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Wikipedia article states as

STS-1 at liftoff. The External Tank was painted white for the first two Space Shuttle launches. From STS-3 on, it was left unpainted.

source Wikipedia source:Wikipedia

I wonder why the early shuttles External tanks are not painted and after NASA started painting the ET's why it painted it in color of rusted iron why not other color's ?

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From STS-3, the tank was left unpainted, the brown color is the natural color of the insulation foam, see this PDF. The color would get darker from exposure to the sun.
The tanks of STS-1 and 2 were painted white, but this took several hundred kg of paint, and after STS-1 and 2 tests showed that the paint wasn't necessary.

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    $\begingroup$ The more interesting question was whether the paint would have helped protect from falling ice or foam chunks. I doubt it but this made me wonder. $\endgroup$ – geoffc Oct 18 '13 at 12:53
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    $\begingroup$ From the linked article: 'The paint also did not prevent foam from popping free of Columbia's fuel tank during its first two launches' $\endgroup$ – Hobbes Oct 18 '13 at 13:14

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