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I'm looking to 3D print a structure that won't deform in high heat, up to about 220 °C. The filament itself can be 3D printed all the way up to about 380 °C.

PEI seems like it could be a viable option. I found some here. This PEI filament specifies the glass transition temperature at 217 °C.

Would this filament work? Are there any other types of materials that would fulfill this engineering requirement?

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Your expected operating temperature exceeds the glass transition temperature by 3 °C. This implies that the structure will become weak and can deform under load.

Note that you cannot simply print PEI on a normal machine, it requires a special high temperature capable printer with hot end temperatures up to 400 °C and heated bed over 120 °C up to 160 °C, furthermore it will need a heated chamber (up to about 80 °C) which requires special care to cooling and placement of electronics and motors.

Not having specified what kind of structure you require, you could look into steel.

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PEEK is also used in applications where dimensional stability (and/or chemical resistance) over a wide range of temperatures is desired. The requirements for printing are similar to those for PEI.

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An easier but less simple solution might be to make a PLA 'pattern' that is the right size and shape, then use that to cast your item in aluminium (melting point ~ 660C) using the 'investment' or 'lost PLA' process.
Links:- https://www.instructables.com/id/3D-Printed-Lost-PLA-Investment-Casting-Aluminium/

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