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Milkweed is a bast fiber. Folks who have spun milkweed are not talking about the fluff from the pod, but the fiber from the stalk. It doesn't have to be retted. When the stalks are a tannish-grey in color, you know they're ready to be collected.... about mid-summer, early fall. Break them off right close to the ground, then bend the stalks and the silky fiber releases easily.
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