Flown astronauts are a little over 350. Unflown are a few dozen.
Cosmonauts and taikonauts are a little over 150.
Like anything else, it's the 10% that are really tough for one reason or another.
Unflown guys like Ted Freeman, Charlie Basset, CC Williams and Elliott See are rare because they died early in the program. There are also a few shuttle astros you've never heard of before who sell for huge money because they died prematurely soon after they earned their wings.
Grissom, White and Chaffee (Apollo 1) are not super rare, but in very high demand. Then there is Bill anders (Apollo 8) who hates signing and is uncommon and in high demand. To make it even more fun, Anders intentionally changes how he signs (when he rarely signs) just to mess with collectors.
Armstrong is common, but demand is so high, signed cards sell for $1000. Photos $1500 and up.
Russian tradition was cosmonauts should not sign until after their flight... A superstition they all followed. So, the cosmonauts who died on their first flight are extremely rare. For example, Dobrovolsky and Patseyev who died on Soyuz 11 only exist on a handful of official documents that reside in Russian museums. A few signed items have appeared on the collector market, however many collectors have serious doubts about these items.
There are various subsets such as all 12 moonwalkers on white spacesuit photos, but there is always a catch. For instance, Jim Irwin hated his space suit portrait and almost never signed it. An Irwin WSS unpersonalized would probably sell for $10,000+.
A single item with all 12 moonwalkers would be huge. Only a handful exist. A baseball with 10 (or was it 11) of the 12 just sold at heritage for $21,000 plus.
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