You can use water but you do need some manner of form otherwise, as you noted, the leather warps. You really should be using at least some kind of form no matter what, even if its just some books to make it flat.
Using wax to harden leather is similar to the water method, except you use melted wax and kind of "paint" it onto hot leather. This can be extremely dangerous mind you so please be careful is you manage to get enough wax and want to give it a go.Anyway, many people seem to use wax to harden leather. I don't know why. When I got some boots from Italy for reenacting, the seller instructed me to always "wax them". Now something may have been lost in translation, but I assumed the wax he was referring to was something like a mink oil (which despite it's name is a waxy substance), or something that the English call "dubbin". The point was to protect and water-proof the boots, not to harden them. This would fit with the other waxed leather products that Ashtagon pointed out.
You'll want to take a look at this guy then: http://www.bronze-age-swords.com/Clonbrin_shield.htmI have a friend who has made reproduction "Ardagas", leather shields that the Spanish adopted from the Moors. One of his is even in a museum. I can double check, but I'm pretty sure that the outside is rawhide that has been soaked and stretched over a frame, making it very hard.
Its a reproduction of what is believed to be a 3000 year old solid leather shield from Ireland. It doesn't appear to have a frame, the reproduction was used in a series of tests with reproduction weapons (made by the same fellow) for an archaeological study.
Also this has some good tips on the process of making cuir boulli:
http://www.personal.utulsa.edu/~marc...eather/hl.html