A very interesting cover signed by 5! MIR visiting crews with relevant postmarks from MIR "post office":

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19.08.96 - Soyuz TM-24 docking to MIR

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19.09.96 - STS-79 docking to MIR

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15.01.97 - STS-81 docking to MIR

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12.02.97 - Soyuz TM-25 docking to MIR

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02.03.97 - Soyuz TM-24 undocking from MIR

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Note, this cover lists the original crew of Soyuz TM-24 (EO-22) that was replaced, but the signatures are of the flown spacemen aboard MIR

STS-60 was the first operational mission of Shuttle-MIR program that included a cosmonaut in the Space Shuttle crew and live communications with MIR space station. Sergei Krikalev became the first Russian cosmonaut to fly on the U.S. Space Shuttle when he launched with his five NASA crewmates onboard Discovery. Krikalev and his backup, Vladimir Titov, joined the STS-60 mission after the U.S. crew had already been assigned; however, Krikalev was able to take full part in the mission. His roles included manipulating the Shuttle’s payload bay "arm" and operating the Space Acceleration Measurement System experiment, as well as participating in the joint science experiments. Krikalev’s backup Titov would go on to fly on the STS-63 "near Mir" mission. Besides gaining practical experience on an American Space Shuttle, Krikalev helped further diplomatic and public relations in ways that hearkened back to the Apollo-Soyuz Test Project of 1975 and pointed forward to the Shuttle-Mir flights.

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The presented Apollo-11 25th anniversary cover issued in the same 1994 is quite interesting giving the direction of the “Next Step” towards the space station. Though not directly connected to the Shuttle-MIR program.

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Quite unusual Houston STS-60 special postmark can be found on the dedicated wide format covers. It looks like a "fantasy" of one of the German dealers. Note missing word STATION. It is not listed in 1994 Postal Bulletins

Pseudo NASA VIP cards.

NASA VIP cards were the series of postcards designed and printed by NASA to be given to the guests invited to attend Apollo mission launches. The last VIP card was actually for SL-2 the first manned Skylab flight. There was a special VIP card for STS-95 the return to orbit of John Glenn. Just about all so-called VIP cards produced after NASA's last VIP card issue for SL-2 in May 1973 were privately printed by space cover dealer Carsten Fuchs of Germany. His cards, which include all Shuttle flights from STS-1, are in no way of any "official" status and can be identified by light-blue ink markings and usually on a heavier-card stock. I have a couple of such “pseudo” NASA VIP cards for STS-79 and STS-86 bearing special Shuttle-MIR docking pictorial postmarks.

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more on NASA VIP cards here

A couple of interesting moments re STS-76 mission:

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Michael Clifford participated in this mission a year after he was diagnosed with Parkinson's disease. During the flight, he worked for 6 hours in the open space. Everything went well, but he told that it was not given to him so easy.

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Another notable achievement was made by Atlantis crew member Shannon Lucid who joined EO-21 and EO-22 and stayed abroad MIR for 179 days, returning home abroad STS-79. She spent a total of 188 days in space that was an absolute record for the woman and non-Russian spaceman in general. The woman-space-stay record was beaten 11 years later by ISS crew member.

The main controversy of Soyuz TM-24 flight was the “last minute” change of the Russian part of the crew, that occurred only one week before the launch. Gennady Manakov suffered from heart problems and the medical decision was to replace him and Pavel Vinogradov with the back-up crew members – Valery Korzun and Alexandr Kaleri. This switch caused a mess in space collector society and astrophilately in particular as many items bearing the original crew names (like covers and patches) were already prepared and dispatched for the launch. This also caused some increase in prices, as the developed story underlined the rarity of the event.

On June 25, 1997, the Russian crew including Vasiliy Tsibliev and Alexander Lazutkin, which just several months ago was battling flames on Mir, plus NASA astronaut Michael Foale, found themselves in the middle of the worst collision in space history. During a docking test with the use of remote control onboard the station, Tsibliev lost control of a tumbling cargo ship Progress M-34. The vehicle collides with the station’s Spektr module and seconds later, the crew onboard Mir hears a hissing sound of air escaping their vessel. Miraculously, almost instantly, the crewmembers were able to locate the air leak to Spektr module. After short struggle to find cutting tools, they severed the cables leading into the Spektr and safely sealed the hatches. The collision damaged one of Spektr’s solar arrays, caused a fracture that depressurized the module. Power restoration required two internal spacewalk in August and October 1997, which restored about 70% of the power capability previously available. The module was left isolated from the Mir complex until the end of the space station’s life.