Good question, I think it’s a bit like glue too. I had a quick look on a few webpages and it seems that the glue/hairspray particles are sprayed on in small droplets. When a droplet hits a hair it runs down the hair until it reaches a point where a second hair is lying across the first one touching it. The droplet stays here and dries, temporarily sticking the two hairs together. Over the whole head this means that all your hairs are connencted in a network that holds the shape together.
It’s cleverer than glue!
Hair is formed of long string like molecules, a protein called keratin, which winds together to make each strand. The keratin molecules are cross-linked in places by sulphur-sulphur (S-S) bonds. This sticks the strands together and also sticks the strand to itself, holding a certain shape. Hair-spray temporarily breaks these S-S bonds and then they re-form as you comb the hair into shape. Once they have re-formed the hair is then ‘set’ in that shape.
But hair spray isn’t permanent. These S-S bonds are attacked by things in the environment like heat, sweat, water etc. etc. and gradually the hair will return to it’s natural shape.
Also when you heat up your hair for example with straightners, the S-S bonds can break and the hair is again more flexible. This is how straighteners work (they stretch the hair whilst it’s hot) and how granny’s perm works.
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