I always pumped first thing in the morning, from both sides, once they were done feeding - straight after the 7am ish feed. There was always enough for the 10am in that case and I could relax in my day knowing that I had the DF ready in the fridge.
If the morning was particularly stressful, I would sometimes have to pump after the 10am feed as well, but only rarely.....
Honestly, with Emma, I gave up pumping after 8-ish weeks. I was DFing her straight from the breast anyway, she was no longer needing 7pm top-ups and I knew I wouldn't be needing much of a stash anyway so I gave up and even didn't need to pump once back in work.
S x