In medieval times a very common way of making armour was to boil vegetable tanned leather, and it would become hard and stiff. This was basically done by soaking the leather in luke warm or cold water for at least ten minutes, to allow it to absorb the water and soften slightly. Then by dipping it in water kept at just below boiling point for about one to two minutes, maybe more or less depending how hard and brittle it is to become. Leather boiled for longer will become harder and more stiff, but it will also become more brittle.
I found good instructions and some back ground information
here, thank you to whoever wrote this article.

I tested 9 small strips of leather (three 5mm thick and 6 2mm thick) soaked for the same length of time (about 10 minutes) and boiled for differing lengths of time to see how stiff and hard each would get. They range from a fairly soft 20 sec thin one that still mostly holds it shape to a solid 90 sec thick one that will only allow limited movement with some force applied.

This was a very small mock up of one of my ideas, to give me a vague idea of how it would look in 3D. I was quite pleased with the result, especially with the way the edges curled up, as it gave the piece more of a flowing, sculptural look.

So naturally I did a slightly larger mock up too see how the thinner leather would hold up to more weight, and how it would react in the way it hangs and curls. I added a small amount of copper chainmail to the bottom because chainmail is an interesting way of extending the piece without having to buy and order in more leather, which is out of my price range at the moment. As you can see, the mock up is a bit too big for the wooden doll I've put it on...
The leather hasn't curled up quite as pleasantly, but with some encouragement during the drying process I think I could achieve the desired result, but not if I have to do this in the thicker leather, which is what I will probably have to do, as this leather is too... uh, floppy. Even at this size it's already looking less like armour than an odd fashion garment.
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