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Sounds like the VR10 may be connected to the wrong 'pair' at the boiler. The DHW sensor connection should be to the pair terminating in the SMALL plug with Orange and Black wires (cut off plug and use a connector block). Not the large plug with Brown & Black wires. The large plug is C1-C2 as shown above in the drawing. These are NOT used, and would fire the boiler when linked in DHW mode.
Glad you got it sorted!Thank you very much guys, I connected VR10 to correct pair and system works the way it should now, problem solved!
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