I have used PVA as sizing for gum bichromate prints. I usually printed cyanotype on buffered papers then coated with PVA before gum bichromate process.
However, a few times I had to print cyanotype on PVA sized paper then apply gum layer over it. My observation was that PVA created a barrier and cyanotype emulsion was not absorbed completely.
It was easy to remove some of the blue areas with finger rubbing.
I will guess that it is similar in your case. Cyanotype emulsion (which is acidic by nature) was not absorbed into the paper fiber and therefore it did not react with the calcium carbonate.
What you have experienced is probably how your emulsion behaves when it is applied to a buffer free paper, I do not think it is PVA specific.
I use improved traditional cyanotype formula (oxalic acid and some dichromate in it like B&S formula). I have almost 2/3 stop printing time difference between buffered and unbuffered papers.
12min with buffered, 7,5 with unbuffered papers
Regards