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## Ceramics: Notes on Glaze Formulation and Firing

I hesitate to write an article on how to make frosting when there is so much on the internet. However, there are some generalizations that may be useful.

A few years ago I classified many glaze compositions by firing temperature and surface finish. I did this for both gloss and matte lead and unleaded glazes. I was surprised how easy it was to relate the composition to the burning temperature (pyrometric cone or buller ring).

You can do the same type of exercise by looking at many frosting compositions, trying to come up with just one. You can start your composition activities using the averages of the composition ranges for each oxide additive in the temperature range you are shooting.

Glaze properties can be calculated by composition. For example, you can calculate the coefficient of thermal expansion. In my experience, the calculation does not match the measured properties of the final glaze. But relative calculations are usually true. You may not be able to calculate the exact measured value, but you know that glaze A has a higher expansion and lower viscosity than glaze B.

My associates made hundreds of glazes over the years for earthenware and fine china. Much of this work was done in a joint effort with frit suppliers, as existing frits are not always up to the task in large production operations.

Here are some factors I found important:

*Glaze composition*

Lead is magic in glazes. It must be used in deep-fried form and in the minimum amount possible to maintain the proper glaze flow in the molten state. Glazed cookware must pass all FDA and other restrictive tests. If lead is allowed, your problems are minimized. If air lead levels exceed OSHA standards, your workers should be monitored for blood lead. Borate frits can help reduce lead content but can increase solubility.

The complexity of the formula is important. Every element you add to the glaze affects the properties of the final glaze. For example, excess alkali content increases the solubility of the glaze, increases its thermal expansion, and generally wreaks havoc. The minimum alkali content gives the glaze meltability. Also, individual alkalis work to different extents. Therefore, more than one alkali should be used and the minimum amount of each that gives the best balance of properties should be used.

The same applies to alkaline earth metals, glaze modifiers and glass formers.

When making your glaze, you should consider the entire periodic table of elements.

Keep in mind that adding a very small amount of a certain element can give you the desired property, but increasing the amount just a little can ruin your progress. As an inconvenience, when making glazes, other elements interfere.

One more thing: you should use a minimal amount of binder. Sometimes it is better to use several binders in small amounts rather than just one binder. Binders can be purified clays or organic compositions such as gums or resins. As I say, a mix is usually best. None would be better.

If you want to learn how to formulate a look from scratch or use fritters, you can find it in my book *Ceramics: Industrial Processing and Testing. * You can read the content at [http://www.tjbooks.com/ceram.htm]

*Burning conditions*

First, in my experience, glazes burn better in batch kilns than in tunnel kilns. Matching a tunnel furnace cycle with a batch furnace cycle may not produce the same results. Spatial configurations vary, as does the atmosphere.

The burn curve naturally has warm-up and cool-down periods.

Between these slopes is a flat or modified soaking time/temperature.

Binders are removed from the glaze during heating.

They must be completely removed and not reduced to carbon during heating (preheating). That doesn’t mean you can’t approach mitigating circumstances. Some compounds, such as MnO and FeO, can significantly improve the melting, although they are often only present in trace amounts as an additive in the glaze. These compounds are not formed under oxidizing conditions. Anyway, don’t reduce binders to carbon. Removing many glazes during the rest of the firing is nearly impossible.

There are several means of determining the nature of burnout of a particular binder. Thermal Gravimetric Analysis (TGA) and Differential Thermal Analysis (DTA) come to this old head.

Preheating or heating is usually the production standard for tunnel furnaces. So, if you don’t get what you are looking for, you need to adjust the burners or heating input in that zone. You don’t want the binder to bubble during the soak. You have enough bubble problems without it.

In the soaking phase and at all higher temperatures, the glaze changes its composition. This means that the glaze loses volatile elements due to high temperatures. This can be tricky because removing one component of the glaze can increase the volatility of the other components.

For you chemical engineers, this would be somewhat similar to steam distillation.

When you lose volatiles, you also increase the viscosity of the glaze in the molten state. For this and other reasons, I think, rapid firing is often better than a long firing cycle. In fact, I have seen glazes that required rapid firing.

Cooling is important for both glazes and ceramics. You can cool rapidly above the silica phase transition and then slowly cool through the transitions. This may not be good for the icing, which is trying to get rid of bubbles after the icing melts. This can put you between a rock and a hard place. The entire cooling zone of the tunnel oven must be able to be controlled from the moment the dishes come out of the hot zone.

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