|Monthly Tech-Tip |
Alternate Names: Calcium Magnesium Carbonate, Raw Limestone
Dolomite as a ceramic material is a uniform calcium magnesium carbonate. In ceramic glazes it is used as a source of magnesia and calcia. Other than talc, dolomite is the principle source of MgO in high temperature raw glazes. 'Dolomite matte' stoneware glazes, for example, are highly prized for their pleasant 'silky' surface texture. Dolomite by itself is refractory, but when combined with the typical oxides in a glaze (especially boron) it readily enters the melt.
Commercial dolomites are not able to achieve the theoretical 54:46 calcium carbonate:magnesium carbonate ratio, they tend to have less magnesia. It is simple to do an LOI test by firing a specimen of powder in a thin bisqued bowl to confirm the consistency of dolomite shipments. The chemistry shown here is theoretical and many commercial materials approach this with much less than 1% of two or three other oxides (e.g. Al2O3, SiO2).
Dolomite is a carbonate (like whiting) in that it loses considerable weight during firing when it disassociates to form MgO, CaO and CO2, this process being complete by about 900C.
In many circumstances where a raw glaze employs both CaO and MgO, dolomite is an economic alternative to sourcing with a mix of calcium carbonate and talc. However care needs to be taken to obtain a consistent grade since dolomites tend to vary more in mineralogy and can contain iron contamination that can darken the fired glaze. Although calcium carbonate and dolomite are plentiful minerals and grinding plants are located through North America, finding a suitable ceramic grade dolomite that will be consistent and available long term is not as easy as it might seem.
Synthetic substitutes to source MgO and CaO (e.g. frits) are worth considering, especially if glazes are not high temperature. Frits have no loss on ignition (therefore do not generate glaze bubbles) and melt far earlier than mineral sources of MgO and CaO. Using glaze chemistry it is quite easy to adjust a recipe to source MgO from a frit instead of raw materials.
It is about the recipe and the "magic material" that makes it work. And about the firing temperature. This is Plainsman BGP, a terra cotta, mixed with 30% dolomite. Note the "DSHR" column in the SHAB test data (third last column): The drying shrinkage still averages over 7% even with the 30% dolomite, so BGP is very plastic. Notice the "FSHR" (fired shrinkage) column, it is negative for the first five test bars fired at cone 05-01, that means the bars grew in size! But notice the shrinkage hits 0% at cone 1 (bar #6). By cone 2 the trend has reversed to 0.3% shrinkage. The #6 bar is appears to be vitrifying, the color is darkening and it is strong. But notice the last "ABS" column (water absorption), it is 18.7%! This body was intended as a high-porosity ceramic at the lower ranges (it has 25% porosity at cone 05), but the dolomite is also slowing the densification as it goes through the vitrification process. Without the dolomite the top bar would be melting! By cone 1 its firing shrinkage would be 7% and the porosity would be zero.
Dolomite is a key material for glazes, especially mattes. When you are forced to adopt a new brand it needs to be tested. Here, three tests were done to compare the old long-time-use material (IMASCO Sirdar) with a new one (LHoist Dolowhite). The first flow test is a very high dolomite cone 6 recipe formulated for this purpose; the new material runs a little more. The second is G2934 cone 6 MgO matte with 5% black stain; the new material runs a little less here. The third test is the high dolomite glaze on a dark burning clay to see the translucency and compare the surface character. They are very close. It looks like it is going to be OK. Does your supplier test new materials when they are forced to switch suppliers?
This chart compares the decompositional gassing behavior of six materials as they are heated through the range 500-1700F. These materials are common in ceramic glazes, it is amazing that some can lose 40%, or even 50%, of their weight on firing. For example, 100 grams of calcium carbonate will generate 45 grams of CO2! This chart is a reminder that some late gassers overlap early melters. That is a problem. The LOI (% weight loss) of these materials can affect your glazes (causing bubbles, blisters, pinholes, crawling). Notice talc: It is not finished gassing until 1650F, yet many glazes have already begun melting by then (especially fritted ones). Even Gerstley Borate, a raw material, is beginning to melt while talc is barely finished gassing. And, there are lots of others that also create gases as they decompose during glaze melting (e.g. clays, carbonates, dioxides).
