|Monthly Tech-Tip |
There is an increasing awareness of the food safety of glazes among potters. Be skeptical of claims of food safety from potters who cannot explain or demonstrate why.
In recent years potters and small manufacturers have become aware (or have been forced to become aware) that ceramics and pottery are not as inert as they once thought. A variety of potential health impacts exist to users of ware they make. These include flaking off of glaze chips (that could be ingested), harboring of bacteria (in glaze cracks and pores of bodies or engobes), possible fracture or cracking of ware when suddenly heated (e.g. by hot coffee), super heating of ware in microwave ovens (presenting a burn hazard) and leaching of metals or other elements from the glaze surface (by hot, acidic or base liquids).
Perhaps the most public and serious of the issues is leaching. There is need for skepticism of claims made by potters who are not conversant on this topic. Glazes are trafficked online and soon lose any non-functional labels they may have had. Potters who produce ware having a transparent or white liner on food surfaces are those most likely to be conscious of this topic. Those producing ware whose food surfaces are brightly colored (without a transparent overglaze), very matte, heavily crystallized or overly melted (and thus running) are the most likely to be unaware of this topic.
Although a ceramic glaze is akin to a glass, it actually can dissolve over time when in contact with liquids if its chemistry is not balanced and stable. This is not really a problem if the glaze is a white or transparent and does not contain any elements that are harmful (e.g. feldspars, kaolin, silica, calcium carbonate, talc). But if it contains metal oxide colorants, barium, lithium or lead these present a problem. It is possible that a glaze containing all of these can be stable and will not dissolve enough to be a hazard. But if the glaze does not have a balanced chemistry it certainly can leach metals into food and drink.
What does balanced mean? It means normal. Consider the some obvious questions:
-Every potter knows that 0.5 or 1% cobalt oxide can produce a strong blue in almost any glaze. What if a recipe contains 5% cobalt? This is a red light, the extra cobalt could very well precipitate from the melt during cooling and crystallize rather than form part of the glaze matrix.
-Does the glaze form crystals on its surface during firing? Crystals in glazes are often unstable and leach.
-We expect to see 3% lithium carbonate in a recipe. What if there is 10%? What if there is 30% barium instead of 5%. Or 20% manganese dioxide instead of 5%? These are obvious issues and many a glaze fails this simple appraisal.
-What if there is only 1% cobalt in a glaze base that melts alot (and runs off the ware if applied too thick)? Likely that glaze does not contain enough SiO2 and Al2O3 (the former is the glass and the latter the stabilizer, all functional glazes must have these).
-What if the glaze is a matte and does not even melt properly? Any colorants in it are going to leach.
-What if a glaze contains 60% feldspar instead of the normal 30%? Feldspar is not hazardous, but it is the base of the glaze into which a hazardous metal oxides can be added to get color. If the host glaze into which the colors are added is not balanced they are likely to leach.
A special class of glaze colorants are stains. These powders have been compounded by mixing metal oxides with stabilizers and firing them at temperatures in excess of what a normal glaze would be fired to. The cooled sintered material is then ground into a powder. In theory, these stain particles do not dissolve into the glaze melt so safety issues are mitigated. However some stains produce very bright reds, yellows and oranges, they are very useful because these colors are difficult or impossible to achieve using metal oxides alone. These stains are also much less stable than others and have lower temperature limits. When used above their recommended temperature some of the toxic metals they contain (e.g. cadmium) will dissolve into the glaze melt and become leaching hazards. Cone 6, for example, can be beyond the range of common encapsulated stains.
Balance is also sought in the chemistry of a recipe. Insight-live.com, for example, can display the oxide chemistry of recipes you enter. But caution is needed. Many people say that safe glazes have a specific chemistry profile and one can recognize predisposition to leaching by simply viewing a chemical formula (to see if certain oxides fall outside limits). There is only some truth to this. For example, we might expect to see 4.0 SiO2 in a middle-temperature glaze, but if a recipe only has 1.5 there is a good chance a stable glass has not been formed. Of course, high percentages of oxides like BaO, MnO, PbO, Li2O would be potential issues, but the high percentages of their source materials would be obvious in the recipe anyway. The point is that absolute limits for all oxides (to prevent leaching) cannot be established, the chemistry is much more complex than that. Besides, this would drastically narrow the range of acceptable compounds from which to make glazes. Remember, leaching is easy to test (see the links on this page) and anyone can do it. Thus, a better application of chemistry is to give direction for change if a glaze fails a leaching test. Still, there is value in being aware of obvious chemistry irregularities (against common base recipes for the same temperature). You will find articles and videos on this site addressing this.
Crazing is often seen by potters as a visual asset, but from a safety point of view crazed ware is unacceptable. The crazing severely weakens ware and provides sites where water can enter and saturate the porosity of the body below. The cracks harbor bacteria and provide weakness points from where thermal shock can propagate them. Simple awareness of crazing is a strong measure anyone can take to improve safety of ware they produce. Crazing happens when glazes are under tension, stretched on to ware. This is fixed by adjusting the recipe to lower the thermal expansion (many articles and videos on this site show how to do this).
Simple methods of physical testing are within the means of everyone. For leaching, a slice of lemon left against the glaze (or some pure lemon juice) overnight will reveal differences in color or surface character if leaching is occurring. Simple visual inspection will reveal crazing or shivering. If a piece of functional ware is used and put in the dishwasher every day crazing will almost certain appear if the glaze is under tension. An ice-water and boiling-water immersion test is even better to reveal if these problems will happen over time.
