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Oxides

Oxide chemistry is one of the most powerful tools available for understanding and adjusting ceramic glazes. The fired properties of a glaze, its melting behaviour, thermal expansion, hardness, durability, colour and surface character, are strongly influenced by its oxide composition. This section documents the individual oxides important in ceramics, their roles in glazes, how they interact with each other and the materials that supply them.

In glaze chemistry, oxides are a way of expressing the chemical composition of a fired glaze. Materials are viewed as warehouses of oxides, supplying SiO₂, Al₂O₃, CaO, MgO, K₂O, Na₂O, B₂O₃ and others to the developing melt. This does not mean that a glaze is simply a collection of individual oxide molecules. Rather, the oxide formula is a model that enables us to calculate, compare and adjust the chemistry of complex glass-forming systems.

Oxides behave differently in mixtures: The properties of an individual oxide can be very different from its contribution to a glaze. Calcium oxide (CaO), for example, is a highly refractory material in its pure form. Yet when incorporated into a suitable glaze melt, in the presence of other oxides with which to interact, it becomes a powerful flux! Likewise, SiO₂ is a highly refractory glass former, but its behaviour depends on the other oxides present, their proportions and the firing conditions. This is why ceramic oxides cannot be assigned simple, absolute properties. Their effects are relative and frequently nonlinear. Increasing an oxide may improve one property while compromising another. Some oxides perform particular roles only within certain composition and temperature ranges. A change that works in one glaze may have a very different effect in another. The information in this section should therefore be interpreted in the context of the other oxides present, not as a set of universal rules.

Ceramic problems can be approached at several levels: the oxide, the mineral, the material, the recipe and the process. Knowing which level is relevant is often the key to solving a problem. For example, consider a glaze that is crazing. An excessive proportion of Na₂O may be contributing to a high thermal expansion. Oxide chemistry can be used to reduce the Na₂O while compensating with other oxides to preserve the desired melting behaviour, colour and surface character. But making that change also requires selecting appropriate materials, adjusting the recipe and testing the result under actual firing conditions.

A calculated oxide formula is not a complete description of glaze behaviour. Two recipes having almost identical chemistry can produce different fired results because of differences in raw material mineralogy, particle size, LOI, decomposition melting behaviour and firing conditions. Chemistry provides a powerful starting point, but testing establishes what actually works.

Oxide chemistry is also relevant to clay bodies, especially for understanding flux content, vitrification and glass formation. However, it is generally less predictive of their physical properties than it is for homogeneous glazes. Unlike a glaze, a fired ceramic body normally contains multiple crystalline phases, a glassy phase and some porosity. Two bodies having similar oxide chemistries can develop very different fired structures and properties because of differences in their mineralogy, particle sizes and firing histories. Thus, understanding clay bodies requires giving greater attention to these physical and mineralogical factors. Silica provides a good example. In a glaze, SiO₂ dissolves into the melt and participates in the glass network, often reducing thermal expansion as its proportion increases. In a clay body, quartz particles may remain as crystalline grains, contributing to the body's thermal expansion, its response to temperature changes and its fired structure. The chemistry may be the same, but the physical role is very different.

Many ceramic oxides have mineral or material equivalents. SiO₂, for example, is commonly supplied as ground quartz (silica). Others are sourced from compounds containing multiple oxides. Some oxides are available as pure powders but are impractical to use because of cost, solubility, instability or other physical properties. Digitalfire connects information at all these levels. The oxide records describe chemical roles and relationships. Mineral and material records document the substances that supply those oxides. Recipe records demonstrate how they are combined, while glossary articles explain the processes and principles involved. The objective is not simply to calculate glaze chemistry, but to use that chemistry alongside material knowledge and practical testing to understand, troubleshoot and improve ceramic products.

Related Information

Ceramic Oxide Periodic Table

Pretty well all common traditional ceramic base glazes are made from less than a dozen elements (plus oxygen). Go to the full picture of this table and click or tap each of the oxides to learn more (on its page at digitalfire.com). When materials melt, they decompose, sourcing these elements in oxide form. The kiln builds the glaze from them, it does not care what material sources what oxide (assuming, of course, that all materials do melt or dissolve completely into the melt to release those oxides). Each of these oxides contributes specific properties to the glass. So, you can look at a formula and make a good prediction of the properties of the fired glaze. And know what specific oxide to increase or decrease to move a property in a given direction (e.g. melting behavior, hardness, durability, thermal expansion, color, gloss, crystallization). And know about how they interact (affecting each other). This is powerful. A lot of ceramic materials are available, hundreds - that is complicated when individual materials source multiple oxides. Viewing a glaze as a simple unity formula of ceramic oxides is just simpler.

Links

Articles	The Four Levels on Which to View Ceramic Glazes By knowing which level to view a glaze from you are much better equipped to understand and control it. The levels are process, recipe, material, oxide.
Articles	Converting between Oxide Weight %, Mole % and Unity Formula Part of changing your viewpoint of glazes, from a collection of materials to a collection of oxides, is learning what a formula and analysis are, how conversion between the two is done and how unity and LOI impact this.
Articles	Understanding Ceramic Oxides Fired glazes are composed of oxide building blocks. Each of the oxides contributes different properties to the fired glaze and interacts with others in different ways. Understanding these gives you control.
Articles	Changing Our View of Glazes A big secret to getting control of glazes is to begin looking at them as formulas of oxides rather than recipes of materials.
Articles	Chemistry vs. Matrix Blending to Create Glazes from Native Materials Is it better to do trial and error line and matrix blending of materials to formulate glazes or is it better to use glaze chemistry right from the start?
Articles	Where do I start in understanding glazes? Break your addiction to online recipes that don't work or bottled expensive glazes that you could DIY. Learn why glazes fire as they do. Why each material is used. How to create perfect dipping and brushing properties. Even some chemistry.
Glossary	Ceramic Oxide In glaze chemistry, the oxide is the basic unit of formulas and analyses. Knowledge of what materials supply an oxide and of how it affects the fired glass or glaze is a key to control.
Glossary	Glaze Chemistry Glaze chemistry is the study of how the oxide chemistry of glazes relate to the way they fire. It accounts for color, surface, hardness, texture, melting temperature, thermal expansion, etc.

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