Author Topic: Hydrazine-fluorine upper stage for early crewed orbital flight?  (Read 19154 times)

Offline the_other_Doug

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I have been re-reading "This New Ocean," the official NASA history of Project Mercury.  And in it, there is a reference to one of the early military plans (it was either MISS or Project ADAM, sorry, I can't find the reference to the specific program) where the developers had decided the "bare Atlas" with no upper stage was far too difficult and dangerous a vehicle to use in launching a human being into orbit.  There were concerns both with the reliability of the Atlas, and the launch profile a stage-and-a-half vehicle like Atlas would have to follow, with its high G loads and its related very high abort G loads and high heating regime if the capsule had to come down on a ballistic trajectory after a launch abort fairly late in the boost phase.

What they came up as an alternative to the Atlas with was a launcher with a Thor first stage, the first stage from Vanguard as the second stage, and a yet-to-be-developed upper stage that would burn hydrazine and fluorine as the oxidizer/fuel combo.

This wasn't the first time a launcher with those first two stages was proposed.  But this is the only place I have seen any reference to a hydrazine/fluorine upper stage.  Does anyone have any clue how this stage would be configured?  Would they have used the Agena (then also under early development) as a basis for the spaceframe, or built an entirely new and different stage?

Also, what would have been the advantages of running hydrazine with fluorine, as opposed to hydrazine and nitric acid/nitrazine, as later hypergolic stages, including Agena, used?  Is the iSP of the fluorine/hydrazine combo better than what eventually became standard for hypergols?  Or was it considered easier/less toxic to handle?  And, to round out the questions that pop up in my head, is hydrazine even hypergolic in combination with fluorine, or does it require an igniter of some kind?

Since we never heard again of such an upper stage, I got curious as to what kind of stage this would have been, and whether or not there was ever any design work done on it that would characterize the stage, how it would have flown, what style of engine it would have used, etc.  So I decided to come out here and ask.

:)

NOTE: Edited to fix my mis-spelling of "fluorine"...
« Last Edit: 09/09/2015 11:57 pm by the_other_Doug »
-Doug  (With my shield, not yet upon it)

Offline DMeader

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have you read "Ignition!: An Informal History Of Liquid Rocket Propellants" by John D. Clark? Long out-of-print but there are PDF versions floating around.  Quite entertaining. I don't know if I can post a link, let me know or just google it.

PS... EVERYTHING is hypergolic with fluorine!

« Last Edit: 09/09/2015 05:08 pm by DMeader »

Offline RonM

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Handling fluorine is extremely dangerous. The exhaust would have HF in it! That's corrosive enough to etch glass.

It would have more performance, but hardly worth the effort.

http://www.astronautix.com/props/lf2azine.htm

http://www.astronautix.com/engines/g1.htm

https://en.wikipedia.org/wiki/Hydrogen_fluoride

Offline Jim

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Would they have used the Agena (then also under early development) as a basis for the spaceframe,

Agena wasn't shared with others.

Offline Jarnis

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have you read "Ignition!: An Informal History Of Liquid Rocket Propellants" by John D. Clark? Long out-of-print but there are PDF versions floating around.  Quite entertaining. I don't know if I can post a link, let me know or just google it.

PS... EVERYTHING is hypergolic with fluorine!

Fluorine? Everyone back away slowly and then run for the hills... :)


Offline the_other_Doug

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Thanks, guys!  Sounds like this was a generalized "fluorine is the future!" bit of babble, and not any kind of well-thought-out rocket stage.  Certainly not at the point where any design engineering had been done.

Just wanted to check... :)
-Doug  (With my shield, not yet upon it)

Offline kch

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Thanks, guys!  Sounds like this was a generalized "fluorine is the future!" bit of babble, and not any kind of well-thought-out rocket stage.  Certainly not at the point where any design engineering had been done.

Just wanted to check... :)

You might find this interesting:

http://www.astronautix.com/engines/g1.htm

Rocketdyne G-1 engine, to be used in Nomad upper stage.  Smaller, with lower thrust and Isp than Bell's Chariot engine (intended for use on a replacement for the Titan 3's Transtage).  Speaking of which ...

http://www.astronautix.com/engines/chariot.htm

:)

Online Herb Schaltegger

I think it was probably a case of "Fluorine is the future!" combined with hand waving optimism. Fluorine is used industrially in the nuclear industry and there is a specialized set of technologies developed to work with it on industrial scale specifically with uranium enrichment and metal production.  The Cold War was in full swing and someone probably thought space could be the next logical use of the chemistry.
« Last Edit: 09/10/2015 05:22 pm by Herb Schaltegger »
Ad astra per aspirin ...

Offline DMeader

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Or, someone saw something flame up dramatically when exposed to fluorine and thought "ooooh...rocket fuel!".

