker it is the more power it has to impose a crack as it shrinks during drying). It also shrinks more during drying because it has a higher water content. But the leading cause: Its high raw clay content increases drying shrinkage. Calcining part of the raw clay destroys its affinity for water (which is what makes it plastic), this is an effective way to deal with this. Or doing a little chemistry to source some of the Al2O3 from materials other than clay (e.g. a frit having a higher Al2O3 content).
Three cone 6 commercial bottled glazes have been layered. The mug was filled with lemon juice over night. The white areas on the blue and rust areas on the brown have leached! Why? Glazes need high melt fluidity to produce reactive surfaces like this. While such are normally subject to leaching, the manufacturers were able to tune the chemistry of each to make them resistant. But the overlaps mingle well (because of the fluidity), they are new chemistries, less stable ones. What is leaching? Cobalt! Not good. What else? We do not know, these recipes are secret. It is much better to make your own transparent or white liner glaze. Not only can you pour-apply it and get very even coverage, but you know the recipe, have control, can adjust to fit your body.