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The sky appears dark instead of blue to an astronaut because there is no atmosphere in the outer space that can scatter the sunlight.
As the sunlight is not scattered, no scattered light reach the eyes of the astronauts and the sky appears black to them.

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When sunlight passes through the atmosphere, the fine particles in air scatter the blue colour (shorter wavelength more strongly than red. The scattered blue light enters our eyes. If the earth had no atmosphere, there would not have been any scattering . Then the sky would have looked dark. The sky appears dark to astronaut flying at very high attitude, as scattering is not prominent at such heights.

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