Fastest CD Write mode - 52x Full CAV (starts at just under 24x and ramps up throughout) - at 52x, the last bit can be rather iffy, so a speed of 40x or 32x is normally optimum if you can't trust the media at full speed.
Fastest CD rewrite mode - 32x on "Ultra" media, often by zone-CLV (16x/24x/32x steps - a few drives do P-CAV mode on CD-RW).
Fastest DVD mode - 16x CAV on DVD+R ... DVD-R is catching up, drives that us Zone-CLV (eg. Pioneer DVR-108/A08) are slower, but may give better results as tuning media strategies is easier under Zone-CLV.
The terms:
CAV - rotates at constant RPM (angular velocity), while transfer rate ramps up throughout.
CLV - maintains a constant linear velocity and transfer rate, therefore the RPM is lowered to compensate for the increasing circumference.
Zone-CLV - Burns in steps of CLV, stopping to bring RPM up to the initial level and continue at the next higher transfer rate (this requires the same kind of linking that is used for underrun recovery).
P-CAV - Starts using CAV, at constant (maximum) RPM, then makes a stepless changeover to CLV, continuing at constant transfer rate.
An interesting result on some DVD writers, is "8x near CLV" - actually 8x P-CAV, but the initial ramp-up from 7-8x is so sort, that the burn time is only a fraction over half the 4x burn time, and the advantage of 16x is no more than 30%, but the price of media is higher and the quality problems are worse.