Sciencemadness Discussion Board

New Energetic Materials - Current Research

 Pages:  1    3  ..  6

chemoleo - 5-5-2004 at 17:01

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!!

PHILOU Zrealone - 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:)

Blind Angel - 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

chemoleo - 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!

chemoleo - 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!

vulture - 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.

Phoenix - 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?

chemoleo - 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.

JohnWW - 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]

Geomancer - 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.

The article is interesting

chloric1 - 21-8-2004 at 19:38

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]

JohnWW - 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.

John W.

HAH

MadHatter - 24-8-2004 at 12:41

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 !

Rosco Bodine - 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 .

Where is this going?

Quince - 1-9-2005 at 23:48

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 7706 times


The_Davster - 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:)

Quince - 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]

Chris The Great - 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]

Quince - 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]

Chris The Great - 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!

To boldy go where no man in his garage has gone before!

Axt - 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 <a href="http://www.sciencemadness.org/scipics/axt/bis-nibgtn.jpg">dinitrobicyclo[2.2.2]octane hexanitrate</a> :P. Maybe a polymer based on <a href="http://www.sciencemadness.org/scipics/axt/bis-nibgtn2.jpg">this</a> 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]

Chris The Great - 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.

Microtek - 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.

Axt - 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.

<a href="http://scipic.ft100.net/images/dinitroinositol.pdf">Cyclizations of Dialdehydes with Nitromethane. VII. Preparation of neo-Inosadiamine- 1,4</a>

a123x - 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]

Thread merge & split

chemoleo - 5-9-2005 at 14:29

because I thought those novel compounds from the paper Quince dug out fit well into this thread.
Because of the broad nature of this thread, I also moved the details on glyoxal synthesis to this location, as this truly is a subject that merits its own attention.

If the subject on glyoxal condensations and energetics thereof is followed up (i.e. with experiments) I'll be happy to move the respective posts to a new dedicated thread.

So please, any major details/methods relating to particular compound discussed in this thread belong into a dedicated one, else it just gets unmanagable!

Chris The Great - 5-9-2005 at 14:52

I was in the middle of making an image of some compounds I found for my post, and when I previewed, everything crashed and I lost my post since you have stuck the topics together! Acck! Anyway, it wasn't that long, so here it is:

I was reading through a recent military document, and found information on two very interesting compounds they are currently researching, DTTO and IsoDTTO. Both have the formula C<sub>2</sub>N<sub>8</sub>O<sub>4</sub>. They have high densities (2.419 and 2.484). high heats of formation (179.5 and 175.7 kcal/mol) and astounding detonation pressures of 131.4 and 131.8 GPa! This puts HMX (38.2GPa) and even tetranitrotetrahedrane (51.2GPa) to shame! These explosives would be brisant to the extreme, and substantially more powerful than any other explosive made!

Here is a picture of their structures:
http://img274.imageshack.us/img274/6791/dtto9sb.jpg

[Edited on 5-9-2005 by Chris The Great]

[Edited on 5-9-2005 by Chris The Great]

((Blasta)) - 5-9-2005 at 17:59

I too have heard of this explosive as well. But, I am curious how it is manufactured. I remember a physics prof talking about an explosive that was one of the most powerful ever made, but it could not be manufactured in a standard atmosphere---it had to be inside a vaccum.

Chris The Great - 5-9-2005 at 22:58

It isn't manufactured, and there are lots of possible routes but I personally think none of them will work. I'll put them up into a graphic tommorrow, they all start from glyoxal, interestingly. Again, I don't think they'll work.

The reason is that the nitrogen rings with the two oxygens are very stable (surprisingly). The charges can resonate, forming alternating positive and negative charges around the ring, greatly stabilizing it. The nitrogen ring without oxygen simply doesn't form and if it does it immediatly decomposes into nitrogen and alkynes. With one oxygen, the ring has moderate stability, and with two it turns out to be very stable.
All proposed methods that I am aware of involve the ring or rings having only one oxygen at some point, and so I think the methods will probably fail. Who knows though, perhaps a method will oxidize the ring before it has a chance to decompose?

