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chemoleo
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[*] posted on 5-5-2004 at 17:01
New Energetic Materials - Current Research


By pure chance I stumbled across an article in the journal Chemists (or something like that) in Britain. I scanned the article, see below:



Isn't that interesting? I always wondered what government/defense/university labs were working on, so this is what they do!

Now, clearly there's the question as to 1) the chemical structures, and 2) synthesis routes.
For 1), I found this at
http://www.ijvs.com/volume5/edition3/section3.htm
Have a look, a full mass spec analysis of the detonation products, plus a few structures:



Particulary interesting seems hydrazinium azide hydrazinate (because once hydrazin/azide is available, synth. should be feasible), whose structure is unfortunately not given. THe picture next to the article apparently shows the structure, but I fail to figure it out.
It seems to be a complex of [N3]- [(N2H4)6H]+, so obvioulsy extremely rich in nitrogen. But why 6 x N2H4? How's this a stable complex?

As to the synthesis of this - I couldnt possibly yet say - all I can think of is hydrazine azide, possibly prepared from hydrazine sulphate and barium azide - which is different to the hydrazinate for sure.

I was hoping that some people would have some interesting insights, or even stumbled across some patents/syntheses (which I wasn't able to find, despite searching).

To do this in a mad science fashion would be a true achievement :D!!




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smile.gif posted on 5-5-2004 at 23:45


Obviously the excess NH2-NH2 aren't bond via conventional bonds...but wel via H bonds.

To me the molecular drawing make me feel like cristallisation water arround salts...
Like in Na2SO4.10 H2O

NH2-NH2 is a polar solvant like NH3 and H2O, CH3-OH ... and so as such it can form like hydrate salts....

Thus the idea is fairly simple:
Make NH2-NH3N3 (volatile and hard to cristallise) via conventional ways and simply add the salt to a concentrated solution of NH2-NH2....

Main Hazards, you will for sure need concentrated NH2-NH2 since water will be a fairly good competitor.
Anhydrous NH2-NH2 will leave after dissollution of anhydrous NH2-NH3N3...unstable adducts of hydraziniumazide hydrazinate
NH2-NH3N3.x NH2-NH2
NH2-NH3N3 is also written NH2-NH2.HN3!

In principe it should work for any hydrazinium salt and so...
NH2-NH3CN (Hydrazinium cyanide)
NH2-NH3C(NO2)3 (hydrazinium nitroformate)
NH2-NH3N(NO2)2(hydrazinium dinitramide)
NH2-NH3NO3 (H. nitrate)
NH2-NH3ClO4 (H. perchlorate)

But also for salts of hydrazin derivatives like:
Semicarbazine NH2-CO-NH-NH2
Carbazine (NH2-NH-)2CO
Guanyl hydrazine (NH2)2C=N-NH2
Guanyl dihydrazine (NH2-NH-)2C=NH
Guanyl trihydrazine (NH2-NH-)2C=N-NH2
N'N'N'Triamino melamine (-N=C(-NH-NH2)-)3
1,3,5 trihydrazino-2,4,6triazidobenzene
N,N,N triamino cyclotriazahexane (reduced trinitroso or trinitroRDX)
....

Endless way of wonderful things to investigate....

:):D;):cool::P:cool:;):D:)




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[*] posted on 6-5-2004 at 03:29


PH Z?!, is that really you?
Oh yeah i reconize your post structure!
The real one is back!
Good to see you again :D




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[*] posted on 6-5-2004 at 12:47


Philou, good to see you are still alive :)
Quote:

Anhydrous NH2-NH2 will leave after dissollution of anhydrous NH2-NH3N3...unstable adducts of hydraziniumazide hydrazinate


Now you mention yourself this is unstable. This is what I would have thought myself. However, if you have a close look at the article, it is specifically mentioned that they are storage stable at least up to 71 deg C. Hardly a property that I would think of this complex, which must be weak and hard to crystallise. Probably it is extremely susceptible to water, to hydrolysis, hell, even access to air. You couldn't possibly use this as rocket fuel, could you?

Anyway, this article also mentions dinitrobiuret, which was commonly used to assay protein concentrations (i.e. protein + CuSO4 + NaOH --> deep blue colour).
It is
H2N-CO-NH-CO-NH2
so presumably the NO2 groups are on the NH2's which gives

O2N-HN-CO-NH-CO-NH-NO2

I seem to remember that biuret is made by the condensation of urea, that is heating it up to its decomposition point. I searched, couldnt find info on it though - at least in my books. But whether that works with nitrourea is definitely a different issue.
Any thoughts?

