Writing a fanfic? Want some accuracy? Here is a (mostly) headache free and reliable timeline of the MCU as well as chapters discussing specific movies and timeline controversies. Spoilers guaranteed.
Best to read introduction before leaving comments...
Timeline for these two characters in the MCU, especially for people who haven't seen the Captain America movies.
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In 1944 while serving for the U.S. Army, Bucky Barnes falls from a mountain train and loses his left forearm. Previous to this, in 1943, he had been a POW in a Hydra prison camp where scientist Arnim Zola had experimented on him in an attempt to replicate the formula that had given Steve Rogers enhanced abilities. This is the only discernible reason for Bucky's survival.
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Hydra scientists recover him and replace his entire left arm and shoulder with a metal limb while Arnim Zola oversees. Zola now has the SSR's (SHIELD's predecessor) money and backing, though Bucky is supposedly kept hidden from them in Russia and later Siberia. According to his own flashback, when Bucky reacts violently to this situation he is cryogenically frozen.
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In the comics, the Winter Soldier works for the Russian KGB, but in the MCU he only works for Hydra. Since the arm of Hydra is long-reaching, it's fair to headcanon that at some point he did work for the KGB, but was still considered property of Hydra. How else does one explain the red star on his arm? Russia.
In 1984 Natalia Alianovna Romanova (Natasha Romanoff) is stated to be born.
The Soviet Union dissolved gradually in 1991, ending on Christmas Day. This is the same month that the Winter Soldier assassinates Howard and Maria Stark in order to steal a super-soldier formula from the trunk of their car.
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