The expansion vessel behind the boiler.
The boilers energy is going into the radiators...the burner will only modulate down once the target temperature set on the front panel is approached.
I'm not convinced yet you have a problem.
You do have a room thermostat in an area with a radiator with fixed valves ie. you don't adjust them.
Its the 100e so only servers CH at 1 temp. I take your point about the expansion vessel.
I guess I maybe jumping the gun on the temperature. What would be a quick way to test it? Shut all the rads down and power on the boiler until it turns off, overheat gets triggered or pressure gets tripped?