These are four cone 6 glazes of diverse chemistry. They have varying melt fluidities. They are soaked (half way up) in lemon juice over night. None show any evidence of surface changes. All contain 2% copper carbonate. If the copper was increased, especially to the point of going metallic or crystallizing, likely the leaching test would have different results. So, if you use copper sensibly (in moderate amounts), there is a good chance you can make a glaze that resists leaching.
There are thousands of ceramic glaze recipes floating around the internet. People dream of finding that perfect one, but they often only think about the visual appearance, not of the usability, function, safety, cost or materials. That resistance to understanding your materials and glazes and learning to take control is what we personify as the dragon. Using the resources on this site you could be fixing, adjusting, testing, formulating your own glaze recipes. Start with your own account at insight-live.com.
A closeup of a glossy Cone 6 glaze having 4% added copper carbonate. The bottom section has leached in lemon juice after 24 hours. This photo has been adjusted to spread the color gamut to highlight the difference. The leached section is now matte.
Three cone 6 commercial bottled glazes have been layered. The mug was filled with lemon juice over night. The white areas on the blue and rust areas on the brown have leached! Why? Glazes need high melt fluidity to produce reactive surfaces like this. While such are normally subject to leaching, the manufacturers were able to tune the chemistry of each to make them resistant. But the overlaps mingle well (because of the fluidity), they are new chemistries, less stable ones. What is leaching? Cobalt! Not good. What else? We do not know, these recipes are secret. It is much better to make your own transparent or white liner glaze. Not only can you pour-apply it and get very even coverage, but you know the recipe, have control, can adjust to fit your body.
There is a direct relationship between the way ceramic glazes fire and their chemistry. Wrapping your mind around that and overcome your aversion to chemistry is a key to getting control of your glazes. You can fix problems like crazing, blistering, pinholing, settling, gelling, clouding, leaching, crawling, marking, scratching, powdering. Substitute frits or incorporate better, cheaper materials, replace no-longer-available ones (all while maintaining the same chemistry). Adjust melting temperature, gloss, surface character, color. Identify weaknesses in glazes to avoid problems. Create and optimize base glazes to work with difficult colors or stains and for special effects dependent on opacification, crystallization or variegation. Create glazes from scratch and use your own native materials in the highest possible percentage.
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 an example of serious crazing in a glaze. The lines have gotten darker with use of the bowl! That means the color is organic, from food. This cannot be healthy.
Left: Ravenscrag G2928C matte liner glaze on inside of mug. Right: A clear glossy. The matte needs to be soaked in the kiln long enough to make sure it develops a functional surface, especially on the bottom. Mattes are not always the best choice for food surfaces, but you can do it if you blend in enough glossy glaze to make it smooth enough not to cutlery mark.
These cone 6 porcelain mugs are hybrid. Three coats of a commercial glaze painted on outside (Amaco PC-30) and my own liner glaze poured in and out on the inside (G2926B). When commercial glazes (made by one company) fit a stoneware or porcelain (made by another company), without crazing or shivering, it is purely an accident! So use them on the outside. But for inside food surfaces make or mix your own. When you know the recipe you can tune the thermal expansion. And the degree of melt. And the application properties. And you can use quality materials to source a balanced chemistry. The place to start understanding your glazes, organize testing and development and document everything is an account at Insight-live.com.
The 80:20 base Alberta slip base becomes oatmeal when over saturated with rutile or titanium (left:6% rutile, 3% titanium; right:4% rutile, 2% titanium right). That oatmeal effect is actually the excess titanium crystallizing out of solution in the melt as the kiln cools. Although the visual effects can be interesting, the micro-crystalline surface is often susceptible to cutlery marking and leaching. This is because the crystals are not as stable or durable as the glass of the glaze.
The cone 6 G1214M glaze on the left melts well. Can it benefit from a silica addition? Yes. The right adds 20% yet still melts as well, covers better, is more glossy, more resistant to leaching, harder and has a lower thermal expansion.
|Tests||Glaze Leaching Test|
|Tests||Boiling Water:Ice Water Glaze Fit Test|
|Tests||300F:Ice Water Crazing Test|
Co-efficient of Thermal Expansion
Ceramics are brittle and many types will crack if subjected to sudden heating or cooling. Some do not. Why? Differences in their co-efficients of thermal expansion.
When sudden changes in temperature cause dimensional changes ceramics often fail because of their brittle nature. Yet some ceramics are highly resistant.
This is a type of stain manufacture that enables the use of metal oxides (like cadmium) under temperature conditions in which they would normally fail.
A term used in ceramic to express the degree to which an item is safe and stands up to everyday use. Functionality embodies strength, hardness, resistance to acid attack and thermal shock, etc.
Liner-glazing ceramic ware is a very good way to assure that your ware has a durable and leach resistant surface. It also signals customers that you care about this.
Ceramic glazes vary widely in their resistance to wear and leaching by acids and bases. The principle factors that determine durability are the glaze chemistry and firing temperature.
Crazed ceramic glazes have a network of cracks. Understanding the causes is the most practical way to solve it. 95% of the time the solution is to adjust the thermal expansion of the glaze.
Dishwasher safety is a concern in ceramic table ware, especially if the ware has been imported or made by a small company or potter.
Microwave safety is a concern in the production of function ceramic ware.
This term refers to critical thinking ability that potters and technicians can develop to recognize recipes having obvious issues and merit, simply by seeing the materials and percentages.