Colored (Coloured) Glasses
Dr. Frank E. Woolley
The Nature of Coloration in Glasses
The two principal methods of creating color in glasses are to dissolve elements that absorb light of specific wavelengths, or to create dispersions of extremely fine particles, called colloids, that also absorb light of specific wavelengths.
The amount of light absorbed by either method depends only on the wavelength and the amount of the colorant that is in its path.
This means that the intensity of the color depends on the product of the thickness of the glass and the concentration of colorant in the glass; thick colored glass looks darker or more colored than thin glass of exactly the same composition, in direct proportion to the glass thickness.
Some glasses are opaque as well as colored; these are opal (white) glasses to which the same colorants that produce transparent colors have been added.
Components That Color Glasses
Solution colorants
The most common dissolved colorants are elements of the transition metal family; the nonmetals sulfur and selenium, and metals of the rare earth family are also used as glass colorants. Author's note: See chart on page 23 for the colorants and the resulting colors when employed in a batch.
The color is created by a process within the atom. This means that a color recipe for one glass will usually work for other glass compositions (if they both have the same oxidation state).
In general, potassium silicate glasses (K O) give “clearer” colors (narrower absorption bands) than sodium silicate glasses (Na20).
Transition metals dissolve in glass as “ions,” which are atoms with one or more of their electrons removed.
The number of electrons removed depends on the “oxidation state” of the glass or how much oxygen is chemically available to react with the transition metal element; this is controlled by adding oxidizing and reducing agents in the batch, and by contact with the furnace atmosphere.
Very pure reds, oranges, and yellows can be obtained by precipitating colloids of cadmium with sulfur (yellow) and selenium (red).
Because of the extreme toxicity of cadmium and selenium, these glasses require careful-batch handling and very effective dust and exhaust removal.
Since both components are lost from the melt by volatilization, the color changes with time in the furnace or the flame as does the LEC.
Adding Colorants to Pre-Mixed Batches
Colorants added to premixed batch need to be fairly well dispersed in the batch; since most of them have higher densities than the clear glass, they tend to drop to the bottom of the melter if they are poorly mixed.
If there is good convection in the melter, the colorants do not need to be mixed throughout the entire charge; they can be dispersed in a portion of the fill. It should be noted though that small tanks and crucibles have very low convection currents.
Interactions between colorants and fining agents
Since oxidation state is important for many of the colorants, and is critical for the colloidal (cadmium and selenium) colorants, there is a natural conflict between the colorants and the fining agents. Fining agents are oxidizers and remove sulfur and selenium during melting.
It should be noted that Spruce Pine and many other batches contain antimony, which creates an oxidizing condition at the fining temperature. Antimony becomes a reducing agent as the glass is cooled; this helps the precipitation of metallic colloids but decreases the intensity of manganese and copper colors
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