GR10-J Ravenscrag dolomite matte base glaze at cone 10R on Plainsman H443 iron speckled clay. This recipe was created by starting with the popular G2571 base recipe (googleable) and calculating a mix of materials having the maximum possible Ravenscrag Slip percentage. The resultant glaze has the same excellent surface properties (resistance to staining and cutlery marking) but has even better application and working properties. It is a little more tan in color because of the iron content of Ravenscrag Slip (see ravenscrag.com).
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.
These glaze cones are fired at cone 6 and have the same recipe: 20 Frit 3134, 21 EP Kaolin, 27 calcium carbonate, 32 silica. The difference: The one on the left uses dolomite instead of calcium carbonate. Notice how the MgO from the dolomite completely mattes the surface whereas the CaO from the calcium carbonate produces a brilliant gloss.
Talc exhibits unique powder characteristics, a product of the particle shape and particle surface characteristics. While most powders slide cleanly from this stainless steel scoop, talc powder leaves a film. Dolomite and calcium carbonate are similar.
An example of how the same dolomite cobalt blue glaze fires much darker in oxidation than reduction. But the surface character is the same. A different base glaze having the same colorant might fire much more similar. The percentage of colorant can also be a factor in how similar they will appear. The identity of the colorant is important, some are less prone to differences in kiln atmosphere. Color interactions are also a factor. The rule? There is none, it depends on the chemistry of the host glaze, which color and how much there is.
Some material data sheets show both the oxide and mineralogical analyses. Dolomite, for example, is composed of calcium carbonate and magnesium carbonate minerals, these can be separated mechanically. Although this material participates in the glaze melt to source the MgO and CaO (which are oxides), it's mineralogy (the calcium and magnesium carbonates) specifically accounts for the unique way it decomposes and melts.
This unbelievable body is made from dolomite, 65% of it. There is 35% ball clay to give it workability and 5% Ferro frit 3110. The frit stabilizes it so that the fired body does not rehydrate. This has a porosity of 35%! And that porosity is stable across the entire range we have fired it at (cone 06-6). The single-layer on the lower portion has been completely absorbed, the double-layer on the upper is almost gone.
Examples of calcium carbonate (top) and dolomite (both mixed with 25% bentonite to make them plastic enough to make a test bars). They are fired to cone 9. Both bars are porous and refractory, even powdery. However, put either of these in a mix with other ceramic minerals and they interact strongly to become fluxes.
Dolomite at mineralszone.com
Dolomite at Wikipedia
Materials that source Na2O, K2O, Li2O, CaO, MgO and other fluxes but are not feldspars or frits. Remember that materials can be flux sources but also perform many other roles. For example, talc is a flux in high temperature glazes, but a matting agent in low temperatures ones. It can also be a flux, a filler and an expansion increaser in bodies.
Generic materials are those with no brand name. Normally they are theoretical, the chemistry portrays what a specimen would be if it had no contamination. Generic materials are helpful in educational situations where students need to study material theory (later they graduate to dealing with real world materials). They are also helpful where the chemistry of an actual material is not known. Often the accuracy of calculations is sufficient using generic materials.
|Materials||Camadil 95 Dolomite|
|Oxides||CaO - Calcium Oxide, Calcia|
|Oxides||MgO - Magnesium Oxide, Magnesia|
Random material mixes that melt well overwhelmingly want to be glossy, creating a matte glaze that is also functional is not an easy task.
|Minerals||Dolomitic Limestone, Dolostone|
|Glaze Matteness||Dolomite can be used in glazes melting over 1170C to produce a silky matte surface. This occurs because high percentages of dolomite help to form diopside crystals (CaMg(SiO3)2) on cooling, and it is these that produce the popular butter-matte effect. This effect is most pronounced in reduction.|