Hi NAF,
Here is an excerpt from Espingarda Perfeyta, a Portuguese gunsmith manual written in the lae 1600s:
"In order to temper iron, however soft it may be, so that it may become as hard as steel itself, the most common and easy secret that there is, is to roast some ox-hooves on the fire, without their taking light, and when they are cold to hammer them, and add to them as much salt, and one part chimney soot. All must be well crushed and put together in any vessel, and then on this is poured enough urine in order to incorporate it all. And let this advice be taken, that the older the mixture be the greater is its force and activity. And then on a steel plate are placed the pieces which are to be tempered so that they fit well, either one or many, and under it a layer and over it another layer of the aforesaid mixture, is such a manner that the pieces be well covered. Then they are put on the fire covered with coal, using the bellows until the fire be strong, and then a fan shall be used for about a quarter of an hour, heating this material until it be burnt, and when touched with an iron, falls away. When it is thus burnt, the pieces shall be put into water, and they will be as hard as steel. Let warning be taken that this semblance, and hardness which the iron attains, does not enter it, but is given to its exterior, entering only to a certain limit, which does not happen with steel, which totally, both outside and inside, remains hard."
As you can see, case hardening goes way back and as Jim said, probably predates the earliest lock mechanism. "Color" casehardening became popular in the gun trade during the early 19th century, although some colors probably resulted in many ancient casehardening efforts.
dave