Get a barrel in the proper bore (.451-.454), deep black powder rifling preferred, probably from Dixie. lathe turn it to your desired diameter, taper, etc and step it at the breech end to fit into your barrel lug, which should be bored to match the barrel extension you turned (or vice-versa) after removing the round portion of the barrel and salvaging the sight and barrel latch.. You can sweat or solder the new barrel into the barrel lug and if the fit is good the joint will be almost invisible, as the barrel changes right there from Octagonal to round so you don't have to try to blend the surfaces.
I noticed that the Open-top 1872 barrel wedge is HARD as a file and has no spring, but uses a flat on the retainer screw head to let it pass after rotating the screw a half or so turn, the screw head fits into a groove cut into the screw end of the wdge. I use it now (bought parts from Cimarron and VTIgunparts) on my percussions and conversions. Though the 1872 wedge is too small for the Walker, you could get some tool steel (4140 or so_ and as you have a Mill, make some hard springless ('Cause that slot weakens the wedge) wedges, might even buy an 1872 wedge just to copy the concept from, if you don't have one to look at. If you have an 1851, 60 or 61 you can use it there. Get the screw too. Just gotta remember to turn the screw before driving the wedge out sso you don't break the screwhead.