In the morning session Williams, the and winner, had little trouble in overcoming Milkins' fellow English qualifier Jimmy Robertson. The year-old was in total control at up after Tuesday's first session and eased through despite losing the first two frames.
He responded by scoring back-to-back centuries for a lead, and although Robertson took the next frame, Williams closed out victory.
Media playback is not supported on this device. Williams has returned to the world's top 10 this season with the help of ranking event wins in Northern Ireland and Germany that have taken his career tally to Who knows if I can win it, but I have as good a chance as anyone," Williams said.
Four-time champion and last year's runner-up John Higgins saw off Thailand's Thepchaiya Un-Nooh in a gripping, attacking match where both players came close to getting maximum breaks.
Higgins, a time ranking event winner, had a chance in frame eight after potting 13 reds and 13 blacks. But he missed a difficult 14th red after leaving himself hampered by the blue.
Crucible debutant Un-Nooh went even closer in frame 12, but rattled the jaws with the 15th red after he appeared to have done the hard work.
Higgins led after the morning session, but Un-Nooh remained impressively calm under pressure and won three of the next four frames to trail by one at Un-Nooh continued to go for his shots - an approach which eventually proved his downfall against the wily year-old Scot, who won the next two for a lead before getting over the line.
Including almost vertical stands, terrifying tunnels and stadiums that actually seem to shake with sound. World Snooker Championship Crucible Theatre, Sheffield Dates: World Snooker Read more on World Snooker.
His search for a maiden final will go on though, as Stuart Bingham whitewashed Milkins 6—0. Milkins has spoken openly about problems with debt, lack of motivation and over-dependence on alcohol consumption.
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