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Rutile Glaze

A type of ceramic glaze in which the surface variegates and crystallizes (on cooling) from the presence of rutile mineral in the recipe.

Details

Many fluid glazes will do magic things (e.g. variegate) with the addition of rutile (usually less than 5%). The effects are often amplified when other colorants are present (especially iron). The classic rutile effect happens when a glaze melt runs in rivulet patterns. Employment of this effect is common across a wide range of stoneware temperatures in both oxidation and reduction. Rutile can produce vibrant blues (cobalt is the most common way to make blue but it is very expensive and does not produce any of the effects of rutile on its own).

Rutile blue glazes can often be problematic, especially if the melt is fluid (blistering and crawling are common issues). In fact, the melt needs to be fluid for the full visual effects of rutile to appear. It does not seem intuitive that a fluid melt glaze should have defects, they should heal better. However fluid glazes can have surface tension and form and hold bubbles that do not break easily (like soap), even if the firing is held at top temperature. MgO, for example, has a high surface tension, and is common in rutile blue glazes. One solution is slow cooling, all the way down to 1400F if needed (a problem with this approach may be excessive crystallization of the surface, making it matte). Another solution is to cool rapidly to a temperature at which increasing viscosity of the melt overcomes the surface tension and the bubbles break. Chosen carefully this temperature will provide sufficient fluidity in the melt for the defects to heal. Cooling can proceed rapidly after that. A third possibility is the reduce the flux the creates the fluidity (usually boron). For example, if the glaze contains 20% frit, reduce it to 15% as a test.

The blue color is normally a product of the cooling curve of the kiln. If you lose the color determine if that is the issue. Perhaps the kiln less or more densely packed than before and therefore cooling faster or slower. Are you using a different kiln, does at a different rate?

Adding spodumene to this floating blue tones down the white patches

Adding spodumene to this floating blue tones down the white patches

GA6-C (left) and GA6-E (right) at cone 6 oxidation. The E version adds 4% spodumene onto the 4% rutile in the C (the base is 80% Alberta Slip and 20% frit 3134). The spodumene eliminate the overly whitish areas that can appear. This glaze requires the "Slow Cool (Reactive Glazes)" firing schedule. It looks the best on dark bodies.

Rutile blue glaze effect completely lost! A temporary solution.

Rutile blue glaze effect completely lost! A temporary solution.

Left: 4% rutile in the Alberta Slip:frit 80:20 base. This glaze has been reliable for years. But suddenly it began firing like the center mug! Three 5 gallon buckets of glaze (of differing ages) all changed at once. We tried every combination of thickness, firing schedule, clay body, ventilation, glazing method on dozens of separate pieces with no success to get the blue back. Even mixed a new batch, still no color. Finally the 'crow bar' method worked, 0.25% added cobalt oxide (right mug). It is identical ... amazing. It is not the same mechanism to get the color and it is not exactly the same, but worked while we figured out the real issue: the firing schedule (the secret turned out to be cooling, soaking, then slow cooling to 1400F).

Alberta Slip Rutile blue glaze too thin on a dark body

Alberta Slip Rutile blue glaze too thin on a dark body

This mug has thin walls and was bisque fired to cone 04 (so it had a fairly porosity). As a result the glaze went on thinner when it was dipped. This was not evident at the time of glazing but at firing the thinner sections produced the brown areas.

Alberta Slip Rutile-blue needs Frit 3134, it does not work with others

Alberta Slip Rutile-blue needs Frit 3134, it does not work with others

These two cone 6 mugs have the same glaze recipe: GA6A Alberta Slip base. 4% rutile has been added to each. They were fired in the same kiln using a slow cool schedule. The recipes and chemistry are shown below (the latter gives a clue as to why there is no blue on the right). The mug on the left is the traditional recipe, 80:20 Alberta Slip:Ferro Frit 3134. Frit 3134 melts at a very low temperature and a key reason for that is its near-zero Al2O3 content. Al2O3 in glazes stiffens the melt and imparts durability to the fired glass (normally we want adequate levels in functional glazes). When Al2O3 levels are low and cooling is slower molecules in the stiffening glass have much more freedom to move and orient themselves in the preferred way: crystalline (fast cooling produces a glass). Thus the rutile in the glaze on the left has had its way, dancing as the kiln cooled, producing all sorts of interesting variegated visual effects. The glaze on the right employs Ferro Frit 3195. It has lots of Al2O3 and has contributed enough to stop the rutile dead.

Rutile blue reactive glazes do not refire well

Rutile blue reactive glazes do not refire well

Rutile blue glazes are difficult, blistering and pinholing are very common. You must get it right on the first firing or pinholes and blisters will often invade on the second. The melt fluidity increases, it runs and creates thicker sections in which the bubbles just percolate and just do not heal well during cooling (even if it is slow). When finishing leather hard or dried ware do not disturb thrown surfaces any more than necessary. Make sure that ware is dry before the glaze firing. Do not put the glaze on too thick. Limit the melt fluidity (so it does not pool too thickly in any section). Do not fire too high.

