Zincite Crystal

Two glazes, same chemistry, different materials. The glaze on the left is sourcing CaO from wollastonite, the one on the right from calcium carbonate. Thus the oxide chemistry of the two is the same but the recipe of materials sourcing that chemistry is different. The difference in the melt flow you see here is an expression of how choosing different mineral sources to source an oxide can produce melting patterns that go outside what the chemistry suggests. The difference here is not extreme, but it can be much more. Glaze chemistry is relative, not absolute. It works best when you are changing material amounts, not material types. When you do introduce a very different mineral then you have a different system which has its own relative chemistry.

Red iron oxide in a high temperature reduction fired glaze

If you add an opacifier to this the color will become pastel and lighter and vary less with thickness.

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.

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.

This is what about 10% iron and some titanium and rutile can do in a transparent base glaze with slow cooling at cone 10R on a refined porcelain.

Fired on a porcelain in a gas kiln.

This bowl was made by Tony Hansen in the middle to late 1970s. The body was H41G (now H441G), it had large 20 mesh iron stone concretions that produced very large iron blotches in reduction firing. Luke Lindoe loved to use these clays to show off the power of the cone 10 reduction firing process that he was promoting in the 1960s and 70s.

This melt flow tester demonstrates how zircon opacifys but also stiffens a glaze melt at cone 6. Zircon also hardens many glazes, even if used in smaller amounts than will opacify.

This is unlike some raw materials which melt suddenly.

The Copper Red effect shows the importance of correct firing to achieve a specific effect with certain glaze recipes. The inside of this vase was more heavily and consistently reduced, simply because it was isolated somewhat from the outside kiln atmosphere. The outside of the vase, by contrast, is grey (a product of periods of oxidation during the firing).

Copper oxide (2%) added to an otherwise stable cone 6 glaze fluxes it considerably

Since iron oxide is a flux in reduction, overglaze iron based pigments run if applied to thickly

This reduction celadon is crazing. Why? High feldspar. Feldspar supplies the oxides K2O and Na2O, they contribute to brilliant gloss and great color (at all temperatures) but the price is very high thermal expansion. Any glaze having 40% or more feldspar should turn on a red light! Thousands of recipes being traded online are high-feldspar, some more than 50%! There are ways to tolerate the high expansion of KNaO, but the vast majority are crazing on all but high quartz bodies. Crazing is a plague for potters. Ware strength suffers dramatically, pieces leak, the glaze harbours bacteria, crazing invites customers to return pieces. The fix: A transparent base that fits your ware. Add colorants and opacifiers to that. Another fix: substitute some of the KNaO for a lower expansion flux (like MgO, SrO, CaO, Li2O) and add as much SiO2 and Al2O3 as the glaze will take (using glaze chemistry software).

An example of how the same dolomite cobalt blue glaze fires much darker in oxidation than reduction. But the surface character is the same. A different base glaze having the same colorant might fire much more similar. The percentage of colorant can also be a factor in how similar they will appear. The identity of the colorant is important, some are less prone to differences in kiln atmosphere. Color interactions are also a factor. The rule? There is none, it depends on the chemistry of the host glaze, which color and how much there is.

It is not just iron oxide that changes character from oxidation to reduction. Of course, cobalt can fire to a bright blue in oxidation also, but this will only happen if its host glaze is glossy and transparent. In this case the shift to reduction has altered the character of the glaze enough so that its matte character subdues the blue.

This is 100% of the pure material. Notice how the iron is fluxing it more on the left, it is beginning to run. And how the reduction atmosphere amplifies the color of the iron (by changing it to the metallic state).

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.

This cone 10R glaze, a tenmoku with about 12% iron oxide, demonstrates how iron turns to a flux in reduction firing and produces a glaze melt that is much more fluid. In oxidation, iron is refractory and does not melt well (this glaze would be completely stable on the ware in an oxidation firing at the same temperature, and much lighter in color).

