I have found amps changing their character for hours of active use: Specifically, most good amps become more dynamic, more 'open' in the frequency extremes. This may or may not be a good thing depending on where the amp starts off from. Example, Bryston 4BST amp which already has a 100 hr burn in in the company before shipping, became more detailed, dynamic and open. On the other hand, Linn Classik amp with a Trianle Titus speaker pair, went from bright and irritating to detailed and smooth.
I guess the same would happen to headphone amps though I am new to the headphone hobby. The changes take hundreds of hours to stabilize and depending on the rest of the system, may or may not be apparent (after all, they are usually rather subtle changes)