I've just had to change the expansion vessel on my own UFH system because the membrane was leaking. Having repaired it, I had a minor loss of pressure until I hung a collector vessel on the overflow to find this is where the leak was coming from. Many of the relief valves have a test facility where you can turn the cap on top, which raises the valve seat a little, before it springs back into place, reseating the valve with a sharp snap. This was my problem, and draining down and repressurising the system must have caused a bit of crud to lodge in the valve seat. This caused the leak, even though I hadn't touched the relief valve during the service.
Worth a try.
If it is not the valve, you may find that you can run the system at say half a bar, instead of the normal one bar. Some leaks only show themselves at greater than a specific pressure.