I'm not sure, but I think not. Here is my reasoning:
1) Ayo was working with Bucky, not Shuri. This leads me to think that whatever solution to the programming was not scientific, but more likely intensive training to resist or block out the commands. While this may have just been due to Letitia Wright being busy filming Small Axe, I feel like this was a conscious decision further explained in my next point:
2) The location of Bucky's Scene with Ayo, if he was really completely free then why take him out into the middle of nowhere, away from the labs.
3) Sebastian Stan's performance: I believe that this was very intentional. Throughout the show, Bucky would get a far-off look. I think that he was constantly having an inner battle against the part of him that was (or is) the Winter Soldier, and these moments were ones where he had to focus on reigning the Winter Soldier in.
Personally, I would like to see Bucky learn to control the Winter Soldier and Utilize that part of himself for the good guys. Maybe even see him eventually become the leader of S.H.E.I.L.D./S.W.O.R.D./(whatever Nick Fury is the leader of at the time) when Samuel L. Jackson retires (The Man on the Wall-ish storyline).