From the Clark book, it seems that back in the days of exuberant experimentation, just about everything that could be coaxed to react with anything else was tried. Most of the results were disappointing. Some just blew the place to smithereens.

Offline kevin-rf

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Why do I have a feeling Fluorine was one of those items that "blew the place to smithereens".
If you're happy and you know it,
It's your med's!

Offline Jarnis

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Why do I have a feeling Fluorine was one of those items that "blew the place to smithereens".

Sure, but there were some far more hilarious things that were tried. Chlorine Trifluoride (CIF3) comes to mind...

Makes pure Fluorine look positively tame. As described in Ignition! :

Quote
”It is, of course, extremely toxic, but that's the least of the problem. It is hypergolic with every known fuel, and so rapidly hypergolic that no ignition delay has ever been measured. It is also hypergolic with such things as cloth, wood, and test engineers, not to mention asbestos, sand, and water-with which it reacts explosively. It can be kept in some of the ordinary structural metals-steel, copper, aluminium, etc.-because of the formation of a thin film of insoluble metal fluoride which protects the bulk of the metal, just as the invisible coat of oxide on aluminium keeps it from burning up in the atmosphere. If, however, this coat is melted or scrubbed off, and has no chance to reform, the operator is confronted with the problem of coping with a metal-fluorine fire. For dealing with this situation, I have always recommended a good pair of running shoes.”

Offline Patchouli

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Sure, but there were some far more hilarious things that were tried. Chlorine Trifluoride (CIF3) comes to mind...

Makes pure Fluorine look positively tame. As described in Ignition! :

Quote
”It is, of course, extremely toxic, but that's the least of the problem. It is hypergolic with every known fuel, and so rapidly hypergolic that no ignition delay has ever been measured. It is also hypergolic with such things as cloth, wood, and test engineers, not to mention asbestos, sand, and water-with which it reacts explosively. It can be kept in some of the ordinary structural metals-steel, copper, aluminium, etc.-because of the formation of a thin film of insoluble metal fluoride which protects the bulk of the metal, just as the invisible coat of oxide on aluminium keeps it from burning up in the atmosphere. If, however, this coat is melted or scrubbed off, and has no chance to reform, the operator is confronted with the problem of coping with a metal-fluorine fire. For dealing with this situation, I have always recommended a good pair of running shoes.”

What's funny and probably scary if you think about it too much is the compound is often used in the semi conductor industry to clean CVD chambers.
« Last Edit: 09/11/2015 11:46 pm by Patchouli »

Offline edkyle99

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Here's a bit about Rocketdyne's Project NOMAD (fluorine/hydrazine)

https://books.google.com/books?id=s1C9Oo2I4VYC&pg=PA45&lpg=PA45&dq=fluorine+Nomad+rocket+engine&source=bl&ots=eO47M3erKU&sig=5_X99OcZSSb-m5p4lYkemF8m444&hl=en&sa=X&ved=0CCcQ6AEwAWoVChMImvfIn5bwxwIVwtSACh2c7Qj8#v=onepage&q=fluorine%20Nomad%20rocket%20engine&f=false

Here's an image of the proposed stage.
http://www.alternatewars.com/BBOW/Space_Engines/NOMAD_Model.png

There was an accident at Santa Susana during a NOMAD test that released a green cloud down the valley.  That caught some people's attention!

 - Ed Kyle
« Last Edit: 09/12/2015 12:02 am by edkyle99 »

Offline Jarnis

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NOMAD or NO, we're not MAD but thanks for asking...?   :P

Offline DMeader

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Sure, but there were some far more hilarious things that were tried. Chlorine Trifluoride (CIF3) comes to mind...

Makes pure Fluorine look positively tame. As described in Ignition! :

Quote
”It is, of course, extremely toxic, but that's the least of the problem. It is hypergolic with every known fuel, and so rapidly hypergolic that no ignition delay has ever been measured. It is also hypergolic with such things as cloth, wood, and test engineers, not to mention asbestos, sand, and water-with which it reacts explosively. It can be kept in some of the ordinary structural metals-steel, copper, aluminium, etc.-because of the formation of a thin film of insoluble metal fluoride which protects the bulk of the metal, just as the invisible coat of oxide on aluminium keeps it from burning up in the atmosphere. If, however, this coat is melted or scrubbed off, and has no chance to reform, the operator is confronted with the problem of coping with a metal-fluorine fire. For dealing with this situation, I have always recommended a good pair of running shoes.”

What's funny and probably scary if you think about it too much is the compound is often used in the semi conductor industry to clean CVD chambers.

... and fluorides are added to your drinking water to harden the enamel of your teeth. Go figure!

Offline the_other_Doug

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Sure, but there were some far more hilarious things that were tried. Chlorine Trifluoride (CIF3) comes to mind...