But, it's late and school starts tommorrow.

Review Article

Ramiel - 6-9-2005 at 03:08

<html>I see that an article reviewing the syntheses of DTTO <i>and</i> iso-DTTO has just been approved for public release. Now, if someone can verify that this article; “<a href="http://www.stormingmedia.us/23/2330/A233034.html"> Synthesis of 1,2,3,4-Tetrazines, 1,2,3,4-Tetrazine Di-N-oxides, Pentazole Derivatives, Pentazine Poly-N-oxides, and Nitroacetylenes</a>”<sup> 1</sup>, is what it says it is – a DARPA/AFOSR generated review – then perhaps we can decide if it is worth getting, and if so, find a way to acquire it.

Its USD$22.95 to buy a PDF for Joe Citizen, but perhaps there are persons who can legally acquire the document (although I wouldn’t recommend violating EULA-type agreements or committing corporate espionage upon a site that claims to be a Pentagon publisher!)

<sup>1</sup> Harold Shechter, M. Venugopal, D. Srinivasulu. 2003, ‘Synthesis of 1,2,3,4-Tetrazines, 1,2,3,4-Tetrazine Di-N-oxides, Pentazole Derivatives, Pentazine Poly-N-oxides, and Nitroacetylenes’, <i>Ohio State University Columbus Dept. of Chemistry</i>, Report Number A233034, 60 p.p.
</html>

Chris The Great - 6-9-2005 at 15:12

It is a general overview of the methods that don't work, and what methods they are probably trying right now. It also includes some information on other compounds but the main focus is DTTO and isDTTO. Yes, it is a DARPA/AFOSR related presentation, it is basically the overheads from some presentation. There is lots of writing on it, so there is a fair amount of information. I can also access it for free from a undisclosed source, but I'd rather it not went the way of the kewl-swarmed source, sorry guys :( (but feel free to PM if you need something specific, I'll try to get it for you)

http://rapidshare.de/files/4807062/Synthesis_of_High_Energy_...
1,671KB

Here are some other files related to the subject of recent high energy materials (non-DARPA/AFOSR stuff, originally from a roguesci torrent).
Here is a review on recent energetic materials, it was an interesting read, and is a good way to see what has been going on recently in the field:
http://rapidshare.de/files/4807149/New_Energetic_Materials.p...
1,989KB

Another similar journal, with some other energetic materials.
http://rapidshare.de/files/4807181/A_review_of_energetic_mat...
283KB

[Edited on 6-9-2005 by Chris The Great]

tetranitro-propane diurea

akinmad - 6-9-2005 at 20:07

I don't know if this substance is covered here (UTFSE yields no results). But while I was reviewing the New Energetic Materials.pdf I saw a substance called tetranitro-propane diurea (p16 shows the structure). The last column states that it's easy to prepare and has a very high VOD (9030) and good thermal stability.

While searching the net, I came across an article about the preparation of this substance. http://doi.wiley.com/10.1002/1521-4087(200104)26:2%3C63::AID-PREP63%3E3.3.CO;2-V

Name of the article is Synthesis, Characterization and Thermal Behaviour of 2,4,6,8-Tetranitro-2,4,6,8-Tetraazabicyclo[3.3.1]Nonane-3,7-Dione (TNPDU) and one of its Methylene Analogues
A. K. Sikder, G. M. Bhokare, D. B. Sarwade, J. P. Agrawal *
Its abstract states that :
2,4,6,8 - Tetranitro - 2,4,6,8 - tetraazabicyclo[3.3.1]nonane-3,7-dione (TNPDU) has been synthesized from propane diurea by nitration with nitric acid-acetic anhydride with a yield of 85 %. The molecular structure of the compound has been determined by elemental analysis, IR and 1H-NMR spectroscopy. Some of the properties including thermal and explosion delay behaviour of the compound and its mixtures with high explosives, are reported. An analogous compound 2,5,7,9-tetranitro-2,5,7,9-tetraazabicyclo[4.3.0]nonane-8-one (TNABN) has also been evaluated for some of the explosive properties considering its good stability and insensitiveness as compared to other nitrodiurea derivatives.

