|Monthly Tech-Tip |
Ceramic glazes that mark from cutlery are either not properly melted (lack flux), melted too much (lacking SiO2 and Al2O3), or have a micro-abrasive surface that abrades metal from cutlery.
In glazes with this fault, rubbing a metal key, knife or spoon on the surface will leave black marks. In tolerable situations, the mark can be rubbed off easily with your finger. But when the problem is worse, it cannot be completely removed or washed off.
This is a common fault in glazes. Even commercial tableware can exhibit the issue. In stable and durable glazes, cutlery marking usually happens when the surface is not smooth (e.g. mattes). Micro-topology can be wavy, as is the case with high-MgO silky mattes, the more irregular the surface the more the marking occurs. Fixing the problem is a matter of choosing a compromise between matteness and marking (by adjusting MgO content or increasing the cooling speed of the kiln). The micro-surfaces of durable glossy glazes can also have angular protrusions because on the presense of excessive zircon particles (added for opacification), these can abrade metal and trap metal particles. The solution is to find a balance between the amount of zircon needed to opacify and the need to minimize marking.
Of course, glazes that are not completely melted will mark easily (because the surface both abrades metal and the metal itself removes fragments of glaze exposing more sharp contours). The degree to which the chemistry of a glaze is unbalanced relates to how soft and susceptible to abrading it is (adequate Al2O3 and SiO2, for example, are very important to hardness and durability). If a glaze is not adequately melting, other issues besides cutlery marking are likely more important (e.g. staining, leaching; use a GLFL melt flow test to see how fluid it actually is).
Sometimes glazes that appear poorly melted are actually the opposite, they have completely crystallized surfaces that are a product of very high melt fluidity. Crystalline mattes (e.g. those high in CaO, SrO) have surfaces covered by a fine mesh of micro-crystals, these commonly cutlery mark badly (because of the angularity of surface). These types of glazes, by design, have low Al2O3, that means they also inherently lack durability. Fixing this type of cutlery marking problem will depend on the degree to which you are willing to compromise the fired appearance (when you add Al2O3 and SiO2) or how much faster you are willing to cool the firing (so crystals have less time to grow). There are other oxides used to promote crystal growth (e.g. ZnO, Li2O), these can produce surfaces that are even more markable than CaO.
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.
This is G2571A cone 10R dolomite matte glaze with added 1% cobalt oxide, 0.2% chrome oxide. The porcelain is Plainsman P700, the inside glaze is a Ravenscrag Slip clear. This recipe can be googled, it has been available for many years and was first formulated by Tony Hansen. This base is very resistant to crazing on most bodies and it does not cutlery mark or stain. It also has very good application properties.
The top glaze is VC71, a popular matte cone 6 glaze used by potters. Bottom is G2934 matte, a public domain recipe produced by Plainsman Clays. The latter is a high-MgO matte, it melts well and does not cutlery mark or stain easily. As evidence that it is a true matte, notice that it is still matte when fired to cone 7 or 8. VC71, while having a similar pleasant silky matte surface at cone 6, converts to a glossy if fired higher. This suggests that the cone 6 matteness is due to incomplete melting. For the same reason, it is whiter in color (as soon as it begins to melt and have depth the color darkens).
G2934 is a popular matte for cone 6 (far left). The mechanism of the matteness is high MgO content (it produces a more pleasant surface that cutlery marks and stains less than other mechanisms such as crystallization or insufficient melting). But what if it is too matte for you? This recipe requires accurate firings, did your kiln really go to cone 6? Proven by a firing cone? If it did, then we need plan B: Add some glossy to shine it up a bit. I fired these ten-gram GBMF test balls of glaze to cone 6 on porcelain tiles, they melted down into nice buttons that display the surface well. Top row proceeding right: 10%, 20%, 30%, 40% G2926B added (100% far right). Bottom: G2916F in the same proportions. The effects are similar but the top one produces a more pebbly surface.
