Organometallic Propellant

Quaoar · 2014-03-31 07:44:15

I've found this interesting article about new organometallic non toxic hypergolic propellant: http://www.sps.aero/Key_ComSpace_Articl … ations.pdf

Some combinations like H2O2-lithium aluminium exahydride (LiAlH6) have a specific impulse of 469 s, even better than LOX-LH2, without all the problems of cryogenics. It may be interesting for a Mars mission?

Last edited by Quaoar (2014-03-31 07:45:01)

GW Johnson · 2014-03-31 09:28:31

Dunno about Mars, but that has potential for launch to LEO or exit trajectory. High-Isp and dense at the same time is quite good. Non-cryo tankage is good.

I cannot speak as to the storage stability of the organometallic fuels, but 90+% strength hydrogen peroxide is storage-unstable beyond several days. It blows up. Quite stable but not usable as a rocket oxidizer at 50% strength and under. In between is, well, in-between.

Some call it "safe" up to 70%, I don't. Needs to be 90+% to be useful as a rocket oxidizer, some prefer even higher. The paper talks about 98+%.

GW

Quaoar · 2014-03-31 12:41:03

GW Johnson wrote:

Dunno about Mars, but that has potential for launch to LEO or exit trajectory. High-Isp and dense at the same time is quite good. Non-cryo tankage is good.
I cannot speak as to the storage stability of the organometallic fuels, but 90+% strength hydrogen peroxide is storage-unstable beyond several days. It blows up. Quite stable but not usable as a rocket oxidizer at 50% strength and under. In between is, well, in-between.
Some call it "safe" up to 70%, I don't. Needs to be 90+% to be useful as a rocket oxidizer, some prefer even higher. The paper talks about 98+%.
GW

In this work ( http://hydrogen-peroxide.us/history-US- … roxide.pdf ) is said that H2O2 can be stored even for 15 years, in tanks of proper materials, with very minimal loss and if it is keep at 5°C, it can be stored fore even 17 years with no loss.

If H2O2 can be really stored for long times, H2O2-LiAlH6 may become the best propellant even for interplanetary travels.

Last edited by Quaoar (2014-03-31 12:42:33)

RobertDyck · 2014-03-31 22:21:36

Interesting. Quoting from the paper

V. Effect of Water Content on Stability of Hydrogen Peroxide
A common understanding by persons familiar with hydrogen peroxide is that as the concentration gets lower, the stability decreases. This phenomenon is sometimes used to test the compatibility of large hydrogen peroxide containers by exposing them, not to high concentration hydrogen peroxide, but to low concentration hydrogen peroxide, as this is a more stressing test of the compatibility of the tank. If the tank is passive with low concentration hydrogen peroxide, the compatibility will improve as the concentration increases. This is somewhat counter intuitive in that it suggests that very high concentrations of hydrogen peroxide, such as 98% or anhydrous hydrogen peroxide are more stable than 90% or 70% and therefore potentially safer to store. Most people would assume that as the concentration increased, the stability would decrease and the propellant would be more dangerous to handle. Some hazards do increase as the concentration increases, such as auto-ignition with flammables, hypergolic reactions, and self-sustained thermal decomposition, however the stability of hydrogen peroxide does improve as the concentration increases. So in terms of the storability of hydrogen peroxide, hydrogen peroxide is more stable as the concentration increases. ... This can be visually seen if one compares identical glass receptacles containing the three concentrations. One will see more “bubbles” in 70% hydrogen peroxide in comparison to 90% or 98% hydrogen peroxide. The physical explanation for this behavior is that water actually acts as a destabilizing contaminant with the hydrogen peroxide.

This paper claims hydrogen peroxide has much lower rate of decomposition than hydrazine, so therefor can be used as an oxydizer. However, the paragraph I just quoted mentioned "auto-ignition with flammables, hypergolic reactions, and self-sustained thermal decomposition". I think it's easy to design a tank that does not contain flammables. And avoid materials that act as a catalyst for hypergolic or decomposition reactions. But what temperature causes thermal decomposition?

