Author Topic: Hydrazine-fluorine upper stage for early crewed orbital flight? (Read 19740 times)

the_other_Doug · « **on:** 09/09/2015 03:33 pm »

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"...

DMeader · « **Reply #1 on:** 09/09/2015 03:48 pm »

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!

RonM · « **Reply #2 on:** 09/09/2015 04:05 pm »

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

Jim · « **Reply #3 on:** 09/09/2015 04:07 pm »

Quote from: the_other_Doug on 09/09/2015 03:33 pm

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

Agena wasn't shared with others.

Jarnis · « **Reply #4 on:** 09/09/2015 05:35 pm »

Quote from: DMeader on 09/09/2015 03:48 pm

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...

the_other_Doug · « **Reply #5 on:** 09/09/2015 10:59 pm »

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...

kch · « **Reply #6 on:** 09/09/2015 11:54 pm »

Quote from: the_other_Doug on 09/09/2015 10:59 pm

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

Herb Schaltegger · « **Reply #7 on:** 09/10/2015 05:21 pm »

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.

DMeader · « **Reply #8 on:** 09/11/2015 11:34 am »

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.

kevin-rf · « **Reply #9 on:** 09/11/2015 12:57 pm »

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

Jarnis · « **Reply #10 on:** 09/11/2015 07:11 pm »

Quote from: kevin-rf on 09/11/2015 12:57 pm

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.”

Patchouli · « **Reply #11 on:** 09/11/2015 11:46 pm »

Quote from: Jarnis on 09/11/2015 07:11 pm

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.

edkyle99 · « **Reply #12 on:** 09/11/2015 11:58 pm »

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

Jarnis · « **Reply #13 on:** 09/12/2015 05:16 am »

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

DMeader · « **Reply #14 on:** 09/12/2015 11:22 pm »

Quote from: Patchouli on 09/11/2015 11:46 pm

Quote from: Jarnis on 09/11/2015 07:11 pm

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!

the_other_Doug · « **Reply #15 on:** 09/13/2015 02:00 am »

Quote from: DMeader on 09/12/2015 11:22 pm

Quote from: Patchouli on 09/11/2015 11:46 pm
Quote from: Jarnis on 09/11/2015 07:11 pm

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...

Donosauro · « **Reply #16 on:** 09/13/2015 03:05 am »

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.

Vultur · « **Reply #17 on:** 09/13/2015 05:05 am »

Quote from: DMeader on 09/12/2015 11:22 pm

... 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.

DMeader · « **Reply #18 on:** 09/13/2015 01:23 pm »

Quote from: Vultur on 09/13/2015 05:05 am

Quote from: DMeader on 09/12/2015 11:22 pm
... 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.

the_other_Doug · « **Reply #19 on:** 09/13/2015 03:50 pm »

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.