One of your mororized valves is faulty.
In your m/valve is a axcillary switch the grey wire is your feed and orange wire is your switch wire to boiler
One of your axcillarys is jamed open and thus sending power to ur boiler even when your time clock is off.
Very common problem
To fix you need to replace one of your motorized valve heads.
Raffelect
November 2009