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Extruded Polystyrene is one of the best insulators.
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Replying to [GoldStar]:
A little correction: EPS stands for Expanded Polystyrene, and XPS for Extruded Polystyrene.
XPS has a slightly higher R value, but is much more expensive. Recycling it as an insulator doesn't make much sense, as it breaks up into tiny chips, while EPS can be ground in a burr mill to small beads. Then it can be used in SIPs (structural insulated panels) or for other purposes.
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