What is the cons and pros of this substance and can somebody who has access to this article upload it to the rapidshare?

S.C. Wack - 7-9-2005 at 04:43

here

A short time after I last mentioned PEP, it was removed from the library catalog and the list of journals, and UTFSE there is fruitless. Other Wiley journals are not affected, leaving me to wonder if they got an email from Wiley, I don't see how else this could have happened. It is still obtainable, however.

DUHHHHHHHHH!!!!!!!!!!!!!!!:

It has been pointed out to me that I uploaded the wrong pdf, starting on page 75 instead of 63. It has been corrected.

The S.C. stands for "Space Cadet" and although this name was chosen as a sort of homage to Wack, I will be the first to admit that it applies, perhaps more often than for most people.

[Edited on 8-9-2005 by S.C. Wack]

Octanitrocubane

franklyn - 18-9-2006 at 01:59

http://cst-www.nrl.navy.mil/%7Erichards/projects/slr1.html

.

deiki - 18-9-2006 at 09:05

I had found this few months ago, but I never seen it mentionned here:

http://www.dtic.mil/descriptivesum/Y2000/OSD/PE0603225D.pdf

"Polymeric carbon monoxide, the first of a new and potentially very interesting class of metastable High Energy Density Materials (HEDM) was synthesized under very high pressure and temperature in the laboratory and recovered for characterization at ambient conditions. Energy content of this class of materials is predicted to exceed that of known high explosives by a factor of 2 to 4."

Polycarbonyl monomer

franklyn - 18-9-2006 at 17:23

is metastable at ambient conditions and is synthesized by compressing liquid carbon monoxide at
pressures exceeding 5GPa , that's 50,000 atmospheres. Fairly straight forward and easier to make
than suboxide of carbon ( C3O2 ). Now if we can only peroxidate this :D

http://arxiv.org/PS_cache/physics/pdf/0112/0112068.pdf
and same here _
http://www.i-b-r.org/docs/polycarweb.pdf#search=%22polycarbo...

http://www.ictp.trieste.it/~pub_off/preprints-sources/1998/I...

.

franklyn - 9-2-2007 at 05:59

Yup works with CO2 also
CO2 glass
http://www.newscientisttech.com/article.ns?id=dn9339&fee...

.

Sauron - 9-2-2007 at 10:10

The REALLY amazing thing about that article is that some gullible reporter bought the notion that an explosive based on hydrazine, proven human carcinogen, is somehow environmentally friendly, what a laugh. TOXIC Al2O3!! that's alumina. Toxic alumina and green hydrazine. ROTF!

Or that a propellant mix that is LESS detectable by radar or satellite is somehow a Good Thing. It might be someone's good thing and someone else's Very Bad Thing all depending on which way it in pointed!

Axt - 31-5-2007 at 22:17

Quote:
Originally posted by Axt
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.

<a href="http://scipic.ft100.net/images/dinitroinositol.pdf">Cyclizations of Dialdehydes with Nitromethane. VII. Preparation of neo-Inosadiamine- 1,4</a>


OK, just ran across the nitration product of dinitroinositol in <a href="http://www.sciencemadness.org/talk/viewthread.php?tid=7518">Organic Chemistry of Explosives</a>, yeh it will form the tetranitrate but the book contradicts its reference, the patent reference GB1107907 says only 1 nitrate group can be introduced via HNO3/H2SO4 and four with HNO3/AcO, where the book says both give the tetranitrate. Supposedly the tetranitrate is too sensitive for practical use but the dinitrate has "significantly better properties" and must have been interesting enough to be studied by Lawrence Livermore Labs as its designated "LLM-101". It can be made by HNO3/chloroform nitration.

It doesnt look it, but accordring to LLNL its energy is estimated to be simular to HMX :o Must be more dense then it looks (though they dont define "energy". Its a simple reaction but crappy yields of dinitroinositol from NM + glyoxal.

