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As I know that the rads used to heat a bit when the hot water was on (only hot water) I may still swap out the full valve and fully drain the system,, any inhibitors that you would recommend for my system & netaheat boilers?
Also, the water going into the expansion tank, if this continues after the thermostat change is there anything that this screams out as, as a fault?
What's the Heat exchanger made from?
If it's anything other than Aluminium I'd use Fernox.
As far as the Tank goes, check the level first. When it's cold it should have 4 or 5 " of water in it.