Thanks ChatNoir, however I think I might have worked out what is happening, at least in my scenario.
I suspect that Unraid (v6.9.2 in this scenario), triggers a stop of services when the array is started and someone clicks on the "Join" button in the SMB Settings > Active Directory Settings section.
16:23:59 Server emhttpd: Stopping services...
16:23:59 Server emhttpd: shcmd (212): /etc/rc.d/rc.libvirt stop
To date, I have only ever used that button when the array was stopped (along with Libvirt and docker in a stopped state). In my scenario, by clicking on join, it causes unassigned devices to dismount any drives mounted in unassigned devices.
16:24:09 Server unassigned.devices: Unmounting All Devices...
My DC VM is located on a drive mounted with unassigned devices, hence the domain join does not work (Libvirt is stopped, stopping the VM) and the drive with the VM is now dismounted so it cannot start it again anyway.
Prior to today, I had a second DC which was not hosted in Unraid, but now must be running into this issue since that second DC failed. Reading up in the forums, it seems like you cannot host a single DC VM in Unraid and also have Unraid use that as the DC it joins the domain with (a bit of chicken and egg I guess).
For now, I am going to use a temporary DC VM until I can get the second DC back.
I think the only thing I could use, to close this off, would be a confirmation that with the array started, clicking on Join under SMB settings will trigger the VM and Docker services to stop and trigger unassigned devices to dismount drives.
Thanks in advance!