The Use of Barium in Clay Bodies

Section: Materials, Subsection: Safety

Description

Hazards of barium carbonate, considerations regarding its use in clay bodies for precipitation of soluble salts

Article

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. 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 and there are pros can cons to this view. On one hand, barium is so very slightly soluble that it is difficult to demonstrate solubility of any material in a simple lab experiment (MSDS sheets list it as insoluble). Nevertheless, the precipitation of dissolved calcium and magnesium salts in the body can only occur if dissolved barium is present. Thus you need to add alot of barium carbonate (in a relative sense) to a body to generate the small amount of dissolved barium needed for the reaction. The undissolved barium remains in the carbonate form and thus can be ingested or inhaled. In some cases even the less than 0.5% typically present could be an issue for hypersensitive people. However on the other side of the issue, 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 silica, thus the conclusion that clay containing barium is a highly toxic material is not necessarily true. 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 several factors that indicate otherwise:

The barium is distributed within the clay matrix and a very small 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, theoretically the insoluble portion is not as toxic.
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.

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Authors

Tony Hansen (Owner)

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