ZnO (Zinc Oxide)
Notes-Together with PbO it is considered one of the metallic oxide fluxes. In smalls amounts zinc helps in the development of glossy and brilliant surfaces the way lead did.
-ZnO starts its fluxing action around 1000C (i.e. bristol glazes) whereas by itself ZnO does not melt until 1975C. It is a late and vigorous melter for low fire glazes and thus useful in fast fire applications.
-ZnO is easily changed to Zn metal by the action of CO and H2 in the reduction phase of a gas-fired kiln (and possibly poorly ventilated electric kilns). Pure Zn metal melts at 419C and then boils and vaporizes at 907C.
-It does take time for zinc to volatilize and meanwhile it does encourage the melting process to begin earlier in stoneware applications, making it more vigorous. However zinc metal in a more molten glaze is also more reduceable.
-ZnO is a low expansion secondary flux which is handy to prevent crazing if used for, or instead of, high expansion fluxes. It improves elasticity so that glazes which might otherwise craze or shiver will fit.
-ZnO can extend firing range.
-In moderate to high amounts it acts to produce mattes and crystalline surfaces, especially if supersaturated (up to 0.8 molar) and cooled slowly (produces crystal phases like Zn2SiO4, that is, willemite). However, these crystalline surfaces can be rough enough to cause cutlery marking.
-Zinc can improve durability in some glazes. In others it can reduce resistance to acid attack.
-At low temperatures small amounts can have a marked effect on gloss and melting, although at temperatures below Orton cone 03-02 it is not normally an active flux.
-At middle temperatures, zinc can be used as a major flux in amounts to 5%.
-At higher oxidation temperatures it is valuable to provide a smooth transition from sintered to melted stage. Zinc is common in fast fire glazes.
-In certain mixtures it is very powerful, even in small amounts. The melting power per unit added drops quickly as the amount used exceeds 5%.
-Zinc can have amphoteric qualities if it is used with boron.
-Zinc has a complicated color response. It can have harmful and helpful effects on blues, browns, greens, pinks and is not recommended with copper, iron, or chrome.
Yikes. Cutlery marking this bad on a popular glaze!
An example of how a spoon can cutlery mark a glaze. This is a popular middle temperature recipe used by potters. The mechanism of its matteness is a high percentage of zinc oxide that creates a well-melted glaze that fosters the growth of a mesh of surface micro-crystals. However these crystals create tiny angular protrusions that abrade metal, leaving a mark. Notice the other matte flow on the left (G2934), it not only has a better surface (more silky feel) but also melts much less (its mechanism is high MgO in a boron fluxed base).
Raw and calcined zinc oxides in a crystalline glaze
Zinc oxide calcined (left) and raw (right) in typical crystalline glaze base (G2902B has 25% zinc) on typical cone 6 white stoneware body. This has been normally cooled to prevent crystal development. The melting pattern is identical. Note how badly these are crazed, this is common since crystalline glazes are normally high in sodium.
A good matte glaze. A bad matte glaze.
A melt fluidity comparison between two cone 6 matte glazes. G2934 is an MgO saturated boron fluxed glaze that melts to the right degree, forms a good glass, has a low thermal expansion, resists leaching and does not cutlery mark. G2000 is a much-trafficked cone 6 recipe, it is fluxed by zinc to produce a surface mesh of micro-crystals that not only mattes but also opacifies the glaze. But it forms a poor glass, runs too much, cutlery marks badly, stains easily, crazes and is likely not food safe! The G2934 recipe is google-searchable and a good demonstration of how the high-MgO matte mechanism (from talc) creates a silky surface at cone 6 oxidation the same as it does at cone 10 reduction (from dolomite). However it does need a tin or zircon addition to be white.
Two stains. 4 colors. Why? The chemistry of the base glazes.
We are looking at two pairs of samples, they demonstrate why knowing about glaze chemistry can be so important. Each pair shows the same stain on two different base glazes (G2934 cone 6 matte and PGF1 cone 6 glossy). Why does the maroon not develop in the left pair, why is the purple stain firing blue on the right? The Mason Colorworks color chart and reference guide specifies that the host glaze must be zincless and have 6.7-8.4% CaO (this is a little unclear, it actually is expressing a minimum, the more CaO the better). But the colorless one has 11% CaO, it should work (the maroon one has only 9% and it is working)! Likewise the purple color develops correctly in the 9% CaO but wrong in the 11% CaO base. Both stains have the same caution on the reference guide. What is going on? It is an undocumented issue: MgO. The 11% CaO base glaze is high in MgO (that is what makes it matte), that impedes the development of both colors. When you talk to tech support at Mason (or any stain company), they need to know the chemistry of your glaze to help, not the recipe.