PS feel free to post other new energetic materials that were prepared of late!




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[*] posted on 11-5-2004 at 13:19


Well... Vulturius Brutus obtained this article, which I wanted to get hold of too, here http://www.sciencemadness.org/talk/viewthread.php?action=att...

It is the original paper describing the making of the hydrazinium azide hydrazinate! (Klapoetke et al)

A few excerpts:

Preparation:
Hydrazinium azide hydrazinate 1 was synthesized in a straightforward, quantitative synthesis from equimolar
amounts of hydrazinium azide and hydrazine in an evacuated Schlenk vessel by heating the vessel for two days to 50 deg C

[H2NNH3+][N3-] + ‡H2NNH2 -->
[H2NNH3+][N3-]:‡H2NNH2


Properties:

It was shown that the detonation velocity of hydrazinium azide at similar densities is greater than the detonation velocity of
RDX, due to the formation of hydrogen during the explosion.
HAH is a colorless solid that is, in contrast to hydrazinium azide alone, not volatile and not hygroscopic (!!).
It showed no sensitivity to an electrical discharge of 20 kV (electrostatic), in a drop hammer test (5 kg=50 cm) and to grinding in a mortar (friction).
Like hydrazinium azide, HAH does not explode when heated slowly (10K=min), but detonates under rapid heating or when put on contact with a hot metal surface.


How interesting is that?? It really does seem that complexation turns this into a stable material! Non-hygroscopic, and not volatile! In my prev. posts I assumed this not to be the case - and I am glad I was wrong! :D

I think someone will get a few more requests regarding this excellent journal!




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[*] posted on 11-5-2004 at 13:46


You also might be interested in looking into DAAT or tetranitratodiformylpiperazine, the latter one is described in a thread by me.



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[*] posted on 15-8-2004 at 11:43


I heard something about mixture of aluminium nano-particles and molybdenum trioxide. It looks like an ordinary flash powder (or thermite), but it has ability of initiating explosives. Knows anybody here sometnig about this stuff, or about making aluminium nano-powder?
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[*] posted on 15-8-2004 at 19:12


Well yes, I would hardly call that novel.
It is a thermite of course (where u will find a big thread on it), and the fact that it may be powerful enough to serve as an initiator is also not novel - becuase CuO/Al is known to do the same.




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[*] posted on 21-8-2004 at 13:33


Quote:
Originally posted by chemoleo
By pure chance I stumbled across an article in the journal Chemists (or something like that) in Britain. I scanned the article, see below:

Isn't that interesting? I always wondered what government/defense/university labs were working on, so this is what they do!
(cut quote. please don't quote whole posts, particularly with images! chemoleo)


Some weeks ago, I found on the internet references to an even more energetic all-nitrogen compound tipped as a possible rocket propellant. It, with a formula N10, consisted of two 5-membered rings of N atoms (pentazole), one positively charged and the other negatively charged, forming an internal salt and also joined by a covalent bond (without a linking azo group). I think it may have been called dipentazole.

John W

[Edited on 22-8-2004 by chemoleo]
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[*] posted on 21-8-2004 at 19:03


Yes, I saw that mentioned. Seemed to be a purely theoretical result. To my knowledge, no exotic molecular nitrogen has ever been made. (Actually, I did hear a rumor that one N6? had been detected via some spectroscopic technique, so they made a molecule or two). However, a covalent network polynitrogen has been recently made in a diamond anvil. The researchers couldn't get it out, though.
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[*] posted on 21-8-2004 at 19:38
The article is interesting


I am thrilled that so many "Green" discoveries are being made in the name of chemistry. Unfortunately, I feel "Green Chemistry" is more of a political angle more than anything. And journalist never cease to misinform the masses. I never thought Al2O3 as being toxic. If it is than I am sure many simular oxides used in ceramics etc are toxic( I am mainly talking of silica, titanium dioxide, mullite etc not heavy metal ceramic compounds). Really, they are irritant dist and nothing more.

This reminds me of the most recent space shuttle crashing and when NASA was not wanting the public to capture fragments as souvenires. They used a scare tactic stating the fragements where contaminated with Hydrazine! Anyone with at least mediocre intelligence would know the fragments would have lost all hydrazine once they got white hot on rentry.
I am not saying everyone should know and understand chemistry, but if someone states a chemical in a story to frighten, the public should least take the time to look it up and find out it is a volatile fuel! People can be so naive.