How much rutile can a glaze take before it becomes unstable?

How much rutile can a glaze take before it becomes unstable?

The 80:20 base Alberta slip base becomes oatmeal when over saturated with rutile or titanium (left:6% rutile, 3% titanium; right:4% rutile, 2% titanium right). That oatmeal effect is actually the excess titanium crystallizing out of solution in the melt as the kiln cools. Although the visual effects can be interesting, the micro-crystalline surface is often susceptible to cutlery marking and leaching. This is because the crystals are not as stable or durable as the glass of the glaze.

Tin oxide can stop the rutile variegation effect dead in its tracks!

Tin oxide can stop the rutile variegation effect dead in its tracks!

This is Alberta Slip (GA6C) on the left. Added frit is melting the Alberta Slip clay to it flows well at cone 6 and added rutile is creating the blue variegated effect (in the absence of expensive cobalt). However GA6D (right) is the same glaze with added Tin Oxide. The tin completely immobilizes the rutile blue effect, it brings out the color of the iron (from the rutile and the body).

A fluid reduction rutile glaze is crawling

A fluid reduction rutile glaze is crawling

The rutile mechanism in glazes

The rutile mechanism in glazes

2, 3, 4, 5% rutile added to an 80:20 mix of Alberta Slip:Frit 3134 at cone 6. This variegating mechanism of rutile is well-known among potters. Rutile can be added to many glazes to variegate existing color and opacification. If more rutile is added the surface turns an ugly yellow in a mass of titanium crystals.

Variegation and phase separation with about 5% rutile

Variegation and phase separation with about 5% rutile

The glaze is a dolomite matte fired to cone 10R. High fire reduction is among the best processes to exploit the variegating magic of rutile.

Alberta Slip rutile blue on a porcelain (left) and buff stoneware (right)

Alberta Slip rutile blue on a porcelain (left) and buff stoneware (right)

The recipe is GA6-C. These are from the same firing (slower cooling is needed to develop the rutile effect).

Blisters in a reduction fired rutile glaze

Blisters in a reduction fired rutile glaze

This is a common problem with these glazes. The visual effect is very compelling but also punishing! Potters experiment with higher bisque firing and soaking during bisque. They try cleaner clay bodies. They employ long hold periods at temperature in the glaze firing. But the problem persists. The solution is actually simpler. These glazes have a high melt fluidity and enough surface tension to hold a bubble static during soaks at temperature (no matter how long you hold it). It is better to cool the kiln somewhat (perhaps 100F) and soak at that temperature. Why? Because the increasing viscosity of the melt overcomes the surface tension that maintains the bubbles. You may need to cool more or less than 100 degrees, but start with that.

6% rutile is too much in this cone 6 oxidation glaze

6% rutile is too much in this cone 6 oxidation glaze

Rutile variegates glaze surfaces. But it also opacifies at higher percentages. The blue effect is a product of crystallization that occurs during cooling, it is thus dependent on a slower cooling cycle, especially above 1400F. This is GA6-C Alberta Slip glaze with 4, 5 and 6% rutile. At 6% the rutile crystallization has advanced to the point of completely opacifying the glaze. At 5% the blue is still strong, even on a buff burning body. The loss of color occurs suddenly, somewhere between 5 and 6 percent. Rutile chemistry varies from batch to batch. The blue develops differently on different bodies. So do you want to play "at the edge", with 5% in the glaze, in view of these other factors and the finicky firing curve needed. Change in any of which could push it into the blueless zone?

Crystallization of Rutile at cone 6 completely subdued? How?

Crystallization of Rutile at cone 6 completely subdued? How?

These glazes are both 80% Alberta Slip, but the one on the right employs 20% Ferro Frit 3249 accelerate the melting (whereas the left one has 20% Frit 3134). Even though Frit 3249 is higher in boron and should melt better, its high MgO stiffens the glaze melt denying the mobility needed for the crystal growth.

MgO can destroy the rutile blue variegation effect

MgO can destroy the rutile blue variegation effect

The rutile blue variegation effect is fragile. It needs the right melt fluidity, the right chemistry and the right cooling (during firing). This is Alberta Slip GA6C recipe on the right (normal), the glaze melt flows well due to a 20% addition of Ferro Frit 3134 (a very low melting glass). On the left Boraq has been used as the flux (it is a calcium borate and also melts low, but not as low as the frit). It also contains significant MgO. These two factors have destroyed the rutile blue effect!

Links

Materials Ceramic Rutile
Glossary Phase, phase changes
Glossary Phase Separation
Phase separation is a phenomenon that occurs in transparent ceramic glazes. Discontinuities in the internal glass matrix affect clarity and color.
Glossary Surface Tension
In ceramics, glazes melt to produce a liquid glass. That glass exhibits surface tension and it is important to understand the consequences of that.
Firing Schedules Cone 6 Drop-and-Soak Firing Schedule

By Tony Hansen


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