[Edited on 2-6-2007 by Axt]

Mardec - 2-6-2007 at 23:33

Quote:
Originally posted by Axt
It can be made by HNO3/chloroform nitration.
[Edited on 2-6-2007 by Axt]


Is a chloroform / HNO3 nitration the same as a DCM/HNO3 nitration?

And can CHCl3 extract HNO3 from a watery solution like DCM?

Or did I misunderstood?

I am currently working on HNO3 100% through DCM, but DCM is a problem for me, where as Chloroform is easely available form me.

[Edited on 3-6-2007 by Mardec]

Axt - 3-6-2007 at 15:07

Yes and Yes, though HNO3 is less soluble in chloroform then DCM, you will still need a dehydrating agent as I assume water is more soluble in DCM/HNO3 then DCM alone.

A progress report by LLNL mentions that diluting the HNO3 helps prevent the tetranitrate but not entirely and that the tetranitrate "is a very sensitive material and should never be isolated dry". Though the dinitrate is insensitive and of interest because "of its energy, which is estimated to be simular to that of HMX. LLM-101 also has an exceptionally high temperature at the Chapman-Jouguet state". Its also a potential precursor to high energy polymers.

[Edited on 4-6-2007 by Axt]

The_Davster - 3-6-2007 at 18:13

Quote:
Originally posted by Axt
<a href="http://mihd.net/g4c6io">Organic Chemistry of Explosives</a>,


I have just spent the last couple days reading that pretty much cover to cover, seeing as this is the 'New energetic materials' thread, that book covers much of the weird and wonderful energetics. Best overview of the recent developments I have seen. Fascinating sections on nitrogen heterocycles.

[Edited on 5-6-2007 by The_Davster]

woelen - 5-6-2007 at 13:01

The link you quoted does not work. It asks for a password and both the whimsy and references passwords do not work. After login it tells me this is a non-existent subforum. Could you (or Axt) give a working link of that book?

Axt - 5-6-2007 at 15:15

Link work for me but kmno4 originally found and uploaded it to here: http://mihd.net/g4c6io

The_Davster - 5-6-2007 at 15:19

http://mihd.net/g4c6io

How strange, at the time I found that link it took me to the right place.
The link has now been edited

h0lx - 6-6-2007 at 00:23

Quote:
Originally posted by Sauron
...that an explosive based on hydrazine, proven human carcinogen, is somehow environmentally friendly, what a laugh...

it is. It decomposes to H2O and N2, when burned. A crash would be a whole another thing.

DeAdFX - 6-6-2007 at 08:15

Hydrazine is rather reactive towards oxygen shouldn't the stuff convert to H2O/N2 after a few weeks or so?

Phel - 25-6-2007 at 00:57

The Sila-Explosives Si(CH2N3)4 and Si(CH2ONO2)4: Silicon Analogues of the Common Explosives Pentaerythrityl Tetraazide, C(CH2N3)4, and Pentaerythritol Tetranitrate, C(CH2ONO2)4
Thomas M. Klapötke, Burkhard Krumm, Rainer Ilg, Dennis Troegel, and Reinhold Tacke

attached

Attachment: ja071299p.pdf (951kB)
This file has been downloaded 13190 times


franklyn - 25-6-2007 at 04:57

Quote:
Originally posted by Phel
The Sila-Explosives : Silicon Analogues of the Common Explosives

That's really cool , I thought for a long time about attaching oxy radicals to
silicones. To bad these " are extremely shock-sensitive materials and very
difficult to handle
".

.

Alternate Propulsion Energy Sources

franklyn - 25-12-2007 at 22:40

Take a walk on the wild side and read about speculative schemes for energetic materials
Metastable Helium , Free radical Hydrogen , Ultra cold neutron cataylsed fission , and so on.
http://stinet.dtic.mil/cgi-bin/GetTRDoc?AD=B088771&Locat...