JoshNH4H · 2014-04-01 00:20:04

Lithium is a no-go as a content of any rocket fuel being considered for Earth launch because it's rather rare abd has demonstrated effects on mood even in small concentrations.

Quaoar · 2014-04-01 00:59:11

JoshNH4H wrote:

Lithium is a no-go as a content of any rocket fuel being considered for Earth launch because it's rather rare abd has demonstrated effects on mood even in small concentrations.

Lithium was used for bipolar disturb therapy: if astronauts go mad it can be benefic .

So, if we want an orbital ship for a Mars mission we have to continue using hypergolics. These new R-4D derived Aerojet rockets have 335 s of Isp with NTO-Hydrazine and 330 with NTO-MMH ( http://ntrs.nasa.gov/archive/nasa/casi. … 001339.pdf ): very impressive!

Last edited by Quaoar (2014-04-01 01:46:05)

GW Johnson · 2014-04-01 09:50:29

Well, claims that high-concentration H2O2 can be long-term stable "if we just clean up our tankage enough" do not ring true to me.

That flies in the face of human experience with high concentration H2O2 since WW2. The Germans used it that way for many things, the most notable being the decomposition-driven launch ramps for the V-1 Buzz Bomb. The Luftwaffe had severe problems with it, too. Their records are full of it. So are Von Braun's from the Wehrmacht V-2 rocket project.

They (the Germans) and we tried using 90+% H2O2 with diesel engines in submarines, to run submerged without air. They and we found the same thing: you can get the engines to work that way, but you kill the crew when the H2O2 tank blows up and sinks the sub.

The last modern rocket company I am aware of that used H2O2 was Beale Aerospace, trying to break into the commercial launch business with a kerosene-H2O2 rocket featuring hypergolic ignition and fully-storable non-cryogenic propellants. They had severe problems, including at least one ground storage tank explosion. That one caught them by surprise; as I recall, it blew up only three days after distillation to 90+%. They routinely stored it for months quite safely at 50%. All of that matches the experiential history since WW2.

So, pardon me if I exhibit extreme skepticism about claims that 90+% H2O2 can be stored safely for years in space. I don't believe it.

GW

JoshNH4H · 2014-04-07 12:25:07

^Sounds a bit like the claim that "Water is a great insulator when pure".

While it is technically true that pure water, H2O, will not conduct electricity, is is effectively impossible to get water this pure. Left open to the air, it will absorb CO2 and become somewhat conductive; Placed in a metal container or even certain kinds of plastics ions will find their way into the water. Sounds possible in theory, but in fact it's just not reasonable to use water as a good dielectric, ever.

GW Johnson · 2014-04-08 12:48:00

Lithium has medical effects which can be dangerous. Has anybody thought to monitor the guys handling it to make the aluminum-lithium metal tanks that seem to be such a savior today? Decades ago there was a medical disaster with people handling beryllium.

GW

JoshNH4H · 2014-04-09 09:28:15

I would hope so but I'm sure NASA is pretty closed-mouthed about it.

RobertDyck · 2014-04-09 09:59:25

From WebMD

Lithium is used for mental illnesses, including bipolar disorder, depression, and schizophrenia; for eating disorders, including anorexia and bulimia; and for blood disorders, including anemia and low white-cell count (neutropenia).
Lithium is also used for headache, alcoholism, epilepsy, diabetes, liver disease, kidney disorders, arthritis, a skin condition called seborrhea, and overactive thyroid. Other uses include treatment of asthma, Huntington’s disease, Graves' disease, herpes simplex, a movement disorder called tardive dyskinesia, Tourette’s syndrome, cyclical vomiting, Meniere's disease, a tingling or “crawling” sensation in the skin (paresthesias), and aggressive behavior in people with attention deficit-hyperactivity disorder (ADHD).
How does it work?
Exactly how lithium works is unknown, but it might help mental disorders by increasing the activity of chemical messengers in the brain.
LITHIUM Side Effects & Safety
Lithium can cause nausea, diarrhea, dizziness, muscle weakness, fatigue, and a dazed feeling. These unwanted side effects often improve with continued use. Fine tremor, frequent urination, and thirst can occur and may persist with continued use. Weight gain and swelling from excess fluid can also occur. Lithium can also cause or make skin disorders such as acne, psoriasis, and rashes worse. The amount of lithium in the body must be carefully controlled and is checked by blood tests.

