Al2O3 | B2O3 | BaO | C | CaO | CO2 | CoO | Cr2O3 | Cu2O | CuO | Fe2O3 | FeO | H2O | K2O | Li2O | LOI | MgO | MnO | MnO2 | Na2O | NiO | O | Organics | P2O5 | PbO | SiO2 | SnO2 | SO3 | SO4 | SrO | TiO2 | V2O5 | ZnO | ZrO | ZrO2Others
Ag2O | AlF3 | As2O3 | As4O6 | Au2O3 | BaF2 | BeO | Bi2O3 | CaF2 | CdO | CeO2 | Cl | CO | CrO3 | Cs2O | CuCO3 | Dy2O3 | Er2O3 | Eu2O3 | F | Fr2O | Free SiO2 | Ga2O3 | GdO3 | GeO2 | HfO2 | HgO | Ho2O3 | In2O3 | IrO2 | KF | KNaO | La2O3 | Lu2O3 | Mn2O3 | MoO3 | N2O5 | NaF | Nb2O5 | Nd2O3 | Ni2O3 | OsO2 | Pa2O5 | PbF2 | PdO | PmO3 | PO4 | Pr2O3 | PrO2 | PtO2 | RaO | Rb2O | Re2O7 | RhO3 | RuO2 | Sb2O3 | Sb2O5 | Sc2O3 | Se | SeO2 | Sm2O3 | Ta2O5 | Tb2O3 | Tc2O7 | ThO2 | Tl2O | Tm2O3 | U3O8 | UO2 | WO3 | Y2O3 | Yb2O3
|COLE - Co-efficient of Linear Expansion||0.031|
The two top clay bars contain 15% hydrous borax. At cone 06, a very low temperature, it has already melted and drained out of the bars, running down over the others as a glass.
Fired at 1850. Notice that Frit 3195 is melting earlier. By 1950F, they appear much more similar. Melting earlier can be a disadvantage, it means that gases still escaping as materials in the body and glaze decompose get trapped in the glass matrix. But if the glaze melts later, these have more time to burn away. Glazes that have a lower B2O3 content will melt later, frit 3195 has 23% while Frit 3124 only has 14%).
This is unlike some raw materials which melt suddenly.
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.
I used a binder to form 10 gram balls and fired them at cone 08 (1700F). Frits melt really well, they do not gas and they have chemistries we cannot get from raw materials (similar ones to these are sold by other manufacturers). These contain boron (B2O3), it is magic, a low expansion super-melter. Frit 3124 (glossy) and 3195 (silky matte) are balanced-chemistry bases (just add 10-15% kaolin for a cone 04 glaze, or more silica+kaolin to go higher). Consider Frit 3110 a man-made low-Al2O3 super feldspar. Its high-sodium makes it high thermal expansion. It works in bodies and is great to incorporate into glazes that shiver. The high-MgO Frit 3249 has a very-low expansion, it is great for crazing glazes. Frit 3134 is similar to 3124 but without Al2O3. Use it where the glaze does not need more Al2O3 (e.g. it already has enough clay). It is no accident that these are used by potters in North America, they complement each other well. The Gerstley Borate is a natural source of boron (with issues frits do not have).
This high boron cone 04 glaze is generating calcium-borate crystals during cool down (called boron-blue). This is a common problem and a reason to control the boron levels in transparent glazes; use just enough to melt it well. If a more melt fluidity is needed, decrease the percentage of CaO. For opaque glazes, this effect can actually enable the use of less opacifier.
Melt fluidity test showing Perkins Studio clear recipe original (left) and a reformulated version that sources the boron from Ferro Frit 3134 instead of Gerstley Borate (right). The later is less amber in color (indicating less iron) and it melts to very close to the same degree.
These two boron frits (Ferro 3124 left, 3134 right) have almost the same chemistry. But there is one difference: The one on the right has no Al2O3, the one on the left has 10%. Alumina plays an important role (as an oxide that builds the glass) in stiffening the melt, giving it body and lowering its thermal expansion, you can see that in the way these flow when melting at 1800F. The frit on the right is invaluable where the glaze needs clay to suspend it (because the clay can supply the Al2O3). The frit on the left is better when the glaze already has plenty of clay, so it supplies the Al2O3. Of course, you need to be able to do the chemistry to figure out how to substitute these for each other because it involves changing the silica and kaolin amounts in the recipe also.
The ulexite in Gerstley Borate melts first, producing an opaque fired glass having the unmelted (and still gassing) particles of colemanite suspended in it. By 1750F the colemanite is almost melted also. Boron-containing frits, by contrast, begin softening at a much lower temperature and gradually spread and melt gradually. Not surprisingly they produce a more stable glaze (albeit often less interesting visually).
The porcelain mug on the left is fired to cone 6 with G2926B clear glossy glaze. This recipe only contains 25% boron frit (0.33 molar of B2O3). Yet the mug on the right (the same clay and glaze) is only fired to cone 02 yet the glaze is already well melted! What does this mean? Industry avoids high boron glazes (they consider 0.33 high boron) because this early melting behavior means gases cannot clear before the glaze starts to melt (causing surface defects). For this reason, fast fire glazes melt much later. Yet many middle temperature reactive glazes in use by potters have double the amount of B2O3 that this glaze has!
Boron (B2O3) is like silica, but it is also a flux. Frits and Gerstley Borate supply it to glazes. In this test, I increased the amount of boron from 0.33 to 0.40 (using the chemistry tools in my insight-live.com account). I was sure that this would make the glaze melt more and have less of a tendency to craze. But as these melt flow tests (10 gram balls melted on porcelain tiles) show, that did not happen. Why? I am guessing that to get the effect B2O3 has to be substituted, molecule for molecule for SiO2 (not just added to the glaze).