Advanced Propulsion Concepts
AFRPL-TR-72-31 , JUN 1972 , AD0750554
http://handle.dtic.mil/100.2/AD750554
or here _
http://stinet.dtic.mil/cgi-bin/GetTRDoc?AD=0750554&Locat...

Abstract:
A study was conducted by an ad hoc group within the Air Force Rocket
Propulsion Laboratory during the calendar year of 1970 in an attempt to predict
the major propulsion developments that may occur in the next 30 to 40 years.
The report evaluates the future of conventional chemical rocketry based on
thermodynamic principles and revolutionary conceptual approaches to system
applications. Advanced concepts falling under the general headings of Thermal,
Field and Photon Propulsion are evaluated to a degree necessary to define their
potential.

The above was an earlier assessment of ongoing research in propulsion schemes which
reminds me ( though somewhat off topic ) of the subsequent Breakthrough Propulsion
Physics investigation that follows _

http://www.nasa.gov/centers/glenn/research/warp/warp.html

http://www.grc.nasa.gov/WWW/bpp/index.html

ABSTRACT:
In 1996, NASA established the Breakthrough Propulsion Physics program to seek the ultimate
breakthroughs in space transportation: propulsion that requires no propellant mass, propulsion
that attains the maximum transit speeds physically possible, and breakthrough methods of
energy production to power such devices. Topics of interest include experiments and theories
regarding the coupling of gravity and electromagnetism, vacuum fluctuation energy, warp
drives and wormholes, and superluminal quantum effects. Because these propulsion goals are
presumably far from fruition, a special emphasis is to identify affordable, near-term, and
credible research that could make measurable progress toward these propulsion goals. The
methods of the program and the results of the 1997 workshop are presented.
http://www.grc.nasa.gov/WWW/bpp/1997-J_AIAA_SpaceDr.pdf
1 9 9 8
http://gltrs.grc.nasa.gov/reports/1998/TM-1998-208400.pdf
2 0 0 5
http://www.grc.nasa.gov/WWW/bpp/2005-J_ANYAS_AssessBPP.pdf

A lighter primer on some proposals _
http://en.wikipedia.org/wiki/Breakthrough_Propulsion_Physics...
Alcubierre Warp drive _
http://en.wikipedia.org/wiki/Alcubierre_drive
Unproven or discounted ideas _
Go here _
http://web.archive.org
and enter this
http://www.grc.nasa.gov/WWW/bpp/ComnErr.html
Jun 03, 2004 , is the last update

.

Polynitrogen moieties

franklyn - 28-12-2007 at 16:57

A concise and informative overview of the current state of the art
of energetic molecular compounds can be viewed at this site here _
http://enermat.org.ru
click the navigational links < back || next > on the bottom of each
page or else their url's in order here _
http://enermat.org.ru/pyrazines.html
http://enermat.org.ru/furazans.html
http://enermat.org.ru/tnaz.html
http://enermat.org.ru/nitro.html
http://enermat.org.ru/ammomium.html

Just a thought
It would be interesting to see if compound number 6 depicted at the botom
of this page => http://enermat.org.ru/pyrazines.html
could add two azide groups by the action of N2O on the two amines. What
interesting heterocyclic variant may isomerize from that ?

______________________________________________


Theoretical analysis of polynitrogen moieties
http://www.qtp.ufl.edu/~bartlett/pdf/polynitrogen.pdf
Abstract:
Provides a theoretical analysis of fanciful hypothetical energetic Nitrogen moieties.

I have an idea that the eight member ring structure depicted on page 52 above
can be acheived , at least as a side group. Take away one carbonyl from cyanuric acid
and you have another simpler organic acid , 1H-1,2,4-Triazol-3,5-diol ( Urazol ) below left
http://www.emolecules.com/cgi-bin/more?vid=595279
which much as TCCA does , also tautomerizes into another pH dependent form
1H-1,2,4-Triazole-3,5-dione ( Urazole ) below right
http://pubchem.ncbi.nlm.nih.gov/summary/summary.cgi?cid=7291...