Doesn't sound too dangerous. Reminds me of Cheech and Chong.

JoshNH4H · 2014-04-09 12:56:50

Lithium is used in amounts of 1.8 g/day of Lithium Carbonate to treat bipolar disorder, because it has significant mood-moderating effect. Keep in mind, the mood swings associated with bipolar disorder are pretty extreme and lithium does a very good job moderating them. 1.8 g of Lithium Carbonate is .2 g of Lithium. To give this dose to 1 million people, the rocket would have to contain just 200 kg of Lithium. Compare this to the 1,000,000 kg of fuel in the two SRBs in the Space Shuttle at liftoff, and perhaps you'll begin to see why this is unacceptable. If your rocket contains 20,000 kg of Lithium and 5% of this is deposited over an area containing 100,000 people, the very soluble lithium is likely to leak into the water supply and affect them for months.

It's just not acceptable. How would you feel if I dumped mood stabilizers in your water?

RobertDyck · 2014-04-09 14:24:15

JoshNH4H wrote:

It's just not acceptable. How would you feel if I dumped mood stabilizers in your water?

Ethanol? Distilled from fermented barley?

Perhaps I should elaborate. In 2003 I worked for a company called MicroPilot. They manufacture autopilots for miniature UAVs. They test their autopilots with model airplanes purchased from a local hobby store. Because it's a test, it doesn't always go well. Occasionally the latest autopilot software will fail. They have a radio control that can override the autopilot, but if it flies out of radio range, they have to chase it until it runs out of fuel. In 2003 they were testing with a then new battery: lithium polymer. After one particular crash, the battery ballooned up. The technician read safety instructions that said safe disposal of the battery required cutting it open, under controlled and well ventilated conditions. He did so outside, on a day with a breeze. He wore heavy gloves and lexan face shield, used a utility knife. Several of us watched; I stood just up wind. The battery spewed black smoke for a several seconds, and I saw a red glow in the battery that looked like charcoal in a BBQ. The technician said he'll never do that again. But we all walked away without harm.

So been there, done that.

Last edited by RobertDyck (2014-04-09 14:36:42)

Terraformer · 2014-04-09 17:20:50

Mood stabilisers? The conspiracy theorists will have a field day...

But what effect does Lithium Oxide have, anyway? We tolerate the use of Hydrazine in rockets, and that is far nastier stuff. We wouldn't be spewing Lithium, but Lithium Oxide.

Of course, replace the Lithium with another Aluminum and you'll be back to HAlO propellent...

GW Johnson · 2014-04-10 08:26:32

Products of hydrazine combustion or decomposition are merely poisons, not other medical effects. Those we have half a century of experience dealing with, and the likelihood of anything unanticipated catching us as an unpleasant surprise is low.

Dosing a nearby population with fallout that has medical effects beyond a dilutable poison is something we probably don't want to do. That speaks against using propellants containing lithium. Aluminum is bad enough, but at least we have experiences with it in solid propellants since WW2. If there's a medical effect, it's a very small one. But, one must always suspect metals, and tiny particles.

Remember the beryllium disaster. And the problems with asbestos. These did sneak up on us. Sometimes the time constant is decades before the damage is evident, as with asbestos.

That being said, using lithium-bearing propellants in space should pose no risks. Not so sure about planetary surfaces, even airless ones, because people could be exposed by surface particles on their suits. The density makes the lithium-bearing propellants easy to launch in smaller packages for the same weight than LOX-LH2. You just have to take the proper precautions and restrict it to uses where you can control the effects, just like we now do with beryllium.

BTW, lithium is used in nuclear weapons. Its effects on the exposed population pale into insignificance compared to the other associated "exposures" from that application. So there is a matter of perspective here.

