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Barium Carbonate

Alternate Names: Barium Carb, Witherite

Oxide Analysis Formula
BaO 77.66% 1.00
CO2 22.34%n/a
Oxide Weight 153.30
Formula Weight 197.40

Notes

Barium carbonate powder is dense and white and is manufactured either from the mineral barite (BaSO4) or from barium chloride. Subsequently a precipitation process is used to get the carbonate form. There are several crystalline forms of BaCO3, alpha is the most stable.

Barium carbonate is very stable thermally and does not readily disassociate unless at least some CO is available in the kiln atmosphere (i.e. reduction). BaCO3 is reduced to the unstable BaCO2 in the reaction:

BaCO3 + CO -> BaCO2 + CO2

While BaCO2 has a high melting temperature, it will break down much readily in a glaze melt (liberating the BaO for glass building). It decomposes even more readily during glaze melting in a reduction atmospheres. The dissolution process happens most quickly if BaCO3 is present in small amounts (e.g. 5% or less). Even if present in larger amounts, the glaze matrix can solidify with both types, one participating in the glass microstructure and the other acting as a refractory filler, opacifier and matting agent (especially in low temperature glazes). Effects produced when baria is acting as a filler are sometimes mistaken for those of a true baria crystal matte. Such will likely leach toxic BaO (other oxides will opacify or produce a low fire matte i.e. CaO, MgO, Alumina, Zircon).

Barium carbonate produces gases as it decomposes and these can sometimes cause many pinholes or blisters in glazes. There are barium frits available (e.g. Fusion F-403 has 35% BaO), incorporating one of them to source it instead is a classic application of glaze chemistry calculations. The resultant glaze will be more fusible and will have better clarity and fewer defects.

In art ceramics barium carbonate is popular for the production of classic barium crystal mattes, BaO readily forms crystalline phases during cooling. These are dependent on adequate kiln temperatures, cooling cycle and the chemistry of the host glaze (a slightly reducing atmosphere is also beneficial). Some have observed that in some formulations, barium crystallizes so well that it will occur even with very rapid cooling. Barium can act to initiate crystal development in other chemistries, for example metallic glazes can benefit by the addition of some barium carbonate.

BaO can often be sourced from a barium frit (like Ferro CC-257) instead of raw barium carbonate, provided that the percentage is not too high. Do not assume that BaO is necessary in every glaze in which it appears. In some recipes BaO can be substituted for SrO or CaO and even MgO (using glaze chemistry software of course) without losing the color or surface (bright glossy blues, for example).

Barium carbonate is commonly added to clay bodies in small amounts (0.2-0.8%) to halt fired surface scumming or efflorescence It is slightly soluble in water and provides Ba++ ions to link with SO4-- ions in the water to form BaSO4 (barium sulfate). This new sulfate molecular form is much less soluble (2-3 mg/L), so it stays internal (rather than migrating to the surface during drying). However companies try minimize the use of barium (or even high clays with high soluble salts) because the barium sulphate generates sulphuric acid during firing and it corrodes kiln refractories. To get the best dissolution it is best to add the barium to the water first and mix as long as possible, then either add the water to the other dry ingredients (for plastic bodies) or add the other ingredients to the water (for slips).

See Metallurgical and Materials Transactions Volume 42B, August 2011. Page 901 for an article exploring Ba-Al-Si systems at higher temperatures.

Related Information

Soluble salts on cone 04 terra cotta clay bodies

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Low temperature clays are far more likely to have this issue. And if present, it is more likely to be unsightly. The salt-free specimens have 0.35% added barium carbonate.

The same clays and firing, but one tiny difference

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An example of how effective barium carbonate is at precipitating the soluble salts in a terra cotta clay. These two unglazed, cone 04 fired, mugs are made from the same clay, but the one on the left has 0.35% added barium carbonate.

The magic of a small barium carbonate addition to a clay body

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Two bisqued terracotta mugs demonstrate efflorescence. The clay on the right has 0.35% added barium carbonate (it precipitated the natural soluble salts dissolved in the clay and prevented them from coming to the surface with the water and being left there during drying). The process is called efflorescence and is the bane of the brick industry. The one on the left is the natural clay. The unsightly appearance is fingerprints from handling the piece in the leather-hard state, the salts have concentrated in these areas (the other piece was also handled).

