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Oxide Interaction

In ceramic glazes each oxide generally makes a specific contributions to the melting and freezing behavior of the glaze. However interactions are also important.

Details

In a glaze melt, oxides do not act alone, they interact. For example, while one material might not melt well by itself, when combined with others the mix as a whole can melt at a significantly lower temperature than any of the ingredients in the mix. Cornwall stone is an example, by itself it does not melt enough to even be a glaze at cone 10, but a glaze can be made using this material in combination with kaolins, silica, etc. Oxides that are even refractory by themselves can be powerful fluxes in combination with silica and alumina, a good example is the material calcium carbonate. By itself it is completely refractory and yet at cone 8-10 it is the principal flux in stoneware glazes. Thus, due to interaction, the function of the oxide is changed completely.

Cornwall Stone off different dates compared to substitute L3617

Cornwall Stone off different dates compared to substitute L3617

This is a cone 11 oxidation melt flow test. Shown (left to right) are the new shipment of Cornwall Stone 2011, the L3617 calculated equivalent (a recipe, see link), the older Cornwall shipment we have been using and the H&G substitute 2011 (far right, mislabelled on the picture). These do not flow well here, a small frit addition is needed to better compare them. However they have melted enough to see some differences in whiteness and degree of melt. Notice the L3617 is more like the old Cornwall than the new Cornwall is.

Calcium carbonate and dolomite are refractory when used pure

Calcium carbonate and dolomite are refractory when used pure

Examples of calcium carbonate (top) and dolomite (both mixed with 25% bentonite to make them plastic enough to make a test bars). They are fired to cone 9. Both bars are porous and refractory, even powdery. However, put either of these in a mix with other ceramic minerals and they interact strongly to become fluxes.

Frits melt so much better than raw materials

Frits melt so much better than raw materials

Feldspar and talc are both flux sources (glaze melters). But the fluxes (Na2O and MgO) within these materials need the right mix of other oxides with which to interact to vitrify or melt a mix. The feldspar does source other oxides for the Na2O to interact with, but lacks other fluxes and the proportions are not right, it is only beginning to soften at cone 6. The soda frit is already very active at cone 06! As high as cone 6, talc (the best source of MgO) shows no signs of melting activity at all. But a high MgO frit is melting beautifully at cone 06. While the frits are melting primarily because of the boron content, the Na2O and MgO have become active participants in the melting of a low temperature glass. In addition, the oxides exist in a glass matrix that is much easier to melt than the crystal matrix of the raw materials.

Ionic forces chart

Ionic forces chart

Cations having high charges and small radiuses (and thus high field forces like boron and silicon), are network formers. Network modifiers have small charges, large radiuses and a big coordination number for oxygen ions. While considering ions as rigid spheres is an over-simplified way to describe reality, it has still proven useful to describe characteristics of each. For instance lithium has a ionic radius smaller than sodium and so it can locate into smaller cavities. The ionic field force of lithium is also stronger than sodium and it is essentially non-directional, thus it more easily produces crystals of a separate phase. Alkaline earth elements locate into cavities of the network as well, but they have double charges and thus act like a bridges between two oxygen ions (preventing the three-dimensional network from being fully destroyed). Moreover bonds between alkaline earth ions and oxygen are stronger than alkaline so we observe neither a rapid decrease in viscosity or a significant increase of the thermal expansion coefficient. It is notable that for similar molar percentages, frits containing magnesium crystallize more easily than frits containing calcium.

Aluminum, titanium and zirconium are classified as intermediate glass formers because they have a strong four-way coordination for oxygen ions, like silicon. Thus, for these oxides, we do not observe any interruption of the three-dimensional silicate-based network. For a better understanding consider more details about aluminum, boron, zirconium and titanium.

Aluminum: Usually aluminum shows a four-way coordination when it acts as a glass former, tetrahedrons are linked to four oxygen atoms while the local excess of negative charge is counterbalanced by an alkaline cation placed close to the aluminum ion. Thus additions of aluminum to a glass help to stop alkaline ions from breaking the three dimensional network of the glass. This produces the characteristic lower melt fluidity and tendency to crystallize and also reduces the thermal expansion and thermal stability. One downside to alumina is that it contributes to a higher viscosity of frit batches during melting (in the furnace tank) making homogenization more difficult. Usually the percentage of aluminum oxide is in the range 4 – 12%.

Boron: Boron is a basic component of frits yet its characteristics are so peculiar that it cannot easilly be compared to other elements. Boron, like aluminum, exhibits a four-way coordination when forming a glass network (being in the center of a tetrahedron of oxygen ions). This is possible only when the molar alkaline percentage is less than 30-40% because above this limit boron has three-way coordination, forming triangles.

Another peculiar characteristic is that boron is not just dispersed as tetrahedrons or triangles in the network of silica tetrahedrons. Rather it forms boric groups, containing from 3 to 5 boron atoms and the groups are randomly dispersed in the glassy matrix. However single BO3 triangles and BO4 tetrahedrons are always present. For quenched frits the presence of these groups is likely minimal but we can presume they form again when glazes containing the frit are fired (there are experimental evidences demonstrating this).

Boron oxide is an important component of low melting frits because it increases fusibility without a proportional increase in thermal expansion. Moreover boron oxide and sodium borate, due to their low melting point, are useful during smelting of frits because they form a glassy matrix early and act as catalysts in the melting and dissolving of other materials.

Zirconium - Titanium: Their influence on surrounding oxygen ions is very strong and scarcely directional so their solubility in frits is poor. Their solubility in glass and actions as glass formers are proportional to temperature. In quenched frits they remain in the dissolved in the glassy matrix but when we fire them again (within a glaze), these oxides easily precipitate crystal compounds.

Links

Oxides CaO - Calcium Oxide, Calcia
Materials Cornwall Stone

By Tony Hansen


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