GW

RobertDyck · 2014-04-10 08:58:52

Ok, so LH2/LOX or RP1/LOX for launch, and this other stuff for OMS and RCS thrusters? Sounds good to me.

By the way, in 1989 my fiancé and her family insisted that they take away the aluminum nickel alloy cooking pots that their grandmother used. The fear at the time was aluminum caused Alzheimer's disease. But pot manufacturers didn't want to stop using aluminum, they just wanted people to throw out their old pots and buy new ones. Corporate greed. So they concocted the excuse that pure aluminum is Ok, aluminum as an alloy with other metals is not. I do not see how the alloy would make any difference: if it's bad then it's bad. So at this point I have to call "bullshit". More importantly, despite decades of study (from 1989 to today is now 25 years = 1/4 century) there is no evidence that aluminum increases risk of Alzheimer's. Scientists continue to study that issue, research is continuing, but there is still no evidence.

So, is lithium the new aluminum? Fear with no evidence? I already listed the effects and side effects from WebMD.

JoshNH4H · 2014-04-10 11:04:06

But what effect does Lithium Oxide have, anyway? We tolerate the use of Hydrazine in rockets, and that is far nastier stuff. We wouldn't be spewing Lithium, but Lithium Oxide.

Since it's the Li+ ion that has the effects, any lithium chemical is the same.

RobertDyck, the effects of lithium are well documented. There are a couple million Americans who take it daily to treat bipolar disorder, because of its mood stabilizing effects. These are effects that one does not want if one does not have bipolar disorder.

Again, please do note that this is medical fact and isn't really subject to your interpretation of WebMD. Quaoar, if you're reading this thread I would appreciate your input.

RobertDyck · 2014-04-10 13:09:47

It's documented. That's why I looked for it on MedMD. What exactly are the effects, and at what dose?

But GW Johnson raised a real issue: stability of hydrogen peroxide. The paper brushes over it, but real experience trumps an academic paper. And to avoid conflict, let me show you what got my interest.

A paper titled GPIM AF-M315E Propulsion System: Green Propellant Infusion Mission (GPIM). This was funded by NASA, to develop more environmentally friendly and less toxic propellant, that's storable. Previously, Aerojet-Rocketdyne had manufactured something called an arc-jet that used monopropellant hydrazine. Not UDMH or MMH, but raw hydrazine. The arc-jet used electricity and a catalyst to produce much more thrust and Isp than straight monopropellant hydrazine. This was intended to replace that.

AF-M315E offers higher performance than hydrazine, yields 12% higher Isp (257 vs. 235 sec), and is 45% more dense (1.47 vs. 1.00 g/cc), affecting both reduced propellant and tank mass.
...
With its lower minimum temperature threshold, AF-M315E yields an additional advantage of mitigating operational concerns related to long-duration system thermal management. Whereas hydrazine space tanks and lines must be heated at all times to prevent freezing, AF-M315E cannot freeze (it has a glass transition). During long coast periods an AF-M315E propulsion system may be allowed to fall to very low temperatures and later reheated for operation without risk of line rupture by phase-change-induced expansion.

That sounds good, but organometallic propellant has signicantly higher Isp.

JoshNH4H · 2014-04-10 14:28:20

robertdyck wrote:

It's documented. That's why I looked for it on MedMD. What exactly are the effects, and at what dose?

Treatment for bipolar disorder, with significant mood stabilizing effects, occurs at a dosage of .2 g of Lithium (normalized to 100%) per person per day. 5 g of Lithium taken as a single dose is probable poison source. However, the source notes that if a person has been exposed to lithium for a good amount of time already the toxic dose is significantly lower because tissues are already saturated with Lithium. Lithium also interacts with various drugs, including NSAIDs, the most common example of which is Advil. Even the effects of mild overdose include "Nausea, diarrhoea, blurred vision, polyuria, light headedness, fine resting tremor, muscular weakness and drowsiness", with moderate and severe overdoses having worse side effects, including, as a possibility, death. According to a different source, reproducing FDA drug warnings, symptoms of Lithium poisoning can occur near a therapeutic dose (again, .2 g of pure Lithium per day). They list the following contraindications:

