The seventh ball of the day saw Paul Best (1)gifting his wicket to Graham Onions when he was caught at square leg by Will Smith.
Brathwaite claimed his fifth wicket when he bowled Miller for 1 and Warwickshire were 349-9.
A direct hit of the stumps by Dale Benkenstein was a possible chance to end the innings but the umpire wasn’t convinced.
No further reward was offered to the bowlers with Rankin and Woakes working hard to last the morning session and at lunch Warwickshire were 426-9.
The last ball of the second over after lunch, when Rankin was caught behind on 28, saw Warwickshire finally dismissed for 429.
Michael Di Venuto and Will Smith batted beautifully to see Durham to the hundred mark without loss.
A cover drive from Di Venuto saw him pass fifty (71 balls, nine fours) in the 27th over and Smith followed shortly after having faced 101 balls, hitting six fours and a six.
At tea Durham were 130-0, Di Venuto 65* and Smith 53*.
The first wicket fell with 166 on the board when Smith (66) clipped the ball to Clarke off Woakes.
Smith was back on the field within a few overs as a runner for Di Venuto who was struggling with injury (awaiting news from physio) but he went on to score his century from 129 balls, striking 17 boundaries
Durham were 192-2 when an lbw appeal was given the nod by the umpire off Woakes which saw Muchall dismissed for 7.
Stokes (5), who was dropped on 1, was out lbw to Miller with the Durham total just past the two hundred mark.
Di Venuto fell on 113, caught by Ambrose, off Clarke, with six overs remaining.
Graham Onions came in as nightwatchman but didn’t make it to the close of play, he was caught by Best off Rankin without scoring with two overs remaining and the Durham total at 222-5.
At the close of play the home side were 230-5, Benkenstein 15* and Blackwell 5*.
We caught up with Will Smith for a quick word at the close of play, “It’s a good cricket wicket and we need to make sure we play the better cricket over the next two days. 429 is an above par score and we’re a bit disappointed to have let them get to that but we’ve got two experienced batsmen in the middle and if we can get near that then it puts them under pressure batting third.”