Assuming you have HR92 valve heads throughout then I think it'll work, but is mixing up two concepts.
If you simply brought the relays to positions 8 and 10 while leaving valve wiring as now then each valve could open under demand control and fire the boiler when needed.
If you want to use what you call the radiator relay in boiler control mode so that it can modulate firing then I think you'd want to also disconnect the UFH valve from boiler supply / return so that it can't also fire boiler.
I'm heading towards a similar setup and think I'll aim for second option. However I haven't set this up yet and do remain a bit unsure how certain options for relay and zone pairing are configured.