•The secret to cool bodies and glazes is a lot of testing.
•The secret to know what to test is material and chemistry knowledge.
•The secret to learning from testing is documentation.
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On the theoretical glaze chemistry level, a flux is an oxide that lowers the melting or softening temperature of a mix of materials. Fluxes are interactors (they often melt poorly on their own but react strongly with high melting materials where Al2O3/SiO2 predominate). There are less than ten common fluxes that we need to be concerned with. When we discuss them, we are talking about specific oxides (not powdered materials). Fluxes are sourced by the materials in the recipe, they are "swimming around" in the glaze melt during firing, making it fluid, giving it the ability to dissolve other particles within and without.
During firing, fluxes interact with the surface molecular structure of raw and refined materials and pull them away (dissolve them) molecule-by-molecule. Glaze chemistry considers how each of the oxides, as individuals, impose their properties on the glass (is assumes they have all melted or dissolved). But it also tries to understand how they interact with each other (e.g. sometimes combinations of fluxes react much more than logic would expect). Normally, the more kinds of fluxes present in a mix the lower its melting temperature (called the 'mixed oxide effect'). Interactions between fluxing oxides trigger on percentages, identities and mixtures of identities, temperature and kiln atmosphere (it is a a lifetime of study).
Glazes made from raw materials that source fluxing oxides (like feldspar, calcium carbonate, talc, dolomite) have flux balances that mirror what is common in rocks on the planet. These melt well at high stoneware temperatures. If we add Gerstley borate or Colemanite (which introduce B2O3) and metal oxides and carbonates (like zinc, lithium, strontium) it is possible to move melting temperatures way down and create a broader range of effects. Finally, by adding frits (artificial materials which release their fluxes more readily and that offer proportions that cannot be achieved with common materials) we can lower temperature even further and create very novel effects. Generally it is best to use as many fluxes in a glaze a possible, both to benefit from the mixed-oxide-effect, and have more options to adjust and tune the recipe.
In common glazes, the fluxing oxides comprise a minor percentage (compared to SiO2 and Al2O3). A high temperature (1300C) stoneware glaze might have 18% fluxes. A middle-fire (1180C) stoneware might contain 22%. A low fire glaze might have 30% flux (including B2O3). This is a narrower range of percentages than one would expect, but we can explain it by the varying potency of the fluxing oxides and the fact that certain oxides predominate in each temperature range. Of course, certain fluxes are supplied by materials that are much more expensive than others.
B2O3 is a special-case flux. It acts as low melting glass (it does not depend on percentage and interaction to activate). It works across the entire temperature range used in traditional ceramics. Much of the ceramic industry would not exist without this valuable oxide. Almost all frits contain at least some B2O3. It is common to see 15% B2O3 in low fire glazes. At middle temperature, 5% B2O3 is common (reactive glazes could have more). But if ZnO and significant KNaO are present, B2O3 could be around 2%. In high fire glazes there is almost always zero boron.
PbO is also a special case since, although it is a highly effective melter at low temperatures, it is no longer used in most circles because of toxicity concerns.
Li2O and ZnO are strong fluxing oxides, they work well at lower temperatures (but must be used judiciously at higher ones to avoid over melting and volatilization). Glazes employ fairly small amounts of these in combination with other fluxes (except for some zero-boron glazes that employ zinc as the power-melter). Over supplying either of these, especially at higher temperatures, can result in radical changes in color and surface characteristics. In stoneware and porcelain glazes it is common to see zero ZnO and LiO2.
At higher temperatures a new set of fluxes burst onto the scene: K2O and Na2O (commonly deemed KNaO), CaO, BaO, SrO, MgO. Although you will find these oxides in glazes at all temperatures, they are much less active at the lower. An exception is KNaO, very active at all ranges but restricted in the amount allowable because of its high thermal expansion (KNaO is very effective at fostering high gloss and brilliant colors). CaO is the most common fluxing oxide found at all temperature ranges (commonly 5-10% of the total). Actually, that is not entirely true. Although it reacts strongly (is very effective) at high temperatures, it is simply present in lower fire glazes, acting more as an intermediate (in fact, it can be a matting agent at low fire). CaO is just there. It is in the raw materials and frits we use (it is in the rocks on this planet). It is not a troublesome oxide (unless in very high amounts where it mattes by crystallizing). MgO is also common in glazes (since dolomite and talc, its sources, are so commonly used). MgO has very low thermal expansion, trading it against higher expansion fluxes is an effective way to deal with crazing. Using it as a predominant flux at middle and high temperatures produces a silky matte surface (while still melting well). SrO and BaO are used in smaller amounts (the latter normally for special colors or to produce micro-crystalline matte surfaces).
