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"I don't know why I write science fiction. The voices in my head told me to!"
- Charles Stross

Space Mittens  
  Protect your hands in space.  

As Khan Noonien Singh says in Star Trek 2: The Wrath of Khan (1982), it is very cold in space.

So, be sure to wear your mittens!

Fumbling feverishly, his fingers impeded by his space mittens, he loosened the straps which bound his magnetic boots to his feet.
Technovelgy from Space Flotsam, by Raymond Z. Gallun.
Published by Astounding Science Fiction in 1934
Additional resources -

Surprisingly, this is not a one-off use of this phrase. In his 1939 story The Luck of Ignatz (1939), Lester Del Rey used it:

Jerry was rocking on his heels, cursing the heat with every labored breath. He wore ice packs on every safe place, and still couldn’t keep cool. The blowers were working again, keeping a steady current of air moving, but the air was hot. Under the Master’s shoes were heavy pads of rubberoid, and he wore stiff space mittens on his hands, but still the heat came through from the hot floor and control rods. A few more degrees would spell the limit.

Gallun uses it again in Coffins to Mars (1950), published in Thrilling Wonder Stories:

That was when, from a thin pearly veil of cloud from the Pole, a few fine dry flakes drifted down. Joan caught two on the palms of her space mittens. She stared at them wonderingly, as if they were a part of home, as if they didn't belong here at this distance from Earth at all.

“Star-shaped," she said. “Just regular snowflakes. Of course it has to be — here or any place. Out to the farthest Earth-like planet in the farthest galaxy." Then she laughed — with real pleasure. “I hardly believe it — on Mars !” she added.

Compare to hinged space suit mittens from The Bluff of the Hawk (1932) by Anthony Gilmore.

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Additional resources:
  More Ideas and Technology from Space Flotsam
  More Ideas and Technology by Raymond Z. Gallun
  Tech news articles related to Space Flotsam
  Tech news articles related to works by Raymond Z. Gallun

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