NRA Black Powder Cartridge Rifle Silhouette Competition rules have never allowed the use of duplex loads.
As associate editor of American Rifleman in 1992 I attended the BPCRSCs at the Whittington Center in Raton, New Mexico.
One of the things that competition staff did, on a random basis while shooters were on the line (before the string started, of course), was pull several cartridges from their ammo loads and break them down to examine them for any traces of a duplex load.
As far as I know no one was ever caught cheating that way.
That said, there are more reasons to shoot black powder cartridges than NRA competition. I know more than a few people who do it just because they want to, they have historic rifles, and they can.
As for what powders are used, I know Unique is occasionally mentioned because it is so flexible and it's also historic in that it was one of our earlier smokeless powders.
Others used are the IMR Sporting Rifle powders 4759 (? can't remember the numbers off hand).
In the "long ago and far away times" when smokeless powder was new, there were smokeless powders called "bulk replacement powders."
These were smokeless powders that were loaded by volume just as black powder was.
Those powders have been off the market for years, unfortunately.
The closest thing we now have to a bulk smokeless replacement is the relatively new Trail Boss. In larger cases like my .44 Special it's been exceptional.
While it is close to a bulk replacement powder, it is NOT a true bulk replacement powder and cannot be treated as such.
BUT, I do not know of anyone who is using Trail Boss as a duplex powder in black powder loads, but I suspect that they are out there. Trail Boss has answered a lot of prayers for people who have wanted a very bulky but low pressure powder for a long time.
Another good resource would likely be
www.castboolits.gunloads.com