Response to @kristyski: "In TWS they said him being out of cryofreeze for a few days(like 4 maybe?) had already "Been too long" so I doubt they had him out very long at all."
"It has been brought to my attention that my previous guesstimate on the proper age of James Buchanan Barnes requires revision. I was reminded, for example, that during the 69 years he spent under HYDRA control, the Winter Soldier is credited with over two dozen assassinations, and that he could only be released for a few weeks at a time before memories would begin to reassert themselves. If we assume that he conducted 26 missions, and that he was released for four weeks at a time, that would amount to a total of only two years in the field. I was also reminded that Bucky lost five years due to Thanos's Snap, so by the time Sam Wilson finally takes up the mantle of Captain America in 2024, Bucky was chronologically 107 years old, but had only been unfrozen for about 35 years."