The Use of Barium in Clay Bodies

MSDS sheets indicate that barium (CAS: 7440-39-3) is poison and toxic if ingested. MSDS sheets also claim that barium is an irritant for inhalation and skin contact. Excessive amounts can cause violent diarrhea, convulsive tremors, and muscular paralysis. Barium is known to affect the heart and nervous system.

In ceramics barium is most commonly inhaled as a fine dust or absorbed through cuts or lesions on the hands of people who handle compounds containing the material. However, some authorities quote exposure limits that are less restrictive than those for silica (e.g. ACGIH lists a Threshold Limit Value at 0.5 mg/cubic meter for barium while quartz is 0.05). OSHA, on the other hand, lists quartz as 10.0 and barium as 0.5. (see the links to learn more about TLV, PEL).

Almost all raw clay materials (including kaolins) contain soluble impurities (i.e. iron stained calcium/magnesium sulphates). When a raw piece of clay is dried, these impurities come to the surface with the water as it evaporates. During firing this often iron stained precipitated scum left on the surface forms a glassy discoloration and in some cases can even creates a glaze-like surface.

Soluble salts are highly prized in sculpture bodies because they highlight surface textures and contours. This is especially so if the salts are iron stained and create variations in coloration. However, in functional pottery and structural products these salts are not wanted. Even after a clay is fired, these soluble salts can come to the surface if the clay is not vitreous and it is rewetted often (this is often the case with red terra cotta brick, the brick industry calls this phenomenon Efflorescence). These surface deposits often affect adherence to the clay and melting patterns of overlying glaze layers. Fused solubles on the surface can also stick ware together or to kiln shelves and they can seal the surface causing premature bloating during firing.

Clay body and material supply companies commonly add barium carbonate to clay bodies in small percentages (0.1-0.8%) to solve this problem (heavy clay industries use more barium, others strive to reduce it to a minimum, often for production reasons). The barium chemically reacts with the sulphates to precipitate insoluble products. In the reaction, very slightly soluble barium carbonate (in contrast with barium sulfate used in medical x-rays which it is insoluble, inert, and non-radioactive) and soluble calcium sulphate convert to insoluble barium sulphate and calcium carbonate. Thus they both remain within the body and do not concentrate on the surface during drying. The ceramic industry has found this strategy to be effective and has not found a viable substitute. It is possible to measure the amount of solubles in a clay body and calculate the minimum amount of barium needed to precipitate them. However in practical terms this does not work because different types and even shipments of barium vary in their effectiveness and the natural salt content within the clays varies greatly. It is far more effective to simply observe the effect of various additions and adjust periodically so that there is just enough to remove the solubles (barium is expensive and industry obviously does not want to use more than is necessary).

Controversy Surrounding Toxicity

The presence of barium in clay bodies is sometimes thought to be a health hazard for hypersensitive people. Barium is so very slightly soluble that it is difficult to demonstrate solubility of any material in a simple lab experiment (MSDS sheets even list it as insoluble). Nevertheless, the precipitation of dissolved calcium and magnesium salts in the body can only occur if dissolved barium is present, this demonstrates some solubility. You need to add alot of barium carbonate (up to 0.5%) to a body to generate the small amount of dissolved barium needed for the reaction. The undissolved barium remains in the carbonate form. It must be remembered that quartz is completely pervasive in almost all ceramic glazes and clay bodies and any balanced view of safety should put primary emphasis on it. In addition lab tests to deduce barium carbonate content in aged pugged clay bodies have shown a much lesser quantity of unreacted barium than the slight solubility suggests is possible. This means the issue cannot be fully understood by considering only the slight solubility of barium. Further, as noted above, permissible limits for barium can be higher than those for quartz, thus the conclusion that clay containing barium is a highly toxic material is questionable since typical clays can contain 20% or more quartz and yet only a tiny fraction of 1% of soluble barium. An MSDS from BassTech International classifies barium as moderately toxic on inhalation, non-toxic on contact or skin absorption, an eye irritant and toxic if ingested at 57mg per kg of body weight (this would be over 1 kg of pugged clay containing the highest proportion of barium normally used).

Leaching Hazard When Used in Clay Bodies?

The practice of adding barium to clay bodies is also questioned by some as posing a leaching hazard in functional ware made from barium-containing clay. However one must consider some factors that indicate otherwise:

The barium is distributed within the clay matrix, only a very tiny fraction of that which is added actually presents itself at the surface.
The barium reacts with comparatively abundant fluxes and silica (and is a flux itself) in vitreous clay bodies to form insoluble silicate glasses within the body.
Functional ware is covered with glaze completely isolating the barium from food surfaces.
Recipes employing highly refined clays and minerals often do not require barium, however many are subjected to a wide variety of chemical processes that also have a bearing on functional safety.
The soluble portion of the barium converts to insoluble and harmless barium sulphate after the body is wetted during preparation.
Barium carbonate makes it possible to make bodies using native natural coarser-grained materials (which are inherently safer because they generate fewer of the minus 1 micron particles that are fine enough to lodge in the lungs).

The US Food and Drug administration does not have a leaching requirement for barium. However, the US EPA has a standard for drinking water of 2 mg/liter or less. This standard was set to protect the population most at risk for heart effects - adult men. Testing can be done at Elemental Research Lab, 309-267 West Esplanade, North Vancouver, B.C. Canada V7M 1A5 604-985-0445 (they test many metals). Also at Kirby Health Center Lab, 71 North Franklin Street, Wilkes-Barre, PA 18701 717-822-4278.

By Tony Hansen
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Related Information

A typical DFAC drying disk of an iron stoneware clay

The center portion was of this DFAC test disk was covered and so it lagged behind during drying, setting up stresses that caused the disk to crack. This test is such that most pottery clays will exhibit a crack. The severity of the crack becomes a way to compare drying performances. Notice the test also shows soluble salts concentrating around the outer perimeter, they migrated there from the center section because it was not exposed to the air.

Soluble salts on cone 04 terra cotta clay bodies

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 magic of a small barium carbonate addition to a clay body

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).

How bad can efflorescence of soluble salts on fired ceramic be?

Like this! This terra cotta clay matures to good strength around 1950F. Notice how the soluble salts have concentrated on the outer and most visible surface. The piece was dried upside down so of course, all the water had to escape through that route. A complicating factor is how handling of the piece at the leather hard stage has made it even more unsightly. This problem is common in many terra cotta materials but can also surface in others. Barium carbonate can be used to precipitate the salts inside the clay matrix so they do not come to the surface on drying. There is good news: Solubles salt deposition can actually be much worse than you see here.

Links

Materials	Barium Carbonate A pure source of BaO for ceramic glazes. This is 77% BaO and has an LOI of 23% (lost at CO2 on firing).
Materials	Barium Sulfate
Oxides	BaO - Barium Oxide, Baria
Hazards	Barium Carbonate
Hazards	BARIUM and COMPOUNDS / Toxicology
Hazards	Understanding Acronyms on MSDS's Understanding the meaning and purpose of acronyms used on materials safety data sheets for ceramic minerals and materials
Minerals	Gypsum Gypsum is hydrated calcium sulphate, CaSO4 2H2O. It is the crystalline mineral from which plaster is
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	Sulfates Soluble sulfates in clay produce efflorescence, an unsightly scum that mars the fired surface of structural and functional ceramic products.
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.

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