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I've hennaed my hair for a while. Chemical colouring irritates my scalp something rotten, and henna is so natural and safe that you can do it three days in a row if you want to (but it's not recommended lol).
I put henna onto my hair with an inch of my natural mid-brown hair showing through my dark red faded to bright dark red PPD-containing salon colour, the first time.
Henna works by adding a translucent red colour to your natural hair colouring. Only Body Art Quality (the stuff for hand decoration for weddings etc) is pure enough to use on top of salon or box colour - there are metallic salts in non-pure henna that will react badly with your chemical colour. The colour you get is added to your normal colour, and you leave it for a certain length of time to get the colour you need.
It's wise to research the subject before you start, though. Different mediums with different 'release' times can be used to release the dye from the powdered henna leaf that you will have. Lemon takes a long time to release the dye but fixes the henna very well to your hair - but some hair finds the acid objectionable. Chamomile tea - strong brewed, especially is it's hot - will cause almost instantaneous release - but remember - fast dye release means fast release from your hair too.
THere are different types of BAQ henna out there - Yemeni has very dark rich, less orange colour, Pure Pakistani is a sort of a standard and is what I use.
Personally, I use lemon to release, leave it mixed to release overnight, and henna for three hours under a shower cap and a towel. Added heat will allow faster fixing to the hair, but I don't mind just chillin with a towel.
Curly or wavy hair may relax a bit with henna, mine has. Also it shines because the hair takes up the henna into the pores and under the natural scales. Many users report better condition of the hair - not hard to believe after chemical dyes! - and I certainly find it so.
Please do research first, online, read some forums. Lush is ok to use but a pain to prepare - you have to grind it and add it hot to your head. Not my fave way of doing it.
Henna is green to start with, and still cowpat green after dye release. It smells of haystacks too and you can put some scented oils into the released mix to make it smell a bit better.
To begin, you will need enough henna for your hair (mine is shoulder-blade long, thick and curly and I use 200g at at time) plus enough release medium to mix it to mashed potato consistency, then leave it (it will get runnier as it releases). You will also need a pair or two pairs of plastic gloves, lots of newspaper and towels - THIS STUFF STAINS for the released application stage, a showercap, or cling film, plus a woolly hat or towel to keep the heat in while it develops.
If you make too much up you can freeze it in an icecube tray and defrost it to use on your roots every so often, so there's no waste.
Please - don't panic if it's very carroty the first time - it darkens for two or three days after as the colour oxidises like the cut face of an apple - only more slowly. Then panic....
Go for it - but only if you want red hair. There are other wholly natural things you can use to fiddle with the colour - cassia to thin the red out a bit, 'indigo' to make dark hair after, and they all have their own develop and application processes when you add them to henna so DO YOUR RESEARCH FIRST.