Ok. Interesting update. I was in a 4G area earlier and made a 4G call! 4G remained through the call, and crucially when I went to settings->general->about & clicked on carrier, the "Carrier Three 23.1" changed to "IMS Status Voice & SMS"
The location in question has regular 4G, and has for ages. It only hooked on to using VoLTE initially after a reboot. After the first signal loss (from walking) it wouldn't go back onto VoLTE at all. Presumably it was on 1.8 Ghz then. With the signal lost on 4G it went to 3G, and then no signal. The VoLTE connection never reappeared even reversing the walk.
SO it looks as if VoLTE is active & enabled, but the switching thresholds/preferences/algorithms are meaning it's rarely working. Or perhaps there's even a bug that it only works just after reboot!