[Edited on 8/22/2004 by chloric1]




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[*] posted on 21-8-2004 at 20:00


How could Al2O3 and other refractory oxides like SiO2 and TiO2 and clays and silicates be toxic, in spite of being unreactive? The only way they could be is by inhalation of the finely divided oxides as dust, causing fibrotic lung diseases like silicosis, asbestosis, and in severe cases lung cancer.

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[*] posted on 24-8-2004 at 12:41
HAH


Before the incident involving iDefense, Mega had discussed
hydrazinium azide to some extent, calling it 1 of the most powerful
new HE's out there. Now along comes HAH. I can't help but wonder
about the complexation of the azide with more hydrazine. I think
back to Astrolite where hydrazinium nitrate, hydrazine, and
aluminum powder form an explosive system far more powerful
than hydrazinium nitrate by itself. Very interesting indeed ! Looks
like I have to do even more research ! Chemoleo, thank you very
much for posting this !




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[*] posted on 9-10-2004 at 16:23


US3155456 Hydrazine Azide

The expense of hydrazine production will probably make bulk explosives derived from it economically impractical . For small amounts of explosives such as primary explosives hydrazine derivatives are already used , because their stability and
power advantages are worth the cost .
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[*] posted on 1-9-2005 at 23:48
Where is this going?


Interesting PDF, if somewhat discouraging. I guess with the lost of interest and funding for research, it may be up to those that do this on the side for fun to move this forward (people like Rosco for example).

[Edited on 2-9-2005 by Quince]

Attachment: Advanced Energetic Materials.pdf (891kB)
This file has been downloaded 5367 times





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[*] posted on 2-9-2005 at 00:08


Many of the new energetics mentioned there seem quite out of reach for people like us, I do, however, believe that CL-20 is definatly within our reaches. Unfortunatly CL-20 has already become somewhat of mainstream energetic, so no groundbreaking breakthroughs for us it would seem.:( Although there is always a chance:)



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[*] posted on 2-9-2005 at 00:48


Some things are not clear from the article. For example, what are these all-nitrogen compounds? They have N_5- and N_5+ (or some other number, forget the exact subscripts). I don't get it. And why are they energetic?

They also don't explain what exactly are the reactive compounds for munition payloads in the later section. The only specific example is the graphite for electrical shortings, but obviously the photos are of some other type of thing.

BTW, they mention that ONC is not as dense as was predicted. Now, in the original ONC synthesis paper, it mentions ONC is expected to be more powerful than CL-20. So does this still hold, given that density turned out lower, or not?

Also, they list a bunch of Russian references, but I'm having trouble locating many of these papers, let alone what I'm really looking for, a summary comparison of such both synthesized and theoretical advanced energetic materials. Which of these candidates (with at least some minimal stability) are expected to be the top performers?

[Edited on 2-9-2005 by Quince]




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[*] posted on 2-9-2005 at 01:02


I think we can do alot more than we think, we just need to find routes to the precursors. For example, if someone found a OTC synthesis of glyoxal, we'd all be up to our ears in extremely high energy nitramines. CL-20, HHTDD, TNGU, etc.

I've been doing alot of research into these areas, and although I haven't yet got enougn info to actually start making alot of these exotic explosives, I think we can do alot more than we think if we really put out brains to it.

Also, when I do begin synthesising (or attempting to synthesize) some of the exotic tetrazoles I've been researching, it will be actual research. As far as I know, some of them haven't even been made before (except maybe in classified military labs, those don't count).

EDIT: I belive ONC is more powerful in some ways then CL-20. It is less dense, but I think it's (predicted) VoD is still a tad higher. It does have a much larger energy content than CL-20 however. But since the synthesis is at the moment very expensive and hard, it's preobably going to be some time before we find out for sure.

[Edited on 2-9-2005 by Chris The Great]
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[*] posted on 2-9-2005 at 01:06


How about making ONC then? The main difficulty there seems not so much the precursors, but the apparatus needed. And it would be hard to tell exactly how much nitration has been achieved after a given step without crystallography (though I'll have my X-ray setup running soon and I can explain to the chemists here how to get a nice one going for under $250, I've been unable to get my hands on reconstruction software).