Makes pure Fluorine look positively tame. As described in Ignition! :

Quote
”It is, of course, extremely toxic, but that's the least of the problem. It is hypergolic with every known fuel, and so rapidly hypergolic that no ignition delay has ever been measured. It is also hypergolic with such things as cloth, wood, and test engineers, not to mention asbestos, sand, and water-with which it reacts explosively. It can be kept in some of the ordinary structural metals-steel, copper, aluminium, etc.-because of the formation of a thin film of insoluble metal fluoride which protects the bulk of the metal, just as the invisible coat of oxide on aluminium keeps it from burning up in the atmosphere. If, however, this coat is melted or scrubbed off, and has no chance to reform, the operator is confronted with the problem of coping with a metal-fluorine fire. For dealing with this situation, I have always recommended a good pair of running shoes.”

What's funny and probably scary if you think about it too much is the compound is often used in the semi conductor industry to clean CVD chambers.

... and fluorides are added to your drinking water to harden the enamel of your teeth. Go figure!

Yeah!  And they put it in our toothpaste, too!  Are they trying to kill us all?

It could explain the repeated reports of spontaneous toothbrush ignition, though...

;)
-Doug  (With my shield, not yet upon it)

Offline Donosauro

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Back in the 1960s, seemingly serious consideration was given to "floxing" the Atlas. I seem to remember an article in "Missiles and Rockets" magazine.

http://www.nytimes.com/1964/02/10/fluorine-backed-as-aid-to-rockets.html?_r=0 mentions the possibility of using the fluorine/oxygen mixture with the Thor, Saturns, and Agena, as well.

https://books.google.com/books?id=6ebcBwAAQBAJ&pg=PA765&lpg=PA765&dq=floxed+atlas&source=bl&ots=DIHXtj52YY&sig=W8PPZX3pQnpvNe0-rI2F4umcMN8&hl=en&sa=X&ved=0CCUQ6AEwA2oVChMI5bzIvIDzxwIVxHYeCh3pXA5o#v=onepage&q=floxed%20atlas&f=false has some technical details about tests of materials for use with fluorine or flox.

Offline Vultur

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... and fluorides are added to your drinking water to harden the enamel of your teeth. Go figure!

Big difference between fluoride (ion/ionic compound) and fluorine (elemental fluorine gas) ... or fluorine-other halogen compounds like ClF3 and ClF5.

Similarly, chloride ion is found in table salt but chlorine gas is very corrosive & toxic.

Offline DMeader

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... and fluorides are added to your drinking water to harden the enamel of your teeth. Go figure!

Big difference between fluoride (ion/ionic compound) and fluorine (elemental fluorine gas) ... or fluorine-other halogen compounds like ClF3 and ClF5.

Similarly, chloride ion is found in table salt but chlorine gas is very corrosive & toxic.

No kidding. Just pointing out that something so hellishly reactive can produce something so benign that we routinely put it in our mouth.

Offline the_other_Doug

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Yeah -- organic chemistry uses a lot of elements (like, say, phosphorous) that, in pure form, are extraordinarily toxic or flammable.  But without them, our terrestrial form of life could not exist.
-Doug  (With my shield, not yet upon it)

Offline savuporo

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Offline Jarnis

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Refering back to classics

http://pipeline.corante.com/archives/things_i_wont_work_with/
And specifically
http://pipeline.corante.com/archives/2012/02/28/one_does_not_simply_walk_into_fluorine_chemistry.php

Thanks for the links. That allowed me to find this entertaining video... Some French people that are FAR braver than I am are exploring the "mild" reactions that Chlorine Trifluoride has with all kinds of things that you'd expect to... you know... protect you.


« Last Edit: 09/14/2015 06:47 pm by Jarnis »

Offline B. Hendrickx

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While the US pretty much gave up on fluorine in the late 1950s, the Soviet Union had an active fluorine program that continued well into the 1970s, probably because the LOX/LH2 combination emerged as a viable alternative much later than it did in the US. Valentin Glushko's Energomash design bureau tested fluorine/ammonia engines at a facility some 120 km northwest of Leningrad on an isthmus between the Gulf of Finland and Lake Vysokinskoye.

Test firings of small experimental chambers began in the late 1950s and by the mid-1970s Energomash was testing a pump-fed fluorine/ammonia engine (RD-301) that was supposed to fly on a newly developed fourth stage for the Proton rocket (the 11S813). At the Baikonur cosmodrome two pads were under construction to launch the Proton/11S813 combination (known as Proton-KF). However, in February 1977 the Soviet government canceled the program, just as the RD-301 was getting ready for integrated test firings with the upper stage. The two Proton pads (nrs. 39 and 40 in Area 200 of the cosmodrome) were eventually only used for launches of the "conventional" Proton with the Blok-DM and Briz-M upper stages.

