|Monthly Tech-Tip |
Modified: 2019-12-16 14:35:54
High fluid melt glaze for reactive effects and super gloss colors
|Ferro Frit 3110||31.10|
|Ferro Frit 3134||6.60|
This is work I did in 2015 (in 2019 a much bigger project developed this further).
The copper and tin to produce the turquoise celadon effect are not included in the recipe shown (3% copper carb, 2.5% tin oxide).
This recipe is for a brilliant fluid-melt transparent base glaze, initially for copper blues and greens, but later for stains. "Fluid-melt" means it runs down off ware if applied too thickly, this is a key for achieving many visual effects.
Initiailly I compared a number of recipes I found on line and finally selected Panama Blue. I removed the colorants and made adjustments to improve slurry properties and lower the thermal expansion (it has serious crazing issues). Fluid-melts have a down side: Crazing is an issue (because the fluid melt requires more fluxes, these have higher thermal expansions).
Then I did three adjustments, each lowering the thermal expansion more than the last. While keeping the same brilliant visual appearance. The recipe ended up being quite different (two materials were eliminated from the recipe, their oxides supplied by the others). The chemistry of this one moves much of the KNaO to low-expansion MgO. This makes it melt a little less, but visually it is the same. Higher ZnO helps melting (since MgO is not nearly as powerful a flux as KNaO). I was even able to add extra SiO2. The calculated thermal expansion has gone from 7.7 down to 7.3.
This worked well on stonewares but still crazed on Plainsman P300 and M370 (but was OK on Polar Ice). Fluid melt glazes look best on porcelains so this was obviously a problem. So I continued development in pursuit of a fluid melt having a lower thermal expansion (see subsequent articles, recipes and posts).
This is not just a typical transparent cone 6 glaze with 2% copper carbonate added (and 2.5% tin oxide). Knowing what is different about this clear base, its trade-offs and how it was developed are important. The porcelains are Plainsman P300 and M370. The liner glaze is G2926B, it is a gloss but has a much lower melt fluidity than the outer glaze, G3806C (as a functional transparent its main job is to fit the body and be hard and durable). But in order for that outer glaze to accommodate the copper and still be super glossy it must have a much higher melt fluidity. It was tricky to develop since that fluidity comes with high sodium and lower silica, that raises the thermal expansion and moves it toward crazing.
The first glaze is a control, a standard non-fluid clear with copper. The other three are the short-listed ones in my project to find a good copper blue recipe starting recipe and fix its problems (which they all have).
The GLFL testers for melt flow at the back and the GBMF test melt-down-balls in front contain 1% copper carbonate. The glazed samples in the front row have 2% copper carbonate. L3806B, an improvement on the Panama Blue recipe, has the best color and the best compromise of flow and bubble clearing ability.
These two glazes are both brilliant glass-like super-transparents. But on this high-iron stoneware only one is working. Why? G3806C (on the outside of the piece on the left) melts more, it is fluid and much more runny. This melt fluidity gives it the capacity to pass the micro-bubbles generated by the body during firing. G2926B (right) works great on porcelain but it cannot clear the clouds of micro-bubbles coming out of this body. Even the glassy smooth surface has been affected. The moral: Two base transparents are needed, each being able to host colors, opacifiers and variegators. But there is a caveat: Although reactive glazes leverage melt fluidity to develop interesting surfaces they are more tricky to use and do not fire as durable.
Wrong. It is the one on the right. While the copper looks so much better in that fluid one on the left, that melt mobility comes at a cost: blisters. As a clear glaze it is no glossier than the other one, but it runs into thicker zones at the bottom and they blister. This is because the high mobility coupled with the surface tension blows bubbles as gases of decomposition travel through (in a normal cooling kiln they break low enough that mobility is insufficient to heal them). The fired glass in the one on the left is also not as hard, it will be more leachable, it will also craze more easily and be more susceptible to boron-blue devritrification. But as a green? Yes it is better.
Fired at cone 6. A melt fluidity comparison (behind) shows the G3808A clear base is much more fluid. While G2926B is a very good crystal clear transparent by itself (and with some colorants), with 2% added copper oxide it is unable to heal all the surface defects (caused by the escaping gases as the copper decomposes). The G3808A, by itself, is too fluid (to the point it will run down off the ware onto the shelf during firing). But that fluidity is needed to develop the copper blue effect (actually, this one is a little more fluid that it needs to be). Because copper blue and green glazes need fluid bases, strategies are needed to avoid them running off the ware. That normally involves thinner application, use on more horizontal surfaces or away from the lower parts of verticals.
The outer green glaze on these cone 6 porcelain mugs has a high melt fluidity. The liner glaze on the lower one, G2926B, is high gloss but not highly melt fluid. Notice that it forms a fairly crisp boundary with the outer glaze at the lip of the mug. The upper liner is G3806C, a fluid melt high gloss clear. The outer and inner glazes bleed together completely forming a very fuzzy boundary.
