I have moved the /usr to another volume in the past. It involved booting to a Rescue Disk, copying /usr to a new destination, mounting the boot image (several “mount --bind” commands, chroot, …), renaming mounts in /etc/fstab, and rebuilding the boot image (mkinitrd).
Is all that really necessary? Can /usr be copied to another volume, the volumes renamed in /etc/fstab, and reboot?