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Underglaze is a combination of clay and colorants mixed into a paste.  Underglazes can be thinned with water.  They can be used much like tempera paints because colors can be blended, tinted and toned.  Underglazes are used when the artist wants to use color in a detailed fashion to decorate pottery.  Underglazes may be applied to greenware or bisqueware.

Glaze is a combination of chemicals and minerals formulated to melt and become  a glass coating when applied to clay products and fired to the proper temperature.
Glaze formulas must contain silica, alumina, and flux .  Colorants in the form of metal oxides are added to give the glaze color.