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## Ceramics: Notes on Glaze Formulation and Firing

I hesitate to write an article on glaze formulations when there are so many on the internet. Still, there are some generalities that may be useful.

A few years ago I classified several glaze formulas according to firing temperature and surface finish. I did this for lead and non-lead glazes, both glossy and matte. I was surprised how easy it was to correlate composition with firing temperature (pyrometric cone or buller ring).

You can run the same exercise if you’re looking at multiple glaze compositions and trying to come up with just one. You can start your formulation activities by using the average of the composition ranges for each oxide addition for the temperature range you are shooting for.

The properties of the glaze can be calculated from the 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. However, relative calculations are generally true. You cannot calculate the exact measured value but you will know that Glaze A will have a higher expansion and lower viscosity than Glaze B.

My collaborators made hundreds of glazes over the years for pottery and fine china. Much of this work was done in joint efforts with frit suppliers as existing frits did not always make the move to large production operations.

Here are some factors that I found to be important:

*Glaze composition*

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

The complexity of the formula is important. Each element you add to the glaze affects the final-glaze properties. For example, too alkaline a material increases the solubility of the glaze, increases its thermal expansion, and generally increases destruction. A minimum amount of alkaline material will give the glaze fusibility. Also, individual bases act to different extents. Thus using more than one alkali and minimal amounts of each produces the best balance of properties.

The same goes for alkaline earths, glaze modifiers, and glass formers.

When making a glaze you must consider the entire periodic table of elements.

Remember that a very small addition of a particular element can give you the property you want, but increasing the amount even slightly can ruin your progress. As an inconvenience to glaze formulators, other elements interfere.

One more thing: You should use a minimum amount of binder. Sometimes it is best to use multiple binders in small quantities instead of one binder. Binders can be pure clay or organic compositions such as gums or resins. As I say, a mix is usually better. Neither will be good.

You can find it in my book to learn how to make hedges from scratch or using frits *Ceramics: Industrial Processing and Testing. * You can read the content on [http://www.tjbooks.com/ceram.htm]

*Firing conditions*

First, in my experience the glaze fires better in a periodic kiln than in a tunnel kiln. Combining a tunnel kiln cycle with a periodic kiln cycle may not produce the same results. Spatial configurations are as varied as environments.

Firing curves naturally have hot and cold periods.

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

During the summer, the binders are removed from the glaze.

They must be completely removed and not reduced to carbon during heating (preheat). That doesn’t mean you can’t reach reduced terms. Some compounds such as MnO and FeO can greatly improve melting although they are often only present in glazes in small amounts as impurities. These compounds do not form under oxidizing conditions. However, do not reduce the binders to carbon. It is almost impossible to remove most of the glaze during the rest of the firing.

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

Preheat or preheat is generally the production standard for tunnel kilns. So if you are not getting what you are looking for, you should adjust the burner or heating input in this area. You don’t want bubbles to form from all the binder during the soaking period. You have enough bubble problems without that.

During the soaking phase and at all high temperatures the glaze is changing structure. That is, the glaze is losing volatile elements due to high temperatures. This can be complicated because when one component of the glaze is removed it can increase the volatility of the other components.

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

As you lose the volatile elements you also increase the glaze viscosity when melted. For this reason, and others I think, rapid firing is often better than long firing cycles. In fact, I have seen glazes that require rapid firing.

Cold is important for both glazes and ceramic ware. You can cool quickly above the silica phase transition and then cool slowly through the transition. This may not be good for glazes that are trying to get rid of bubbles created after the glaze melts. This can put you between a rock and a hard place. You should be able to control the entire cooling zone of the tunnel kiln from the minute you exit the hot zone.

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