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What material was commonly used for support structures before PVA was developed?

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Depends on the printer brand and type. FDM-printers and most laser-cured liquids use the same material as the print itself, in fine support structures.

Powder based printers don't use any support: the powder supports the model.

Some expensive industrial printers (50.000...100.000 euro) that I have seen, sometimes used a support material that dissolved in caustic (I don't know what material exactly). And the Objet-printers which have a system that looks like an inkjet printer (=ejecting liquid drops, which are cured by UV-light) also uses some sort of gummy washable material: it is washed off with a high pressure water jet. Could be PVA-based, could be something else?

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