[Edited on 2-9-2005 by Quince]




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[*] posted on 2-9-2005 at 01:59


You seem to misunderstand the nitration of cubane and why it is difficult. It proceeds one nitro group at a time so there is no need to try and figure out how nitrated it is, there is only one possibility. Cubane cannot be nitrated with normal nitrating agents (NO2+) so they figured out this method:

First the sodium salt of tetranitrocubane is made. This is dissolved in a solvent (IIRC dioxane) and frozen with liquid nitrogen, and frozen N2O4 is placed on top. The solvent thaws and the nitro-group is added. Repeat until heptanitrocubane is made. Octanitrocubane cannot be made by the same process, instead NOCl is passed through a solution of it at -75*C followed by ozone until the blue colour of the nitroso compound is gone. You are left with octanitrocubane (55% yeild based on heptanitrocubane).

Tetranitrocubane is made by first making tetraminocubane and oxidizing it. Further derivatives of cubane cannot be made by this method, because if an amino and nitro group are next to each other they break the carbon-carbon and destroy the cubane skeleton, and you end up with messy oxidation products.

I'm currently researching it, it seems like something that can't be made in large amounts but being the first to make nitrocubanes in your garage... well that would just be cool. Heck, even making tetranitrocubane would be a huge accomplishment. Doing so would be a large investment of time in research and experimentation but it would certainly be extremely fun!

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[*] posted on 2-9-2005 at 07:23


Quote:
Originally posted by Chris The Great
For example, if someone found a OTC synthesis of glyoxal, we'd all be up to our ears in extremely high energy nitramines. CL-20, HHTDD, TNGU, etc.


I've been looking at glyoxal condensations myself lately, some interesting possibilities.

Nitromethane-glyoxal condensation then nitration to a 8 carbon caged dinitrobicyclo[2.2.2]octane hexanitrate :P. Maybe a polymer based on this is more likely :( Ive found reference that nitromethane-glyoxal will at least go to the cyclic dinitroinositol, an excess of NM was used to achieve this.

Depending on the extent of condensation, glyoxal-acetaldehyde may be interesting as well. I've no references to nitrates derived from glyoxal. Anyone?

Peroxides based on glyoxal-amines are also a possibility, that could out-perform the formaldehyde analogues. Nitration of these peroxides to nitramines another possibility. Many, many routes to explore.

[Edited on 2-9-2005 by Axt]
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[*] posted on 2-9-2005 at 20:09


Very cool stuff :) The problem however, is that most people do not want to use their precious nitric acid to make glyoxal. However, the air oxidation of ethylene glycol seems very promising- it was how I originally figured I would make glyoxal. After finding no mention of this process I decided it might not be worth it. And since formaldehyde has already been made in the home lab like this it is probably the easiest method, IMHO. Of course, buying it is even better. I'll have to look into that and see how it goes.

So far the most promising glyoxal condensation products are those or ureas, or formamide and then urea (this makes the HHTDD precursor, HHTDD > CL-20), and those with tetrazoles. Diaminotetrazole should make a product, that when nitrated should be very dense and very powerful. Chemsketch says 4.12g/cm3 +-0.1 but I don't trust it.
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[*] posted on 4-9-2005 at 05:19


I read an article a few weeks ago concerning all-nitrogen HEDMs. It was mostly a theoretical and computational paper, but they did state that one of the already synthesized salts containing the N5+ ion had a VOD of well over 10 km/s ( I think it was the SnF5- salt, and I think it was about 12 km/s VOD ). Unfortunately I haven't yet been able to find the paper again so I can't check the numbers.

Axt: I had that same idea concerning the cage compound from condensation of glyoxal and NM. I carried out the condensation which resulted in a caramel like water soluble product. I haven't tried nitrating it yet.
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[*] posted on 4-9-2005 at 07:14


Nice to see you around Microtek. I'm attaching the article relating to NM-glyoxal condensation to dinitroinositol. Which is run at low temp, excess NM and precipitates from methanol solution. Hopefully that means further condensation is possible. In the very least it does present an easy method for retrieving a pure product from the condensation reaction.

Cyclizations of Dialdehydes with Nitromethane. VII. Preparation of neo-Inosadiamine- 1,4
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[*] posted on 5-9-2005 at 13:21


Quote:
Originally posted by Quince
Some things are not clear from the article. For example, what are these all-nitrogen compounds? They have N_5- and N_5+ (or some other number, forget the exact subscripts). I don't get it. And why are they energetic?

[Edited on 2-9-2005 by Quince]


N10 is a solid. It detonates to release N2 which is a gas. Also, the formation of the nitrogen to nitrogen triple bonds releases considerable energy. Hence it's a powerful energetic material.

[Edited on 5-9-2005 by a123x]
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