Lithium should generally not be given to patients with significant renal or cardiovascular disease, severe debilitation or dehydration, or sodium depletion, and to patients receiving diuretics, since the risk of Lithium toxicity is very high in such patients. If the psychiatric indication is life-threatening, and if such a patient fails to respond to other measures, Lithium treatment may be undertaken with extreme caution, including daily serum Lithium determinations and adjustment to the usually low doses ordinarily tolerated by these individuals. In such instances, hospitalization is a necessity.

Given that the general population would be exposed to the Lithium, there would probably be deaths caused by the launch of even one Lithium-fueled rocket on Earth's surface.

GW Johnson · 2014-04-10 15:10:17

As far as dangers from metals go, the really heavy ones cause toxicity effects (lead, etc), and the really light ones seem to have various bad effects (beryllium is not expellable from the lungs leading to death by edema, lithium alters the brain's functioning, etc). The ones in between don't seem to bother folks much, like iron. I remember the scare over aluminum cookware, too, but I've seen no evidence that was anything but fearmongering, at least as far as Alzheimer's disease is concerned.

On the other hand, very small particles do cause problems in the lungs, that's why 2.5 micron and finer carbon soot is now considered a bad actor in air pollution from diesel engines. Aluminum is used in solid propellants, and in paints, in powdered form. I'm not sure how fine in those applications, but the finer, the more risk there is to evaluate. That seems to be the message.

It's just something to be aware of, before jumping in with both feet on something utterly new to human experience, like organo-metallic propellants bearing lithium. Actually, organo-metallic anything compounds the potential danger of metals.

For example, it is a whole lot harder to really get lead poisoning from metallic lead pipes, solder, or pewter utensils than it from minute amounts of lead bound in organic compounds. Same is true of mercury. Busting a mercury thermometer in your mouth is unlikely to hurt you (except as cuts and punctures from the glass fragments), even if you swallow the mercury. Trace amounts of methyl mercury in your drinking water most certainly will hurt you, usually as both toxic poisoning and as birth defects.

On the other hand, there is a well-known historical incident from the start of the industrial revolution involving mercury poisoning. The expression "mad as a hatter" comes from this. People who made hats from felt in steam-heated molds all day long every day for years had severe problems. They used mercury in the hats to force the felt out against the mold, and handled it barehanded. Skin exposure wasn't the problem, it was inhalation. At steam temperatures (NOT at room or body temperature), mercury actually does have a noticeable vapor pressure. The heated mercury vapors got to them, over about a 20 year working career. Symptoms were violent insanity from brain damage done by the metal.

BTW, the "amalgam" in standard tooth fillings has been around the best part of a thousand years now. It's in part mercury and lead. No one has ever, ever, ever had a problem with it. Trust long experience. It usually doesn't lie to us.

GW

Last edited by GW Johnson (2014-04-10 15:15:52)

JoshNH4H · 2014-04-10 15:20:03

It is quite a shame, though, given that if a Lithium engine has the same energy efficiency as a H2/LOX engine it would have an exhaust velocity of approximately 500 s.

GW Johnson · 2014-04-11 09:43:15

I copied the article in the first post this thread. Let me digest it a bit, and see if the ballistics matches what they claim. Easy storables with performance between kerolox and LOX-LH2 might be just the ticket for ventures fueled from home.

GW

GW Johnson · 2014-04-14 09:12:29

OK, that 469 sec Isp reported in the article for anyhydrous H2O2/Li3AlH6 is for theoretical perfect expansion all the way to vacuum at 100% nozzle efficiency, starting from a chamber pressure of 500 psia. Nothing you build will match that. It would be more helpful to report chamber c* velocity, which can be combined very quickly with a realistic thrust coefficient for the application, to produce a realistic Isp.

