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.
The Chemistry, Physics and Manufacturing of Glaze Frits
A detailed discussion of the oxides and their purposes, crystallization, phase separation, thermal expansion, solubility, opacity, matteness, batching, melting.
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.
In ceramic glazes each oxide generally makes a specific contributions to the melting and freezing behavior of the glaze. However interactions are also important.
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