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I believe cotton clothing is flame retardant, even without extra chemicals. Of course, pure cotton clothing is the more expensive alternative...
I know wool is. That may be what you are thinking of.
I found a fiber burn test with wool, cotton, bamboo, and acrylic fibers. The wool singes but doesn't burn up completely while the others do. I can't speak to whatever she says in the video as my speakers don't seem to be working now.
Wool would be extra beneficial for homeless as well as it retains most of its insulating properties when wet and stays cleaner with less washing than other fabrics.
Yes, wool is definitely a flame retardant. I seem to remember that while cotton fibres will burn up, woven cotton textiles will burn only poorly and slowly. That is, they are flame retardant, but not flame resistant. Most synthetic clothes will first melt, and if it's hot enough that the melt burns, they'll burn quite well.
I saw comments about tight woven cotton being flame resistant. It sounds like it helps deprive oxygen from the flame. Any frays and stray thready bits lose that protection.
Textiles are surprisingly interesting!