Militao has suffered a serious thigh injury involving a tendon and it's expected he will be sidelined for four months.
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The injury occurred just before halftime of Sunday's 2-0 home defeat to Celta Vigo.
This is Militao's third injury of the season, following the bruise in the derby and the right adductor strain he suffered against Tunisia, which forced him to miss two matches.
In addition to Militao, Dani Carvajal (arthroscopy on his right knee), Trent Alexander-Arnold (torn left quadriceps anterior rectus), Dean Huijsen (knee problems), David Alaba (problems with his right soleus), and Ferland Mendy (torn right hamstring).