Not sure if I am with you, UFH is generally run at temperatures < 50C, say in the 35C to 45C range, so if the TMV is set to 45C and the boiler stat to 70C, then, initially, all the flow through the manifold will be from the boiler with no recirc, once the boiler temperature & TMV are > 45C then the TMV will start recirculating some of the cooler return manifold water to mix with the incoming, eventually, 70C boiler water to maintain that 45C, IMO, even from cold, the troubled UFH, on its own, should reach that 45C in < 15 minutes at the very most. So question remains, is the temperature taking ages to rise even to this 45C or whatever, there is no reason whatsoever IMO as to why it shouldn't. That is why I'm asking to note (again) from cold that UFH manifold (total) flow rate and manifold temperature rise up to say 45C or whatever the TMV is set to. The troubled UFH TMV is set to index 4.8 (48C??), can't see the other one. If the TMV is faulty and on full recirc then the temperature will never rise but the boiler flow temp will and should rise in a few minutes to its setpoint and the burner should cut out.
What are the two pipe stats controlling?, one seems to be set to 60C. They may be wired as safety stats to stop the manifold pump if the manifold temperature rises too high? or maybe shut the zone valve which then tells the manifold pump to stop.