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[Anthemjack]

Is there any workshops that makes any pig iron items? I can't find any, and I looked around for a while now. I am really confused.

[UberNube]

Sometimes mandates/demands are bugged so that they request an impossible item (pig iron items for example). However, I suspect that in this case bars count as items so it may be possible to fulfil it. Try forging some pig iron bars and see if that works. If not, then I suggest you give the noble the honour of pulling the flood-his-room-with-magma lever. Try and get an artefact bauxite mechanism for best results.

[Sweedumz]

Smelters are used to make pig iron bars and steel bars, but you need a flux stone as well as iron and pig iron bars to make them respectively. If you don't have a flux stone, then the option to make pig iron, etc, won't show up on the smelter. The flux stones are listed on this page.

[Lemunde]

Under normal circumstances the only thing you can make with pig iron is steel.  Alternatively you can use it to make vertical/horizontal bars, which you can use any metal for.  Crafts or similar items are out of the question except on the rare occasion a dwarf with a mood uses it to make something ridiculous.

[Shurhaian]

UberNube had it right. For brittle metals, i.e. pig iron and bismuth, you need to make the bars.

Making alloys that use those bars does NOT count. Steel bars are not "pig iron items", even though they're made using pig iron.