Password manager master passwords, disk encryption passphrases, GPG/SSH key passphrases, and admin/root credentials. These are the keys that protect everything else, so they deserve the maximum entropy available. 32 characters with all four sets provides over 200 bits of entropy.
Each additional character multiplies the search space exponentially. Moving from 16 to 32 characters squares the already-enormous search space. A 32-character password with all sets has roughly 2^200 possible combinations — effectively impossible to brute force with any currently foreseeable technology.
A 32-character password isn't meant to be memorized. Store it in a password manager (1Password, Bitwarden, iCloud Keychain) and let the manager autofill it. You only need to remember the manager's own master password. Use the bulk generator to create separate 32-char passwords for each critical service.