When was grisaille painting introduced at Limoges?

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The technique of grisaille painting was introduced at Limoges by approximately 1530–1540.1

This method, which involves using monochromatic shades to create the illusion of three-dimensional sculpture, became a specialty of the Pénicaud family, particularly Jean Pénicaud III. In this process, artists apply pulverized white vitreous enamel onto a dark ground, using varying thicknesses to achieve light and shadow effects.23