Colorants can also be powerful fluxes. Copper, cobalt and manganese all melt very actively in oxidation and reduction. However iron, a refractory material in oxidation, is a strong flux in reduction.
When the term flux is used on the material level, it is referring to the fact that the chemistry of the material contributes a significant amount of one or more of the fluxing oxides. Feldspar is an excellent example of a natural mix of refractory SiO2 and Al2O3 and fluxing oxides that, together, melt at a fairly low temperature. However, raw materials commonly as glazes fluxes, do not always melt well by themselves. Dolomite, like calcium carbonate, is a stoneware glaze fluxing material. But by itself it can be dead-burned and used as a heavy duty refractory for ladles and slag furnaces! Talc, in small percentages in middle temperature clay bodies, acts as a strong flux. However in large percentages, it is refractory also. Calcium carbonate is another example. While being a strong glaze flux at higher temperatures, it is refractory in a 75:25 plastic mix with bentonite (where the conditions for interaction to produce a glass are not present).
Fluxing oxides in frits melt much better than in raw materials. MgO is an excellent example. Glazes that employ a frit to supply the MgO melt much better than those employing dolomite or talc. SrO is a similar story.
Understandably, predicting the effects of a flux addition to a glaze (e.g. melting temperature) is very complex (involving interactions, eutectics, proportions, premelting, atmostphere and the physical and mineralogical properties of the particles). For this reason, glaze chemistry is applied much more in a relative sense than absolute to predict melting temperature.
Add 5% calcium carbonate to a tenmoku. What happens?
In the glaze on the left (90% Ravenscrag Slip and 10% iron oxide) the iron is saturating the melt crystallizing out during cooling. GR10-K1, on the right, is the same glaze but with 5% added calcium carbonate. This addition is enough to keep most of the iron in solution through cooling, so it contributes to the super-gloss deep tenmoku effect instead of precipitating out.
Firing shrinkage variation between various clays
Example of various materials mixed 75:25 with volclay 325 bentonite and fired to cone 9. Plasticities and diring shrinkages vary widely. Materials normally acting as fluxes (like dolomite, talc, calcium carbonate) are refractory here because they are fired in the absence of materials they react normally with.
Frits work much better in glaze chemistry
The same glaze with MgO sourced from a frit (left) and from talc (right). The glaze is 1215U. Notice how much more the fritted one melts, even though they have the same chemistry. Frits are predictable when using glaze chemistry, it is more absolute and less relative. Mineral sources of oxides impose their own melting patterns and when one is substituted for another to supply an oxide in a glaze a different system with its own relative chemistry is entered. But when changing form one frit to another to supply an oxide or set of oxides, the melting properties stay within the same system and are predictable.
How do metal oxides compare in their degrees of melting?
Metallic oxides with 50% Ferro frit 3134 in crucibles at cone 6ox. Chrome and rutile have not melted, copper and cobalt are extremely active melters. Cobalt and copper have crystallized during cooling, manganese has formed an iridescent glass.
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.
At 1550F Gerstley Borate suddenly shrinks! The melt fluidity ball tells us.
These GBMF test balls were fired at 1550F and were the same size to start. The Gerstley Borate has suddenly shrunk dramatically in the last 40 degrees (and will melt down flat within the next 50). The talc is still refractory, the Ferro Frit 3124 slowly softens across a wide temperature range. The frit and Gerstley Borate are always fluxes, the talc is a flux under certain circumstances.
Stains having varying fluxing effects on a host glaze
Plainsman M340 Transparent liner with various stains added (cone 6). These bubbles were fired on a bed of alumina powder, so they flattened more freely according to melt flow. You can see which stains flux the glaze more by which bubbles have flattened more. The deep blue and browns have flowed the most, the manganese alumina pink the least. This knowledge could be applied when mixing these glazes, compensating the degree of melt of the host accordingly.
A highly fluxed body, when over fired can do this!
