Rust Bluing
Rust Bluing and it's brother Browning are the oldest metal finishes for firearms, with browning being the oldest. These were the first finishes found on early muzzle loading commercial and military arms.
Rust bluing is also one of the toughest and hardest wearing finishes for firearms. It is not uncommon for many firearms 140+ years old to still look great. Of course, those pieces probably have not seen much hard use, and were well cared for.
Rust blue is found on most all early military and commercial firearms. Slow rust blueing is also the go-to finish for many custom rifle builds thanks to it's durability and excellent appearance (when properly carried out).
While not used on American handguns, foreign pistols such as the Broomhandle and Luger do have this finish.