Calculated Thermal Expansion
Digitalfire Insight-live and desktop Insight calculate the thermal expansion of a glaze from its oxide chemistry (based on the contributing expansion factors and amounts of each oxide in the formula). These numbers are very small and recorded in scientific notation (e.g. 6.5 x 10-7 which is 0.00000065). Typically the power-of-ten is dropped, so a number might simply be: 6.5. Higher numbers indicate higher expansion.
The high thermal expansion of a low-fire talc body
Talc is employed in low fire bodies to raise their thermal expansion (to put the squeeze on glazes to prevent crazing). These dilatometer curves make it very clear just how effective that strategy is! The talc body was fired at cone 04, the stoneware at cone 6. The former is porous and completely non-vitreous, the latter is semi vitreous. This demonstrates something else interesting: The impracticality of calculating the thermal expansion of clay bodies based on their oxide chemistry. Talc sources MgO and low fire bodies containing it would calculate to a low thermal expansion. But the opposite happens. Why? Because these bodies are composed of mineral particles loosely sintered together. A few melt somewhat, some change their mineral form, most remain unchanged. The body's COE is the additive sum of the proportionate populations of all the particles. Good luck calculating that!
A down side of high feldspar glazes: Crazing!
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).
The unexpected reason for this crazing can be seen in the chemistry
This liner glaze is 10% calcium carbonate added to Ravenscrag slip. Ravenscrag Slip does not craze when used by itself as a glaze at cone 10R on this body, so why would adding a relatively low expansion flux like CaO make it craze? It does not craze when adding 10% talc. This is an excellent example of the value to looking at the chemistry (the three are shown side-by-side in my account at Insight-live.com). The added CaO pushes the very-low-expansion Al2O3 and SiO2 down by 30% (in the unity formula), so the much higher expansion of all the others drives the expansion of the whole way up. And talc? It contains SiO2, so the SiO2 is not driven down nearly as much. In addition, MgO has a much lower expansion than CaO does.
Adding silica will fix crazing, right? Not here.
G2926B (center and right) is a clear cone 6 glaze created by simply adding 10% silica to Perkins Studio clear, a glaze that had a slight tendency delay-craze on common porcelains we use. Amazingly it tolerated that silica addition very well and continued to fire to an ultra gloss crystal clear. That change eliminated the crazing issues. The cup on the right is a typical porcelain that fits most glazes (because it has 24% silica and near-zero porosity). The center one only has 17% silica and zero porosity (that is why it is crazing this glaze). I added 5% more silica to the glaze, it took that in stride, continuing to produce an ultra smooth glossy. It is on cup on the left. But it is still crazing just as much! That silica addition only reduces the calculated expansion from 6.0 to 5.9, clearly not enough for this more severe thermal expansion mismatch. Substituting low expansion MgO for other fluxes will compromise the gloss, so clearly the solution is to use the porcelain on the right.
Compare fired glaze melt fluidity balls with their chemistry and lights come on!
10 grams balls of these three glazes were fired to cone 6 on porcelain tiles. Notice the difference in the degree of melt? Why? You could just say glaze 2 has more frit and feldspar. But we can dig deeper. Compare the yellow and blue numbers: Glaze 2 and 3 have much more B2O3 (boron, the key flux for cone 6 glazes) and lower SiO2 (silica, it is refractory). That is a better explanation for the much greater melting. But notice that glaze 2 and 3 have the same chemistry, but 3 is melting more? Why? Because of the mineralogy of Gerstley Borate. It yields its boron earlier in the firing, getting the melting started sooner. Notice it also stains the glaze amber, it is not as pure as the frit. Notice the calculated thermal expansion: That greater melting came at a cost, the thermal expansion is alot higher so 2 and 3 glaze will be more likely to craze than G2926B (number 1).
Why is this crystalline glaze not crazed? Even in the pool at the bottom?
Because this is Plainsman Crystal Ice, it contains 40% silica (quartz). It also does not vitrify, so as much of the quartz remains undissolved as possible. This produces a body with a much high thermal expansion so it can put more of a squeeze on the high-expansion glazes used in the crystal glazing process (it is very common for such glazes to be crazed, it is accepted as part of the process).
Do you know the purpose of these common Ferro frits?
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 (for the abrasives industry) has a very-low expansion, it is great for fixing 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).
Do your functional glazes do this? Fix them. Now.
These cone 6 porcelain mugs have glossy liner glazes and matte outers: VC71 (left) crazes, G2934 does not (it is highlighted using a felt marker and solvent). Crazing, while appropriate on non-functional ware, is unsanitary and severely weakens the ware (up to 300%). If your ware develops this your customers will bring it back for replacement. What will you do? The thermal expansion of VC71 is alot higher. It is a product of the chemistry (in this case, high sodium and low alumina). No change in firing will fix this, the body and glaze are not expansion compatible. Period. The fix: Change bodies and start all over. Use another glaze. Or, adjust this recipe to reduce its thermal expansion.
Insight-Live comparing a glossy and matte cone 6 base glaze recipe
Insight-live is calculating the unity formula and mole% formula for the two glazes. Notice how different the formula and mole% are for each (the former compares relative numbers of molecules, the latter their weights). The predominant oxides are very different. The calculation is accurate because all materials in the recipe are linked (clickable to view to the right). Notice the Si:Al Ratio: The matte is much lower. Notice the calculated thermal expansion: The matte is much lower because of its high levels of MgO (low expansion) and low levels of KNaO (high expansion). Notice the LOI: The matte is much higher because it contains significant dolomite.
Match calculated COE to dilatometer-measured body COE? No!
Why? Firing temperature, schedule and atmosphere affect the result. Dilatometers are only useful when manufacturers monitor bodies AND glazes over time and in the same firing conditions. Calculated values for glazes are only relative (not absolute). The best way to fit glazes to your clay bodies is by testing, evaluation, adjustment and retesting. For example, if a glaze crazes, adjust its recipe to bring the expansion down (your account at Insight-live has the tools and guides to do this). Then fire a glazed piece and thermal stress it (300F into ice-water). If it still crazes, move it further. If you have a base glossy glaze that fits (and made of the same materials), try comparing its calculated expansion as a guide. Can you calculate body expansion from oxide chemistry? Definitely not, because bodies do not melt.
A high expansion glaze is bowing the foot of the bottom bowl
The glaze has a calculated thermal expansion of 8.8 (because of high KNaO and low SiO2). Very high. It is basically stretched on. These plates are not glazed on the bottom. The glaze on the inside of the upper plate fits, the base is flat. But the glaze on the inside of the lower plate is pulling the base upward. The built-in stresses will eventually cause the piece to fail (likely fracturing into many pieces) if bumped. It is also almost certainly crazing. And the low SiO2 implicates it for leaching. The solution? Reduce the KNaO in favour of MgO and increase the SiO2 as much as possible without compromising the fired character.
This is crazing. Really bad crazing!
These two glazes look the same, they are both cone 6 satin mattes. On the same porcelain. But the matteness "mechanism" of the one on the left is a low Si:Al ratio melted by zinc and sodium. The mechanism of the one on the right is high MgO melted by boron (with the same Si:Al ratio). The "baggage" of the mechanism on the left is high thermal expansion. And crazing (which drastically reduces strength and provides a haven for bacteria). The glaze is "stretched" on the clay (because it has a higher thermal contraction). When the lines are close together like this it indicates a more serious issue (I have highlighted them with dye). If the effect is intended, it is called "crackle" (but no one would intend this on functional ware). The glaze on the left calculates to a high thermal expansion so the crazing is not a surprise.
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