Hi Travis;
I don't have a
cob oven yet, but I have played with
water glass (sodium silicate) on my
rocket mass heater.
Years ago I had an all cast, fire clay perlite core. The
feed tube was constantly wearing and needing repair.
Brushing the water glass on fired
cob worked just fine as far as application goes. It would apply in your oven as well.
My opinion of it for a
RMH is low as it only hardens the face and easily breaks a thicker piece if banged.
So I would say Yes, you can apply it in a used oven.
My question is , What are you hoping for?
Is your roof cracking / failing?