This flow test compares the base and base-plus-iron version of a popular CM recipe called "Tenmoku Cone 6" (20% whiting, 35% Custer feldspar, 15% Ball Clay and 30% silica, 10% iron oxide). Although iron is not a flux in oxidation, it appears to be doing exactly that here (that flow is just bubbling its way down the runway, the white one also fires to a glassy surface on ware). It looks melted in the tray on the right but notice how easily it is scratching on the tile (lower left). This demonstrates that looks can be deceiving. Cone 6 functional glazes always have some percentage of a power flux (like boron, lithia, zinc), otherwise they just do not melt into a hard glass. Maybe a glaze looks melted, but it has poor durability.
This is G2934Y (a version of the G2934 cone 6 matte base recipe that supplies much of the MgO from a frit instead of dolomite). Like the original, it has a beautiful fine silky matte surface and feels like it would not cutlery mark. But, as you can see on the left, it does! The marks can be cleaned off easily. But still, this is not ideal. The degree of matteness that a glaze has is a product of its chemistry. But can we fix this without doing any chemistry? Yes. By blending this with G2926B clear glossy (90:10 proportions) the marks are gone and the surface is only slightly changed.
Left: VC71 cone 6 silky matte glaze. Right: An adjustment that adds boron melter and SiO2/Al2O3 (which preserving their ratio). The dramatic improvement in melting was unexpected. Even though B has the same Si:Al ratio, it is completely glossy. Why? A (left) is simply not melting completely, that is why it is silky matte (not a true matte). Yet A feels like a good silky matte and is resistant to cutlery marking. Why? Feel alone can be misleading. Cutlery marking usually happens with matte glazes or heavily opacified whites, this is neither, it is an under-fired glossy glaze, fired just high enough not to mark.
These 10 gram balls were fired and melted down onto a tile. The one the left is the original G2934 Plainsman Cone 6 MgO matte with 6% Mason 6600 black stain. On the right the adjustment has a 20% glossy glaze addition to make it a little less matte. Notice the increased flow (the ball has flattened more) with the addition of the glossy. In addition, while the percentage of stain in the one on the right is actually less (because it was diluted), the color appears darker! Tuning the degree of matteness when making color additions to a base is almost always necessary to achieve a glaze that does not cutlery mark.
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.
The glaze is cutlery marking (therefore lacking hardness). Why? Notice how severely it runs on a flow tester (even melting out holes in a firebrick). Yet it does not run on the cups when fired at the same temperature (cone 10)! Glazes run like this when they lack Al2O3 (and SiO2). The SiO2 is the glass builder and the Al2O3 gives the melt body and stability. More important, Al2O3 imparts hardness and durability to the fired glass. No wonder it is cutlery marking. Will it also leach? Very likely. That is why adequate silica is very important, it makes up more than 60% of most glazes. SiO2 is the key glass builder and it forms networks with all the other oxides.
This is an example of cutlery marking in a cone 10 silky matte glaze lacking Al2O3, SiO2 and having too much MgO. Al2O3-deficient glazes often have high melt fluidity and run during firing, this freezes to a glass that lacks durability and hardness. But sufficient MgO levels can stabilize the melt and produce a glaze that appears stable but is not. Glazes need sufficient Al2O3 (and SiO2) to develop hardness and durability. Only after viewing the chemistry of this glaze did the cause for the marking become evident. This is an excellent demonstration of how imbalance in chemistry has real consequences. It is certainly possible to make a dolomite matte high temperature glaze that will not do this (G2571A is an example, it has lower MgO and higher Al2O3 and produces the same pleasant matte surface).
An example of how a spoon can cutlery mark a glaze. This is a popular middle temperature recipe used by potters. The mechanism of its matteness is a high percentage of zinc oxide that creates a well-melted glaze that fosters the growth of a mesh of surface micro-crystals. However these crystals create tiny angular protrusions that abrade metal, leaving a mark. Notice the other matte flow on the left (G2934), it not only has a better surface (more silky feel) but also melts much less (its mechanism is high MgO in a boron fluxed base). It is does not cutlery mark at all!
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.
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