G3806C has been our recommended base recipe for reactive glazes (by the addition of colorants and opacifiers). It excels for copper blues, for example. But its thermal expansion is high enough that it crazes on some bodies (e.g. Plainsman P300). To adjust it (via glaze chemistry) I introduced some low expansion Li2O (from Spodumene) at the expense of high expansion KNaO, this dropped the calculated COE from 7.1 to 6.6. The melt fluidity, shown here at cone 6 (its most important feature), is exactly the same. The color is bluer. But not as dark, so copper oxide might be better. Or a higher percentage of copper carbonate. The base recipe (without the copper and tin) is potentially very valuable to create other reactive effects that depend on melt mobility. Why? Because it is very difficult to create a high gloss melt fluid glaze that also has a low 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 GLFL tests and GBMF tests for melt-flow 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, low run volatility, susceptibility to leaching). As a final step the recipe will be adjusted as needed. We eventually evolved the G3806B, after many iterations settled on G3806E or G3806F as best for now.
I am comparing 6 well known cone 6 fluid melt base glazes and have found some surprising things. The top row are 10 gram GBMF test 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. Out of this work came the G3806E and G3806F.
This is the winner of a five-way cone 6 copper blue glaze comparison that started with my dissatisfaction with Panama blue. When I compared these glazes I did not just eyeball them on a tile. I compared the melt flow, thermal expansion and slurry performance of the bases (without the copper and tin). Ball-melt GBMF tests also showed bubble and color development for very thick sections. Then I tried more copper and did more flow tests. I also did leaching tests. Where needed I adjusted recipes to increase clay content (while maintaining chemistry) so the slurries would work better. Without my account at insight-live.com to keep all of this organized it would have been so much more difficult, actually, I probably would not even have bothered with the project. The final recipe, G3806C, was an adjustment to reduce the thermal expansion of this one.
Crystallization (also called devritrification). You can see the tiny crystals on the surface of this copper stained cone 6 glaze (G3806C). The preferred orientation of metallic oxides is crystalline. When kilns cool quickly there is simply not enough time for oxides in an average glaze to organize themselves in the preferred way and therefore crystals do not grow. But if the glaze has a fluid melt and it cools slowly through the temperature at which the crystals like to form, they will. There is another issue here also: There are tiny dimples in the surface. This is because copper carbonate was used here instead of copper oxide. During firing, it generates carbon dioxide (because it is a carbonate) that bubbles out of the melt, leaving behind dimples that may or may not heal during cooling.
These porcelain mugs were decorated with the same underglazes (applied at leather hard), then bisque fired, dipped in clear glaze and fired to cone 6. While the G2926B clear glaze (left) is a durable and a great super glossy transparent for general use, its melt fluidity is not enough to clear the micro-bubbles generated by the underglazes. G3806C (right) has a more fluid melt and is a much better choice to transmit the underglaze colors. But I still applied G2926B on the inside of the mug on the right, it has a lower thermal expansion and is less likely to craze.
The glaze on the left (as shown in my account at insight-live.com) is a crystal clear at cone 04. The high frit content minimizes micro-bubbles. The high B2O3 melts it very well (this has 0.66 B2O3, that is three times as high as a typical cone 6 glaze). The recipe on the right is the product of a project to develop a low-thermal-expansion fluid-melt transparent for cone 6 (with added colorants fluid melts produce brilliant and even metallic results and they variegate well). While the balance of fluxes (the red numbers in the formula) is pretty different, look how similar the B2O3, Al2O3 and SiO2 levels are (yellow, red and blue backgrounded numbers in the formula), these mainly determine the melting range. That means that a fluid-melt cone 6 glaze is actually just a low temperature glaze being overfired to cone 6.
G2926B - Cone 6 Whiteware/Porcelain transparent glaze
A base transparent glaze recipe created by Tony Hansen for Plainsman Clays, it fires high gloss and ultra clear with low melt mobility.
GR6-A - Ravenscrag Cone 6 Clear Glossy Base
This Plainsman Cone 6 Ravenscrag Slip base is just the pure material with 20% added frit to make it melt to a glossy natural clear.
In ceramics, glazes melt to produce a liquid glass. That glass exhibits surface tension and it is important to understand the consequences of that.
Understand your a glaze and learn how to adjust and improve it. Build others from that. We have bases for low, medium and high fire.
Thixotropy is a property of ceramic slurries. Thixotropic suspensions flow when you want them to and then gel after sitting for a few moments. This phenomenon is helpful in getting even, drip free glaze coverage.
A way of establishing guideline for each oxide in the chemistry for different ceramic glaze types. Understanding the roles of each oxide and the limits of this approach are a key to effectively using these guidelines.
G3806C/G2926B Cone 6 Transparent Glazes
2019 Development of G3806 melt-fluid low-expansion clear base glaze
<recipes>XML not functional: We are working on this problem.</recipes>
|By Tony Hansen|
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