When it comes to underwear in particular, the 5% man made fibre is usually the elastic in the waistband (and leg holes in some type of undies). The majority of the garment, especially that touches your sensitive parts, is pure cotton.
Now, stuff like jumpers that are 40% wool and 60% acrylic are different; I expect they either weave the strands in regular intervals, or more likely twist the 2 materials together so each strand has the correct proportion
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