I have identified the error :
When creating a Flat Rate Delivery Method, there is a zero prefilled in the first “Cost” field. This needs to be removed if completing the “Delivery class costs” filed by eg a formula to charge poer item.
I did not appreciate this previously as for other Flat Rates I had incorrectly inserted a value to the upper cost field, then deleted the value when I realised I needed to insert a formula in the Class field, thus deleting the first value & leaving the field blank, rather than zero.
This is trivial & therefore annoying.