I have a bad habit of getting up at 3am to pee. OPKs never work for me then. I get a little better at an 8am pee. But I never get a "positive" like one expects to. I just keep testing and save them so I can visually compare to determine if the lines are getting darker; if they start getting lighter then I know the surge happened.
It's possible that LH peaks for me in afternoon, but since I work late I can't test; all I know is that I've only gotten one actually positive according to the instructions OPK in a year+ of testing. But blood tests are very clear that I am ovulating.
here is my most recent batch:
http://imgur.com/o1Hs3Nt
Top two my LH was around 12.5 based on bloodwork, doctors said I would likely ovulate in the next day. the third is the closest I got to a positive. I'm going to guess it was around 27. Last one was the next morning, and I had definite ovulation pains that afternoon.
Sometimes you just have to make do with suboptimal tests. If I weren't going to monitoring with my RE I would have missed it entirely; the second test was on CD10, which is more than a week before I normally ovulate. But the sono showed I had a 26mm follicle, so we could guess that the 12.6 was leading up to an actual surge.