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On the track, German Rosberg was half a second clear of Red Bull's Mark Webber in practice, while reigning world champion Sebastian Vettel came fourth.
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German Nico Rosberg finished eighth for Williams ahead of Force India's Adrian Sutil and outgoing champion Lewis Hamilton, who was 10th for McLaren Mercedes.
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Brawn have now been renamed Mercedes Grand Prix and have already signed German Nico Rosberg as one of their drivers, with his compatriot Nick Heidfeld the favourite for the second seat.
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Seven-time champion Michael Schumacher is returning to F1 with Mercedes this year after a three-year retirement, and is joined by German Nico Rosberg, who is yet to win a race but is highly rated by the car manufacturer's hierarchy.
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The 41-year-old German took over from Nico Rosberg with about an hour and a half of the Valencia session remaining, and ended up posting a time more than a second faster than his younger teammate.
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The German's team-mate Nico Rosberg finished fifth to cap off a good weekend for Ross Brawn's team.
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Hulkenburg will start from 10th on the grid on Sunday with his Williams team-mate Rubens Barrichello in eighth, sandwiching the Mercedes of Nico Rosberg who was the second quickest German of the six in the field.
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The 24-year-old German, who is the son of former F1 world champion Keke Rosberg, switches from Williams where he has spent the last four seasons.
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The German has subsequently returned to the sport with the new Mercedes team and will drive alongside Nico Rosberg this season at the age of 41.
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Rosberg, who drove for Williams last year before Mercedes took over world champions Brawn and signed the German, completed 39 laps and Schumacher was on the track for 40, according to Web site autosport.com.
CNN: Massa upstages Schumacher in F1 return