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I would say that if botox was genuinely helping migranes then you could possibly get it done on the NHS.
I've heard about people having boob jobs done on the NHS for reasons such as back ache (reduction) or low self esteem (enlargment). So I would say it would be possible to have botox even more so for the fact it costs a lot less, really though it would depend on how bad/often they were and I would reccomend talking to a doctor about other solutions.
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I don't know why anyone would get botox. My mom gets it done like all the time and I'm like MOM, you're going to look like a blow-up doll if you keep it up, you won't be able to make any facial expession because all of the muscles in your face will be frozen.
Anyway, if it works for your mom's headaches and it makes her pretty, score for her and I hope your health-care provider will cover it for you!