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With Full Disk Encryption, the data is stored on the disk encrypted at all times.
This applies whether the machine is powered on or not or whether a user is logged in or not to Windows.
Without the private key used to encrypt the disk, it will not be possible to recover the data from the raw drive.

Once you've logged into the pre-boot (i.e. provided the appropriate credentials), Windows will see the FDE-encrypted drive the same way it sees an unencrypted drive.
All data read/written from/to the physical device will go through the FDE driver, but you will be able to access the data on the drive if you're logged into Windows with a user that can access the data.