These two mugs are made from the same material: Ravenscrag Slip plus 20% Ferro Frit 3134. The one on the right has been bisque fired to 1550F. The one on the left has been clear glazed and fired to cone 03 (1950F). That means that this body vitrifies well below cone 03, likely well below cone 06. Thus strength, maturity, vitrification are not a matter of temperature, they are a matter of how much flux is available in the body to mature it to a dense, strong matrix.
Copper oxide (2%) in an otherwise stable cone 6 oxidation glaze fluxes it
Copper fluxes a matte glaze at cone 6
4% copper carbonate and 6% rutile have been added to G2934 cone 6 matte base. Using a green stain should prevent this. Or some B2O3 could be substituted with SiO2 (via glaze chemistry).
The amazing fluxing power of boron (in borax)
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.
2% Copper carbonate in two different cone 6 copper-blues
The top base glaze has just enough melt fluidity to produce a brilliant transparent (without colorant additions). However it does not have enough fluidity to pass the bubbles and heal over from the decomposition of this added copper carbonate! Why is lower glaze passing the bubbles? How can it melt better yet have 65% less boron? How can it not be crazing when the COE calculates to 7.7 (vs. 6.4)? First, it has 40% less Al2O3 and SiO2 (which normally stiffen the melt). Second, it has higher flux content that is more diversified (it adds two new ones: SrO, ZnO). That zinc is a key to why it is melting so well and why it starts melting later (enabling unimpeded gas escape until then). It also benefits from the mixed-oxide-effect, the diversity itself improves the melt. And the crazing? The ZnO obviously pushes the COE down disproportionately to its percentage.
Why you should not paint pure stain powders over glaze
On the left is a pure blue stain, on the right a green one. Obviously, the green is much more refractory. On the other hand, the green just sits on the surface as a dry, unmelted layer. For this type of work, stains need to be mixed into a glaze-like recipe of compatible chemistry (a medium) to create a good, paintable color. The blue is powerful, it would only need to comprise 5-10% of the recipe total. Its medium would need to have a stiffer melt (so the cobalt fluxes it to the desired degree of melt fluidity). A higher percentage of the green stain is needed, perhaps double. It's medium needs much more melt fluidity since the stain is refractory. Of course, only repeated testing would get them just right. Guidelines of the stain manufacturer for chemistry compatibility need to be consulted also (as certain stains will not develop their color unless their glaze medium host has a compatible chemistry). And, to be as paintable as possible, use use a gum-solution/water mix (e.g. 2 parts water to one part gum solution).
Iron oxide goes crazy in reduction
Cone 6 iron bodies that fire non-vitreous and burn tan or brown in oxidation can easily go dark or vitreous chocolate brown (or even melting and bloated in reduction). On the right is Plainsman M350, a body that fires light tan in oxidation, notice how it burns deep brown in reduction at the same temperature. This occurs because the iron converts to a flux and the glass development that occurs brings out the dark color. On the left is Plainsman M2, a raw high iron clay that is quite vitreous in oxidation, but in reduction it is bloating badly. When reduction bodies are this vitreous there is a much great danger of black coring.
Out Bound Links
ZnO - Zinc Oxide
Refractory, as a noun, refers to a material that does not melt at normal kiln temperatures (of the industry being referenced). The term also refers to the capacity a material to withstand heat without deforming or melting. Kiln shelves and firebricks are refractory. Many natural clays and minerals a...
Li2O - Lithium Oxide, Lithia
MgO - Magnesium Oxide, Magnesia
BaO - Barium Oxide, Baria
SrO - Strontium Oxide, Strontia
A ceramic glass that has been premixed from raw powdered minerals and then melted, cooled by quenching in water, and ground into a fine powder (search youtube for interesting videos). Huge quantities and varieties of frits are manufactured for the ceramic industry every year (especially for tile) by...
CaO - Calcium Oxide, Calcia
B2O3 - Boric Oxide
K2O - Potassium Oxide
Target Formula, Limit Formula
The term 'limit formula' historically has typically referred to efforts to establish absolute ranges for mixtures of oxides that melt well at an intended temperature and are not in sufficient excess to cause defects. These formulas typically show ranges for each oxide commonly used in a specific gla...
Na2O - Sodium Oxide, Soda
In Bound Links
By Tony Hansen