Ceramic Oxide Periodic Table in SVG Format
The periodic table of common ceramic oxides in scalable vector format (SVG). Try scaling this thumbnail: It will be crystal-clear no matter how large you zoom it. All common pottery base glazes are made from only 11 elements (the grey boxes) plus oxygen. Materials decompose when glazes melt, sourcing these elements in oxide form; the kiln builds the glaze from these. The kiln does not care what material sources what oxide (unless the glaze is not melting completely). Each of these oxides contributes specific properties to the glass, so you can look at a formula and make a very good prediction of how it will fire. This is actually simpler than looking at glazes as recipes of hundreds of different materials.
A super glassy ultra-clear brilliantly glossy cone 6 clear base glaze? Yes!
I am comparing 6 well known cone 6 fluid melt base glazes and have found some surprising things. The top row are 10 gram balls of each melted down onto a tile to demonstrate melt fluidity and bubble populations. Second, third, fourth rows show them on porcelain, buff, brown stonewares. The first column is a typical cone 6 boron-fluxed clear. The others add strontium, lithium and zinc or super-size the boron. They have more glassy smooth surfaces, less bubbles and would should give brilliant colors and reactive visual effects. The cost? They settle, crack, dust, gel, run during firing, craze or risk leaching. In the end I will pick one or two, fix the issues and provide instructions.
Why fast fire glazes flux using zinc
We are comparing the degree of melt fluidity (10 gram balls melted down onto a tile) between two base clear glazes fired to cone 6 (top) and cone 1 (bottom). Left: G2926B clear boron-fluxed (0.33 molar) clear base glaze sold by Plainsman Clays. Right: G3814 zinc-fluxed (0.19 molar) clear base. Two things are clear: Zinc is a powerful flux (it only takes 5% in the recipe to yield the 0.19 molar). Zinc melts late: Notice that the boron-fluxed glaze is already flowing well at cone 1, whereas the zinc one has not even started. This is very good for fast fire because the unmelted glaze will pass more gases of decomposition from the body before it melts, producing fewer glaze defects.
In pursuit of a reactive cone 6 base that I can live with
These melt-flow and ball-melt tests compare 6 unconventionally fluxed glazes with a traditional cone 6 moderately boron fluxed (+soda/calcia/magnesia) base (far left Plainsman G2926B). The objective is to achieve higher melt fluidity for a more brilliant surface and for more reactive response with colorant and variegator additions (with awareness of downsides of this). Classified by most active fluxes they are: G3814 - Moderate zinc, no boron G2938 - High-soda+lithia+strontium G3808 - High boron+soda (Gerstley Borate based) G3808A - 3808 chemistry sourced from frits G3813 - Boron+zinc+lithia G3806B - Soda+zinc+strontium+boron (mixed oxide effect) This series of tests was done to choose a recipe, that while more fluid, will have a minimum of the problems associated with such (e.g. crazing, blistering, excessive running, susceptibility to leaching). As a final step the recipe will be adjusted as needed. We eventually chose G3806B and further modified it to reduce the thermal expansion.
2% Copper carbonate in two different cone 6 copper-blues
The top base glaze has just enough melt fluidity to produce a brilliant transparent (without colorant additions). However it does not have enough fluidity to pass the bubbles and heal over from the decomposition of this added copper carbonate! Why is lower glaze passing the bubbles? How can it melt better yet have 65% less boron? How can it not be crazing when the COE calculates to 7.7 (vs. 6.4)? First, it has 40% less Al2O3 and SiO2 (which normally stiffen the melt). Second, it has higher flux content that is more diversified (it adds two new ones: SrO, ZnO). That zinc is a key to why it is melting so well and why it starts melting later (enabling unimpeded gas escape until then). It also benefits from the mixed-oxide-effect, the diversity itself improves the melt. And the crazing? The ZnO obviously pushes the COE down disproportionately to its percentage.
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