Stull chart showing the SiO2-Al2O3-(0.7CaO+0.3KNaO) system

Phase diagram and stull chart showing the SiO2-Al2O3-(0.7CaO+0.3KNaO) system

Adding a little blue stain to a medium temperature transparent glaze can give it a more pleasant tone. Some iron is present in all stoneware bodies (and even porcelains), so transparent glazes never fire pure white. At cone 10 reduction they generally exhibit a bluish color (left), whereas at cone 6 they tend toward straw yellow (right). Notice the glaze on the inside of the center mug, it has a 0.1% Mason 6336 blue stain addition; this transforms the appearance to look like a cone 10 glaze (actually, you might consider using a little less, perhaps 0.05%). Blue stain is a better choice than cobalt oxide, the latter will produce fired speckle.

GR10-G Silky magnesia matte cone 10R (Ravenscrag 100, Talc 10, Tin Oxide 4). This is a good example silky matte mechanism of high MgO. The Ravenscrag:Talc mix produces a good silky matte, the added tin appears to break the effect at the edges.

The fluxing power of boron (in borax): The two top clay bars contain 15% hydrous borax. At cone 06 it has melted and drained out of the bars, running down over the others as a glass.

Right: Ravenscrag GR6-A transparent base glaze. Left: It has been opacified (turned opaque) by adding 10% Zircopax. This opacification mechanism can be transplanted into almost any transparent glaze. It can also be employed in colored transparents, it will convert their coloration to a pastel shade, lightening it. Zircon works well in oxidation and reduction. Tin oxide is another opacifier, it is much more expensive and only works in oxidation firing.

On Plainsman H443 iron stoneware in reduction firing. Notice Tin does not work. Also notice that between 7.5 and 10% Zircopax provides as much opacity as does 15% (Zircon is very expensive).

Because this glaze employs 10% dolomite instead of 10% calcium carbonate it has a lower thermal expansion and is less likely to craze. While the dolomite is contributing MgO, which normally mattes glazes, there is not enough to do it here.

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.

Zinc oxide calcined (left) and raw (right) in typical crystalline glaze base (G2902B has 25% zinc) on typical cone 6 white stoneware body. This has been normally cooled to prevent crystal development. The melting pattern is identical. Note how badly these are crazed, this is common since crystalline glazes are normally high in sodium.

The cone 6 G1214M glaze on the left melts well. Can it benefit from a silica addition? Yes. The right adds 20% yet still melts as well, covers better, is more glossy, more resistant to leaching, harder and has a lower thermal expansion.

A closeup of a glossy c6 glaze having 4% added copper carbonate. The bottom section is leaching in lemon juice after 24 hours. This photo has been adjusted to spread the color gamut to highlight the difference. The leached section is now matte.

2, 5, 10, 15% calcium carbonate added to Ravenscrag Slip on a buff stoneware fired at cone 10R. It gets progressively glossier toward 15%, crazing starts at 10% (test by Kat Valenzuela). Adding a flux only reduces the SiO2 and Al2O3, this pushes the thermal expansion upwards. 5% is actually sufficient. An alternative would be to use wollastonite, it supplies SiO2 also.

The cone 6 glazes on the left have double the boron, but they flow less because they have much higher Al2O3 and SiO2 contents. This effect renders them quite milky white with no opacifier!

This cobalt underglaze is bleeding into the transparent glaze that covers it. This is happening either because the underglaze is too highly fluxed, the over glaze has too high of a melt fluidity or the firing is being soaked too long. Engobes used under the glaze (underglazes) need to be formulated for the specific temperature and colorant they will host, cobalt is known for this problem so it needs to be hosted in a less vitreous engobe medium. When medium-colorant compounds melt too much they bleed, if too little they do not bond to the body well enough. Vigilance is needed to made sure the formulation is right.

These bowls were made by Tony Hansen using a mixture of white and stained New-Zealand-kaolin-based porcelain (Plainsman Polar Ice) fired at cone 6. The body is not only white, but very translucent.

