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"The writing is clicking away in my head and piling up, and unless I get it on paper somehow it's going to create uncomfortable pressure in my skull."
- Isaac Asimov

Unobtainium  
  A humorous reference to a substance both rare and unlikely.  

Although Brin did not coin the word "unobtainium" he might well be the first user of it in science fiction. See the discussion below.

None of the other moons in the Kthsemenee system had the one attribute this one possessed: a core of almost one percent unobtainium. Already thirty of the Brothers' ships had landed, to begin construction of the Weapon.
Technovelgy from Startide Rising, by David Brin.
Published by Bantam in 1983
Additional resources -

The best guesses as to the origin of the word place it in the field of aerospace, which has been pushing the envelope in the field of materials science for at least a century.

As reported in the Marshall Evening Chronicle (Marshall, Michigan) on February 27, 1956:

Scientists are now working on a new metal to be used in making the noses on intercontinental ballistics missiles. The metal is so hard to come by that the scientists have devised a lugubriously-humorous name for it. They call it ‘unobtainium’.

However, it can be found even earlier in a 1930 German work "Dechema-Monographium Vol 39 page 12 link:

...Gewicht gleich Null. Ein Amerikaner hat diesen Werkstoff scherzhafterweise einmal das Element "Unobtainium" genannt.

[Google Translate: ...Weight equal to zero. An American has jokingly called this material once the element "Unobtainium".]

The earliest reference to something like this (that is, a humorous name for a material that does not exist) is as far as I know "Bolognium" from Transactions of Amer Soc for Steel Treating, by Edgar Bain, in 1926.

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Additional resources:
  More Ideas and Technology from Startide Rising
  More Ideas and Technology by David Brin
  Tech news articles related to Startide Rising
  Tech news articles related to works by David Brin

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