|Monthly Tech-Tip |
Blistering is a common surface defect that occurs with ceramic glazes. The problem emerges from the kiln and can occur erratically in production. And be difficult to solve.
Glaze blisters are a surface defect in fired ceramic glazes. They have caused every potter and company grief at one time or another. The problem can be erratic. The blisters trace their origins to the generation of gases as particles in the body and glaze itself decompose during firing (loosing H2O, CO, CO2, SO2, etc). If the glaze melt has sufficiently high surface tension these bubbles can grow quite large. Many mineral particles gas when heated, each type has its own firing thermal history (temperatures at which it releases gases). If a glaze has already begun melting while gases are still being generated, bubbles grow within it. Bubble populations and distributions of sizes depend on several properties of the glaze melt (e.g. viscosity, surface tension, thickness of application). As populations and sizes of bubbles increase they begin breaking at the surface. Bodies often generate gases during early stages of the firing (to expel water and carbon). This tapers off but then can begin again at higher temperatures if certain mineral particles present are late gassers.
Strategies to deal with the problem often involve minimizing gas expulsion by adjusting body and glaze recipes to favour materials of lower LOI. Lowering the surface tension of the melt is another option. Employing glaze fluxes that melt later in the firing can be very effective since pretty well all gases of decomposition will have been expelled. Glaze thickness can be reduced. Firing curves can be adjusted to slow the rate of rise as the top of the curve approaches. Holding at temperatures on the up-ramp can give gases more time to escape. Holding at top temperature can help if the surface tension is low enough. If not, the bubbles will just stay, and grow. In these cases, and drop-and-hold firing schedule will often remove the blisters (giving them a chance to heal because the increased viscosity of the glaze melt can overcome the surface tension holding the bubbles in place). Testing is required to determine how much the drop should be (e.g. 100F).
The glaze is running down on the inside, so it has a high melt fluidity. "High melt fluidity" is another way of saying that it is being over fired to get the visual effect. It is percolating at top temperature (during the temperature-hold period), forming bubbles. There is enough surface tension to maintain them all the way down to the body, and for as long as the temperature is held. To break the bubbles and heal up after them the kiln needs to be cooled to a point where decreasing melt fluidity can overcome the surface tension. The hold temperature needs to be high enough that the glaze is still fluid enough to run in and and heal the residual craters. A typical drop temperature is 100F.
A closeup of a cone 10R rutile blue (it is highlighted in the video: A Broken Glaze Meets Insight-Live and a Magic Material). Beautiful glazes like this, especially rutile blues, often have serious issues (like blistering, crazing), but they can be fixed.
Plus the glaze ran even more. The main problem was that the original firing was taken too high, about cone 02 (seven hour schedule). This body nears zero porosity there and is beginning to decompose. That generates gases. The second firing was taken to cone 03 in four hours. But the glaze just percolated more. However freshly glazed bisque ware in that same firing came out perfect. Lessons were learned. Fire faster. Keep it cone 03 or lower. Do not put the glaze on too thick. Use self-supporting cones to verify the electronic controller, they are much more accurate than regular cones.
This glaze creates the opaque-with-clear effect shown (at cone 7R) because it has a highly fluid melt that thins it on contours. It is over fired. On purpose. That comes with consequences. Look at the recipe, it has no clay at all! Clay supplies Al2O3 to glaze melts, it stabilizes it against running off the ware (this glaze is sourcing some Al2O3 from the feldspar, but not enough). That is why 99% of studio glazes contain clay (both to suspend the slurry and stabilize the melt). Clay could likely be added to this to increase the Al2O3 enough so the blisters would be less likely (it would be at the cost of some aesthetics, but likely a compromise is possible). There is another solution: A drop-and-soak firing. See the link below to learn more. One more observation: Look how high the LOI is. Couple that with the high boron, which melts it early, and you have a fluid glaze melt resembling an Aero chocolate bar!
These are the same glaze, same thickness, Ulexite-based G2931B glaze, fired to cone 03 on a terra cotta body. The one on the right was fired from 1850F to 1950F at 100F/hr, then soaked 15 minutes and shut off. The problem is surface tension. Like soapy water, when this glaze reaches cone 03 the melt is quite fluid. Since there is decomposition happening within the body, gases being generated vent out through surface pores and blow bubbles. I could soak at cone 03 as long as I wanted and the bubbles would just sit there. The one on the left was fired to 100F below cone 03, soaked half an hour (to clear micro-bubble clouds), then at 108F/hr to cone 03 and soaked 30 minutes, then control-cooled at 108F/hr to 1500F. During this cool, at some point well below cone 03, the increasing viscosity of the melt becomes sufficient to overcome the surface tension and break the bubbles. If that point is not traversed too quickly, the glaze has a chance to smooth out (using whatever remaining fluidity the melt has). Ideally I should identify exactly where that is and soak there for a while.
There is a direct relationship between the way ceramic glazes fire and their chemistry. Wrapping your mind around that and overcome your aversion to chemistry is a key to getting control of your glazes. You can fix problems like crazing, blistering, pinholing, settling, gelling, clouding, leaching, crawling, marking, scratching, powdering. Substitute frits or incorporate better, cheaper materials, replace no-longer-available ones (all while maintaining the same chemistry). Adjust melting temperature, gloss, surface character, color. Identify weaknesses in glazes to avoid problems. Create and optimize base glazes to work with difficult colors or stains and for special effects dependent on opacification, crystallization or variegation. Create glazes from scratch and use your own native materials in the highest possible percentage.
An extreme example of blistering in a piece fired at cone 03. The glaze is Ferro Frits 3195 and 3110 with 15% ball clay applied to a bisque piece. Is LOI the issue? No, this glaze has a low LOI. Low bisque? No, it was bisqued at cone 04. Thick glaze layer? Yes, partly. Holding the firing longer at temperature? No, I could hold this all night and the glaze would just percolate the whole time. Slow cooling? Close, but not quite. The secret I found to fix this was to apply the glaze in a thinner layer and drop-and-hold the temperature for 30 minutes at 100F below cone 03. Doing that increased the viscosity of the glaze melt to the point that it could break the blisters (held by surface tension) while still being fluid enough to smooth out the surface.
An example of how calcium carbonate can cause blistering as it decomposes during firing. This is a cone 6 Ferro Frit 3249 based transparent (G2867) with 15% CaO added (there is no blistering without the CaO). Calcium carbonate has a very high loss on ignition (LOI) and for this glaze, the gases of its decomposition are coming out at the wrong time. While there likely exists a firing schedule that takes this into account and could mature it to a perfect surface, the glaze is high in MgO, it has a high surface tension. That is likely enabling bubbles to form and hold better.
Why are these happening (on this piece by Paul Briggs)? It is not completely clear. The glaze has plenty of carbonates, including copper, enough for over 20% LOI. But these normally produce high populations of small blisters, this is the opposite. The melt appears to have enough surface tension that the bubbles survive and endure top-temperature-soaking. And they don't pop until the temperature has dropped so far that insufficient melt-mobility remains to heal them. The glaze has an unconventionally low SiO2 content, that makes it flow vigorously, well enough that the melt is moving and collecting in surface contours. The glaze recipe is quite unconventional, any effort to "improve" its adherence to limits would likely lose the visual aesthetic. A drop-and-hold firing schedule is likely the key to alleviating this.
Cone 6 Drop-and-Soak Firing Schedule
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Questions and suggestions to help you reason out the real cause of ceramic glaze blistering and bubbling problems and work out a solution