For those interested, I wrote a lengthy history of the Soviet fluorine effort for Quest magazine, Vol. 21 nr. 4 (2014) ("The Development of Fluorine-Based Engines in the USSR").

Offline savuporo

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However, in February 1977 the Soviet government canceled the program, just as the RD-301 was getting ready for integrated test firings with the upper stage.
See, soviets were not completely and inherently evil. This was a good thing :D

Quote
For those interested, I wrote a lengthy history of the Soviet fluorine effort for Quest magazine, Vol. 21 nr. 4 (2014) ("The Development of Fluorine-Based Engines in the USSR").
Thank you, bought the issue :
http://www.spacehistory101.com/Quest_The_History_of_Spaceflight_Volume_21_4_p/v214.htm

Thanks to this, I now also learned that the soviet fluorine dreams lived on even through Spiral and BOR-4 ...
http://www.bis-space.com/belgium/wp-content/uploads/2015/05/bor-41.pdf
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Offline savuporo

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Just finished reading this piece. And also learned about "Heavy Launch Vehicles of the Yangel Design Bureau", including the thing called RK-100.

Now, i would say that from here on, lets reserve the term "monster rocket" to something that weighs over 2 000 tons at lift off, is mostly filled with hydrazine but is planned to carry fluorine and ammonia in its upper stages and is potentially tipped with a nuclear reactor powered upper stage. The people of Dnepropetrovsk, headed by certain gospadin Valentin Kovalchuk must have been clinically insane.


EDIT:
Also, this paper is comedy gold:

http://ntrs.nasa.gov/archive/nasa/casi.ntrs.nasa.gov/19790024198.pdf
« Last Edit: 09/27/2015 01:13 am by savuporo »
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Offline Bob Shaw

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No. Really, no.
« Last Edit: 09/27/2015 01:27 am by Bob Shaw »

Offline redliox

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Fluorine is one of the few oxidizing elements more potent than oxygen itself; which in turn means it's a horrible, horrible, horrible chemical to work with.  Hydrazine and its kin are dangerous enough, but fluorine is a step above them. So, to quote Bob Shaw before...

No. Really, no.
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Offline MattMason

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Fluorine is one of the few oxidizing elements more potent than oxygen itself; which in turn means it's a horrible, horrible, horrible chemical to work with.  Hydrazine and its kin are dangerous enough, but fluorine is a step above them. So, to quote Bob Shaw before...

No. Really, no.

So, what we can take for all this is:

What doesn't react with fluorine?
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Offline kch

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Fluorine is one of the few oxidizing elements more potent than oxygen itself; which in turn means it's a horrible, horrible, horrible chemical to work with.  Hydrazine and its kin are dangerous enough, but fluorine is a step above them. So, to quote Bob Shaw before...

No. Really, no.

So, what we can take for all this is:

What doesn't react with fluorine?

Not much:

https://en.wikipedia.org/wiki/Fluorine#Noble_gases

Offline MattMason

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Fluorine is one of the few oxidizing elements more potent than oxygen itself; which in turn means it's a horrible, horrible, horrible chemical to work with.  Hydrazine and its kin are dangerous enough, but fluorine is a step above them. So, to quote Bob Shaw before...

No. Really, no.


So, what we can take for all this is:

What doesn't react with fluorine?

Not much:

https://en.wikipedia.org/wiki/Fluorine#Noble_gases

Just after reading this article yesterday I watched a news report about a plant explosion at an Exxon-Mobil factory. A large chunk of debris was hurled hundreds of feet, barely missing a tank containing hydrofluoric acid. The estimated toll of affected people spanned out for miles from that tank with 200,000 casualties probable.

The dreadful possibilities from such a disaster makes the shockwaves from the PEPCON rocket fuel plant explosion seem like a small brush fire.
"Why is the logo on the side of a rocket so important?"
"So you can find the pieces." -Jim, the Steely Eyed

Offline savuporo

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What doesn't react with fluorine?

Well, it seems that Valentin Glushko figured that out pretty well, seeing as he put two decades into building working fluorine engines.
If he didnt, Soviets would have perhaps stood a better chance of actually getting anywhere close to the moon, if Glushko focused on LOX/LH2 instead
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Offline acsawdey

Well, it seems that Valentin Glushko figured that out pretty well, seeing as he put two decades into building working fluorine engines.
If he didnt, Soviets would have perhaps stood a better chance of actually getting anywhere close to the moon, if Glushko focused on LOX/LH2 instead

Didn't know about Glushko and fluorine. But his refusal to build a LOX/RP1 engine for Korolev led to the NK-33 being commissioned from a jet engine manufacturer and we know how many tears have been shed over that between the N-1 and Anteres. That and a whole lot more is in Chertok's excellent memoir Rockets and People which you can get here:

http://www.nasa.gov/connect/ebooks/rockets_people_vol1_detail.html

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