But, c* is a power function of selected chamber pressure: c* = K P^m. You also need an idea of specific heat ratio to get the thrust coefficient "right", but those are nearly always in the vicinity of 1.20. For LOX-LH2, at 100 psia and r = 4.5, c*= 7840 ft/sec; and at 1000 psia r = 4.0, c* = 7950 ft/sec. Those are for real combustion chamber efficiencies, not ideal thermochemical-code values.

My old Pratt & Whitney vest-pocket handbook reports a 100 psia vacuum isp for LOX-LH2 of 454. Yet at 3000 psia with finite expansion in the Shuttle engine, Isp was typically reported to be 467. So all these things do make a real difference.

I haven't got a good handle on the organometallic c* yet at 500 psia, much less its pressure dependence. But I'll see if I can get you a realistic estimate, and post it here.

The way you use it is estimate a thrust coefficient CF at application backpressure-limited expansion (and a realistic nozzle efficiency, usually near 0.983). Then CF c* / gc = Isp, where gc is the units-converting gravity constant in your F=ma/gc equation. That's the most realistic way I know to get a realistic Isp for your engine calculations.

GW

GW Johnson · 2014-04-14 14:13:53

On the assumption that the specific heat ratio of the exhaust gases really is 1.2, I get right at an exit Mach of 5.57 for the 250:1 exit bell area ratio quoted in the article. That corresponds to a chamber/exit pressure ratio of 4767; or for 500 psia chamber, an exit static pressure near 0.1 psia. The corresponding vacuum thrust coefficient calculates as 2.0048, unpenalized for any nozzle inefficiencies. For this, c* has to be 7527 ft/sec, which is right up there close to the values quoted for LOX-LH2. So, this is very good stuff.

On the other hand, I get a peroxide/fuel ratio by mass of 3.790 at stoichiometry. The optimium ought to be only somewhat smaller than that, not smaller by a huge amount. Yet the data table in the article says the optimum O/F ratio is 0.7 by mass, which is very wildly different. In comparison, stoichiometric for LOX-LH2 is by mass O/F 7.936, while opt r = 4 to 4.5.

That says at least some of the items in the table are not what everyone would normally interpret them to be. That casts quite a bit of doubt on just using stuff out of that article without independent verification, because somebody was playing sales games with this. A second indicator pointing the same direction is the claim of non-toxicity, which doesn't square well with the medical effects of small doses of lithium we were discussing earlier.

Now I tried estimating c* from chamber temperature out of their table, and my assumption of sp.ht. ratio=1.2, plus my stoichiometric estimate of exhaust gas molecular weight. I got about 5514 ft/sec. That was WAY off the CF-based value, which casts a lot of doubt on even my CF-based estimate. My assumption of sp.ht. ratio=1.2 is quite probably wrong.

Of the two, I think the CF-based estimate of c* is a lot more reliable than the first-principles estimate. It quite probably is in the 7000+ ft/sec ballpark. This stuff really is almost as good as hydrogen. I'd rather not use it in an atmosphere because of the lithium medical risks, but out in space, this is good stuff for very short term use.

The peroxide stability issue does come into play here. It's supposed to be 98+% to anhydrous, and that stuff is stable but for a handful of days at best.

GW

Mars_B4_Moon · 2022-07-02 07:14:25

Bacteria for blastoff: Using microbes to make supercharged new rocket fuel
https://www.spacedaily.com/reports/Bact … l_999.html

some other old new mars discussion on engine, space planes, and fuel in alternative rockets , LOX-Acetylene/CO rocket by Landis for a complete ISPP
https://newmars.com/forums/viewtopic.php?id=6993 ,
transportation Hybird Rockets https://newmars.com/forums/viewtopic.php?id=2471 High Isp storable propellant rocket https://newmars.com/forums/viewtopic.php?id=8800 Best propellant & stuff for a Mars spaceship and lander https://newmars.com/forums/viewtopic.php?id=8297 Alternative fuel aircraft https://newmars.com/forums/viewtopic.php?id=9842

,

New Mars Forums

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Organometallic Propellant

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