All common traditional ceramic base glazes are made from only a dozen elements (plus oxygen). Materials decompose when glazes melt, sourcing these elements in oxide form. The kiln builds the glaze from these, 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. And it is simpler than looking at glazes as recipes of hundreds of different materials (each sources multiple oxides so adjusting it affects multiple properties).
Look at recipes before wasting time and money on them. Are they serious? This is a cone 6 melt flow comparison between a matte recipe, found online at a respected website, and a well-fluxed glossy glaze we use often. Yes, it is matte. But why? Because it is not melted! Matte glazes used on functional surfaces need to melt well, they should flow like a glossy glaze. How does that happen? This recipe has 40% nepheline syenite. Plus lots of dolomite and calcium carbonate. These are powerful fluxes, but at cone 10, not cone 6! To melt a cone 6 glaze boron, zinc or lithia are needed. Boron is by far the most common and best general purpose melter for potters (it comes in frits and gerstley borate, colemanite or ulexite; industry uses more boron, zinc and lithia frits). The lesson: Look at recipes before trying them.
The cone 6 glazes on the left have double the boron of those on the right so they should be melting much more. But they flow less because they have much higher Al2O3 and SiO2 contents. This effect renders them milky white vs. the transparent of those on the right. Why? Because G and H are trapping micro-bubbles because of the increased viscosity of the melt. In spite of this, the two on the left do fire almost transparent when applied to ware, they have enough fluidity to shed most of the bubbles when in a thin layer. The ones on the right are too fluid, they will run excessively on ware unless applied thinly. The sweet-spot is a little more fluidity than those on the left. But there is another very important factor: Durability. The increased Al2O3 in G and H make them fire harder, more resistant to abrasion. The added SiO2 adds resistance to leaching.
I am comparing 6 well known cone 6 fluid melt base glazes and have found some surprising things. The top row are 10 gram balls of each melted down onto a tile to demonstrate melt fluidity and bubble populations. Second, third, fourth rows show them on porcelain, buff, brown stonewares. The first column is a typical cone 6 boron-fluxed clear. The others add strontium, lithium and zinc or super-size the boron. They have more glassy smooth surfaces, less bubbles and would should give brilliant colors and reactive visual effects. The cost? They settle, crack, dust, gel, run during firing, craze or risk leaching. In the end I will pick one or two, fix the issues and provide instructions.
These melt-flow and ball-melt tests compare 6 unconventionally fluxed glazes with a traditional cone 6 moderately boron fluxed (+soda/calcia/magnesia) base (far left Plainsman G2926B). The objective is to achieve higher melt fluidity for a more brilliant surface and for more reactive response with colorant and variegator additions (with awareness of downsides of this). Classified by most active fluxes they are: G3814 - Moderate zinc, no boron G2938 - High-soda+lithia+strontium G3808 - High boron+soda (Gerstley Borate based) G3808A - 3808 chemistry sourced from frits G3813 - Boron+zinc+lithia G3806B - Soda+zinc+strontium+boron (mixed oxide effect) This series of tests was done to choose a recipe, that while more fluid, will have a minimum of the problems associated with such (e.g. crazing, blistering, excessive running, susceptibility to leaching). As a final step the recipe will be adjusted as needed. We eventually chose G3806B and further modified it to reduce the thermal expansion.
These are the inside uppers on two mugs made from the same clay with the same clear glaze. The one on the left was fired in a large electric kiln full of ware (thus it cooled relatively slowly). The one on the right was in a test kiln and was cooled rapidly. This glaze contains 40% Ferro Frit 3134 so there is plenty of boron and plenty of calica to grow the borosilicate crystals that cause the cloudiness in the glass. But in the faster cooling kiln they do not have time to grow.
Both mugs have the same cone 6 oxidation high-iron (9%), high-boron, glossy glaze. Iron silicate crystals have completely invaded the surface of the one on the right, turning the near-black glossy into a yellowy matte. Why? Three things. It was slow-cooled and the other free-fall-cooled (firings done in the same kiln). The glaze has a fluid melt (it runs) and its percentage of iron is high enough that it could precipitate out from solution in the melt (given the time). Susceptible glazes have a temperature at which crystals form the best and that temperature can be hundreds of degrees down from the firing cone (or higher if precipitation is occurring). In industry, devitrification is regarded as a defect. But potters call it crystallization. Understanding (especially the chemistry and materials) and experimental firings are needed to learn to control and exploit the effect in a glaze.
Out Bound Links
This term is very generic, referring of course to ...
Colemanite, Calcium Borate, Borocalcite
Boracic acid, Orthoboric Acid, Hydrous Boric Oxide
Sodium TetraBorate Decahydrate, Borax 10-hydrate, 10 Mol Borax, Neobor, Borax
Anhydrous Boric Acid, B2O3
Borax 5 Mol, Sodium Tetraborate, Borax 5-hydrate
The term 'limit formula' historically has typicall...
In Bound Links
This is a frit based boron base glaze that is easily adjustable in thermal expansion, a good base fo...
In functional ceramics this term generally refers ...
A key lesson because it explains the difference be...
On the theoretical glaze chemistry level, a flux i...
The term 'boron' refers to the oxide B2O3. 'Borate...
A base glaze is one having no opacifiers, variegat...
An oxide is a combination of oxygen and another el...
By Tony Hansen