Because of the expense of lapis lazuli, substitutes were often used. Prussian blue, the oldest modern synthetic pigment, was discovered by accident in 1704. By the early 19th century, synthetic and metallic blue pigments included French ultramarine, a synthetic form of lapis lazuli. Ultramarine was manufactured by treating aluminium silicate with sulfur. Various forms of Cobalt and Cerulean blue were also introduced. In the early 20th century, Phthalo Blue, a synthetic metallo-organicc pigment was prepared. At the same time, Royal Blue, another name once given to tints produced from lapis lazuli, has evolved to signify a much lighter and brighter color, and is usually mixed from Phthalo Blue and titanium dioxide, or from inexpensive synthetic blue dyes.