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 are two cone 6 matte glazes (shown side by side in an account at Insight-live). G1214Z is high calcium and a high silica:alumina ratio (you can find more about it by googling 1214Z). It crystallizes during cooling to make the matte effect and the degree of matteness is adjustable by trimming the silica content (but notice how much it runs). The G2928C has high MgO and it produces the classic silky matte by micro-wrinkling the surface, its matteness is adjustable by trimming the calcined kaolin. CaO is a standard oxide that is in almost all glazes, 0.4 is not high for it. But you would never normally see more than 0.3 of MgO in a cone 6 glaze (if you do it will likely be unstable). The G2928C also has 5% tin, if that was not there it would be darker than the other one because Ravenscrag Slip has a little iron. This was made by recalculating the Moore's Matte recipe to use as much Ravenscrag Slip as possible yet keep the overall chemistry the same. This glaze actually has texture like a dolomite matte at cone 10R, it is great. And it has wonderful application properties. And it does not craze, on Plainsman M370 (it even survived and 300F to ice water plunge without cracking). This looks like it could be a great liner glaze.

The flow on the left is an adjusted Perkins Frit Clear (we substituted frit for Gerstley Borate). It is a cone 6 transparent that appeared to work well. However it did not survive a 300F oven-to-icewater test without crazing on Plainsman M370. The amount of flow (which increases a little in the frit version) indicates that it is plenty fluid enough to accept some silica. So we added 10% (that is the flow on the right). Now it survives the thermal shock test and still fires absolutely crystal clear.

These glaze cones are fired at cone 6 and have the same recipe: 20 Frit 3134, 21 EP Kaolin, 27 calcium carbonate, 32 silica. The difference: The one on the left uses dolomite instead of calcium carbonate. Notice how the MgO from the dolomite completely mattes the surface whereas the CaO from the calcium carbonate produces a brilliant gloss.

These cone 04 glazes both have 50% Gerstley Borate. The other 50% in the one on the left is PV Clay, a very low melting plastic feldspar. On the right, the other 50% is silica and kaolin, both very refractory materials. Yet the glaze on the right is melting far better. How is that possible? Likely because the silica and kaolin are supplying Al2O3 and SiO2, exactly the oxides that Gerstley Borate needs to form a good glass.

A melt fluidity comparison between two cone 6 matte glazes. G2934 is an MgO saturated boron fluxed glaze that melts to the right degree, forms a good glass, has a low thermal expansion, resists leaching and does not cutlery mark. G2000 is a much-trafficked cone 6 recipe, it is fluxed by zinc to produce a surface mesh of micro-crystals that not only mattes but also opacifies the glaze. But it forms a poor glass, runs too much, cutlery marks badly, stains easily, crazes and is likely not food safe! The G2934 recipe is google-searchable and a good demonstration of how the high-MgO matte mechanism (from talc) creates a silky surface at cone 6 oxidation the same as it does at cone 10 reduction (from dolomite). However it does need a tin or zircon addition to be white.

Left: a cone 6 matte glaze (G2934 with no colorant). Middle: 5% Mason 6006 chrome-tin red stain added. Right: 5% Mason 6021 encapsulated red stain added. Why is there absolutely no color in the center glaze? This host recipe does not have the needed chemistry to develop the #6006 chrome-tin color (it lacks enough CaO). Yet this same matte glaze intensifies the #6021 at only 5% (sometimes 20% or more encapsulated stain is needed to develop the color).

G2934 cone 6 matte (left) with 10% zircopax (center), 4% tin oxide (right). Although the cutlery marks clean off all of them, clearly the zircopax version has the worst problem and is the most difficult to clean. To make the best possible quality white it is wise to line blend in a glossy glaze to create a compromise between the most matteness possible yet a surface that does not mark or stain.

We are looking at two pairs of samples, they demonstrate why knowing about glaze chemistry can be so important. Each pair shows the same stain on two different base glazes (G2934 cone 6 matte and PGF1 cone 6 glossy). Why does the maroon not develop in the left pair, why is the purple stain firing blue on the right? The Mason Colorworks color chart and reference guide specifies that the host glaze must be zincless and have 6.7-8.4% CaO (this is a little unclear, it actually is expressing a minimum, the more CaO the better). But the colorless one has 11% CaO, it should work (the maroon one has only 9% and it is working)! Likewise the purple color develops correctly in the 9% CaO but wrong in the 11% CaO base. Both stains have the same caution on the reference guide. What is going on? It is an undocumented issue: MgO. The 11% CaO base glaze is high in MgO (that is what makes it matte), that impedes the development of both colors. When you talk to tech support at Mason (or any stain company), they need to know the chemistry of your glaze to help, not the recipe.

