The head would probably have still called himself ‘The Duke of Württemberg’. Some of the dynasties call their heads “the” whatever their title was before they were elevated to a higher title. This is why we have the Landgrave of Hesse, the Margrave of Baden, etc. It’s just another way to differentiate the head from the rest (even though they are all princes and landgraves of Hesse, princes and margraves of Baden, etc).
These elevations, however, didn’t really eliminate their original titles. Hence, the kings and princes of Bavaria remained also dukes of Bavaria even if that title fell out of daily use.
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