Did try contacting Vodafone support for guidance and can unfortunately confirm that they did indeed live up to their very poor reputation!
First experience was on the chat line where the support agent was obsessed with it being a Wi-Fi issue despite repeatedly stating that my desktop PC was directly ethernet connected to the hub, gave up eventually when he agreed that the issue should be escalated to level 2 support at my request.
VF level 2 support did actually make contact by phone within the promised 48 hour scale.
The agent had very poor english, had great difficulty understanding, sounded like a Filipino but of course could have been anywhere, I felt embarrased repeatedly asking to say again, he must have thought I was deaf.
Unfortunately, he was equally obsessed with perceived Wi-Fi issues, concluding that I would need to disconnect some of my Home Assistant Wi-Fi devices, too many on the system??
Tried to steer him towards a possible DNS issue, he stated that the hub must be left on "auto DNS server" selection in order to use the VF DNS resolver.
So, gave up on Vodafone support.
Having consulted with a number of very helpful and knowledgable patrons on the Vodafone members forum took their advice and set the hub DNS server selection to manual selecting 1.1.1.1 (Cloudflare) as primary and 8.8.8.8 (Google) as secondary, this appeared to cure the issue completely.
I run PiHole/Unbound on a RPi-3B as a recursive server, had taken this out of the system as process of elimination with the issue in hand.
The Pi was running on Debian "Buster" OS which was becoming troublesome to update, re-installed PiHole/Unbound on a fresh install of Debian "Bullseye" OS.
When happy that system was stable, reset the hub DNS server selection primary to the Pi IP address, secondary to 1.1.1.1 (Cloudflare), left Windows PC IPv4 DNS server selection at auto (default).
All stable so far