Opacifying a cone 10 reduction magnesia matte glaze. On the left: G2571A dolomite matte, a popular recipe (from Tony Hansen). Right: 10% Zircopax has been added. Both are on a buff stoneware (H550 from Plainsman Clays).

Even commercial dinnerware can suffer cutlery marking problems. This is a glossy glaze, yet has a severe case of this issue. Why? Likely the zircon opacifier grains are protruding from the surface and abrading metal that comes into contact with it.

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).

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.

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).

Cobalt carbonate (top) and copper carbonate (bottom). Left is the raw powder plastic-formed into a sample (with 2% veegum). Right: fired to 1850F. The CuCO3 is quickly densifying over the past 100 degrees and should begin to melt soon. It is long past the fuming stage.

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%).

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 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).

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.

We are comparing the degree of melt fluidity (10 gram balls melted down onto a tile) between two base clear glazes fired to cone 6 (top) and cone 1 (bottom). Left: G2926B clear boron-fluxed (0.33 molar) clear base glaze sold by Plainsman Clays. Right: G3814 zinc-fluxed (0.19 molar) clear base. Two things are clear: Zinc is a powerful flux (it only takes 5% in the recipe to yield the 0.19 molar). Zinc melts late: Notice that the boron-fluxed glaze is already flowing well at cone 1, whereas the zinc one has not even started. This is very good for fast fire because the unmelted glaze will pass more gases of decomposition from the body before it melts, producing fewer glaze defects.

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.

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.

These are four cone 6 glazes of diverse chemistry. They have varying melt fluidities. They are soaked (half way up) in lemon juice over night. None show any evidence of surface changes. All contain 2% copper carbonate. If the copper was increased, especially to the point of going metallic or crystallizing, likely the leaching test would have different results. So, if you use copper sensibly (in moderate amounts), there is a good chance you can make a glaze that resists leaching.

Why the difference? The one on the right (Plainsman M370) is made from commodity American kaolins, ball clays, feldspars and bentonite. It looks pretty white-firing until you put it beside the Polar Ice on the left (made from NZ kaolin, VeeGum plasticizer and Nepheline Syenite as the flux). These are extremely low iron content materials. M370 contains low iron compared to a stoneware (less than 0.5%) that iron interacts with this glaze to really bring out the color (although it is a little thicker application that comes nowhere near explaining this huge difference). Many glazes do not look good on super-white porcelains for this reason.

Insight-Live displays the chemistry of glazes like this. In oxide formulas it is typical to express the total of K2O plus Na2O as KNaO. The reason goes to the heart of why viewing glazes as formulas of oxides is so much better than seeing them as just recipes of materials.

This glaze consists of micro fine silica, calcined EP kaolin, Ferro Frit 3249 MgO frit, and Ferro Frit 3134. It has been ball milled for 1, 3, and 6 hours with these same results. Notice the crystallization that is occurring. This is likely a product of the MgO in the Frit 3249. This high boron frit introduces it in a far more mobile and fluid state than would talc or dolomite and MgO is a matting agent (by virtue of the micro crystallization it can produce). The fluid melt and the fine silica further enhance the effect.

This happens. They are glossy, but lack thickness and body. They are also prone to boron blue clouding (micro crystallization that occurs because low alumina melts crystallize much more readily on cooling). Another problem is lack of resistance to wear and to leaching (sufficient Al2O3 in the chemistry is essential to producing a strong and durable glass). This is a good example of the need to see a glaze not just as a recipe but as a chemical formula of oxides. The latter view enables us to compare it with other common recipes and the very low Al2O3 is immediately evident. Another problem: Low clay content (this has only 7.5% kaolin) creates a slurry that is difficult to use and quickly settles hard in the bucket.

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.

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