Hi Joe,
It would be making that noise it all the time to be honest- but the most amount of vibration the DMF would have to suffer is on initial start up, hence why you are mainly hearing it at that point.
Too 100% make sure it is the DMF giving up....I did this - put the car on some ramps, then get someone to listen to the gearbox when you turn it on from start up and also give the car a few revs. If the DMF is knackered then you will be able to hear it knocking all the time and every time you apply a little throttle the knock should in turn get louder with the extra vibration applied. This vibration can then be removed by pressing the clutch down whilst still revving the car, and obviously when the clutch is engaged the noise should go away if it is the DMF coming loose.
Obviously when you are in the car you have all the other gubbins to listen through before you hear the DMF e.g SAI, Carbon canister and every other little tapping noise under our cars. I first heard my noise when I was starting my car up after leaving work as I work in a multi storey car park so the noise of the DMF was able to be heard knocking a lot easier with the sound bouncing off the walls.
After my discovery of the knocking I drove the car for about 1000 miles or so, then I upgraded to a SMF kit as I got annoyed the DMF gave up and I will never had that issue with a SMF
(I'm not to mechanically involved in my car when it comes to things like this so I didn't carry out any of the work to change it- but hope some of that information helps.)
Chris