Rado which introduced its historic DiaStar watch in 1962, touting it as "The world's first scratch-proof watch." The DiaStar had a case and bracelet made from tungsten carbide, which by the strictest scientific definition is actually a metal/ceramic hybrid (aka a "metal matrix composite"), as it blends tungsten and carbon elements and has many metallic properties, hence its use for products like drill bits and surgical tools. Nevertheless, the DiaStar is generally considered to be the first commercially available "Ceramic Watch".
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In 1986, IWC introduced the Da Vinci Perpetual Calendar (Ref. 3755), made of scratch-resistant black zirconium oxide ceramic.
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Omega "Cermet" model, as part of the Seamaster line, was issued in 1982 (Ref. YR 396.0945)(2). It was equipped with cal. 1420 (cal. 1380 for the ladies version) and had a case and bracelet elements made of Cermet.