Frits instead of raw zinc, lithium, barium, strontium

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zinc, lithium, barium, strontium oxide powders

These materials have many issues. They can create problems in glaze slurries (like precipitates, higher drying shrinkage), cause issues with laydown density and produce fired surface defects (like pinholes, blisters, orange peeling, crystallization). Lithium and barium carbonates have toxicity issues and the carbon burns off during firing (with lithium, for example, 60% of its weight is lost). Yet the oxides that these materials supply to the glaze melt - ZnO, Li2O, BaO and SrO can be sourced from frits (removing most of the problems and imparting better glaze melting). Fusion Frit F-493 has 11% LI2O, F-403 has 35% BaO, F-581 has 39% SrO and FZ-16 has 15% ZnO. Of course, these frits source other oxides (but such are common in most glazes). Using glaze calculation you can often duplicate the chemistry of glazes while sourcing these oxides from frits. This being said, using the frits is about achieving a quality and avoid defects over concerns about their extra cost. Often the benefits lower the overall cost of production.

Links

URLs http://www.epa.gov/epaoswer/hazwaste/id/inorchem/docs/barium.pdf
Information on baruim manufacturing methods
URLs http://en.wikipedia.org/wiki/Barium_carbonate
Barium carbonate at Wikipedia
URLs http://ceramicartsdaily.org/ceramic-glaze-recipes/glaze-chemistry-ceramic-glaze-recipes-2/leaving-bariumville-replacing-barium-carbonate-in-cone-10-glazes/
Article on substituting BaO for SrO, CaO, MgO
URLs http://www.solvay.com/en/binaries/Bariumcarbonat_prevention-efflorescence-en-188992.pdf
Document of using Barium Carbonate in Brick to prevent efflorescence
Hazards Barium Carbonate
Hazards BARIUM and COMPOUNDS / Toxicology
Hazards The Use of Barium in Clay Bodies
Considerations regarding the use of barium carbonate in pottery and structural clay bodies for precipitation of soluble salts.
Temperatures Barium carbonate melts (1360-)
Temperatures Decomposition of Barium Carbonate (1025-)
Troubles Crawling
Ask yourself the right questions to figure out the real cause of a glaze crawling issue. Deal with the problem, not the symptoms.
Typecodes Generic Material
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.
Typecodes Flux Source
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.
Oxides BaO - Barium Oxide, Baria
Minerals Barytes, Barite
Barite (65.7% BaO, 34.3% SO4) is the main mineral from which barium carbonate is sourced. It is mine
Minerals Witherite
Barium carbonate mineral.
Minerals Gypsum
Gypsum is hydrated calcium sulphate, CaSO4 2H2O. It is the crystalline mineral from which plaster is
Articles Soluble Salts in Minerals: Detailed Overview
There are a wide range of soluble materials that can be in clay, this article enumerates them, provides procedures on identifying and measuring them and outlines what to do about the problem.
Glossary Sulfates
Soluble sulfates in clay produce efflorescence, an unsightly scum that mars the fired surface of structural and functional ceramic products.
Glossary Efflorescence
A common problem with dry and fired ceramic. It is evident by the presence of a light or dark colored scum on the dry or fired surface.
Glossary Matte Glaze
Random material mixes that melt well overwhelmingly want to be glossy, creating a matte glaze that is also functional is not an easy task.
Materials Ferro Frit CC-257
Materials Sodium Bicarbonate
Media A Broken Glaze Meets Insight-Live and a Magic Material
Use Insight-Live.com to do major surgery on a feldspar saturated cone 10R glaze recipe with multiple issues: blistering, pinholing, crazing, settling, dusting and possibly leaching!

Data

Density (Specific Gravity) 4.27

Mechanisms

Glaze OpacifierIf available in sufficient amount, barium oxide will promote crystallization of a melt during cooling, thus imparting a measure of opacity.
By Tony Hansen
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