The speed increase that you probably see here in PHP using NFS on top of memcached is deceptive in nature. PHP Session Storage by default blocks first-come-first-serve retrieval. This means that two simultaneous requests made for PHP for one session will force the first request to lock the session until PHP is executed, or you explicitly call session_write_close()from your code to release the lock.
But in the file-based session store, PHP relies on flock, which doesn't work on NFS.
NFS protocol (versions 2 and 3) does not support file locking
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