[img]http://pubchem.ncbi.nlm.nih.gov/image/imgsrv.fcgi?t=l&cid=72916[/img]
More references _
http://www.emolecules.com/cgi-bin/more?vid=595279
http://dtp.nci.nih.gov/dtpstandard/servlet/ChemNameServlet?t...
http://www.ncbi.nlm.nih.gov/sites/entrez?term=3232-84-6%7E%5...
Properties _
http://www.acros.com/DesktopModules/Acros_Search_Results/Acr...
http://iaspub.epa.gov/srs/srs_proc_qry.navigate?P_SUB_ID=113...
The following link in beteween < > pointy brackets will not parse correctly
copy and paste it into the address bar of your browser
< http://toxnet.nlm.nih.gov/cgi-bin/sis/search/r?dbs+toxline:@term+@rn+3232-84-6+@OR+@all+"" >
Equilibrium acidity constants have been determined for 1,2,4-triazolidine-3,5-dione (urazole),
several substituted urazoles, and other related acids, in both dimethyl sulfoxide (DMSO) and
aqueous solution. In DMSO, urazole has a pKa of 13.1. In water, urazole has a pKa of 13.1. In
water, urazole has a pKa of 5.8. In general, N-methyl and N-phenyl substituents are found to
acidify the urazole moiety, in both DMSO and water. The acidifying effects of these substituents
are attenuated by a factor of 3.3 in water. The solvent effects are ascribed to the aqueous
stabilization of urazole anions via hydrogen-bonding interactions and the aqueous-promoted
relief of lone pair-lone pair electronic interactions that manifest themselves upon deprotonation
of a hydrazyl proton in 1 and related species. That a hydrazyl proton in 1 is at least as acidic as
the imide proton in 1 is confirmed by comparison of 13C NMR spectra for the urazoles and
related nitrogen acids with 13C spectra for
- - - - - - - - - - - - - - - - - - - - - - - -


N-Chlorination of the amines to obtain 1,2,4-Trichloro-1,2,4-Triazole-3,5-dione _ 1 )
and reacting this with NaN3 should yield , 1,2,4-Triazido-1,2,4-Triazole-3,5-dione _ 2 )
essentially a symetric di-azido-hydrazyl group
which could isomerize producing an octagonal nitrogen ring _ 3 )

A much more fanciful notion would be to further substitute the Urazole carbonyls with hydrazine
C:O + H2NNH2 => H2O + C:NNH2 , to form Hydrazone groups _ 4 )
these can be reacted with nitrous oxide N2O
C:NNH2 + N2O => H2O + C:N-N=NN to obtain N4 Azidamines _ 5 )
( related thread here _ http://www.sciencemadness.org/talk/viewthread.php?tid=9370 )

polynitrogen.jpg - 20kB

chemoleo - 28-12-2007 at 17:14

Are there examples in the literature of carbonyls next to N-azides? Just wondering because surely the carbonyl will destablise any azide moiety due to its electron-withdrawing effect?

Beautiful summary in the enermat.org site... almost worth saving it and uploading it here!

franklyn - 28-12-2007 at 18:08

Quote:
Originally posted by chemoleo
Are there examples in the literature of carbonyls next to N-azides?

literature ? what literature :D , no none that I know of , bear
in mind I'm not a chemist so if it's not feasible then that's that.
Quote:
Originally posted by chemoleo
Beautiful summary in the enermat.org site... almost worth saving it and uploading it here!


U P D A T E
New Energetic Materials Is available as a pdf here _
http://my-lair.narod.ru/New_Energetic.pdf
* N O T E *
You must copy this url and paste it into the address bar of your browser to download
_________________________________

Way ahead of you , I already had , good notion to post it , only 1/2 MB
unfortunatley I know of no way to do this in the forum server itself
using the zip format ( problems unpacking )
For those who like me their unzipping utilities are " no good "
here is are three tested outside hosts , download and save
before opening _

http://www.keepmyfile.com/download/f364832074487

http://www.badongo.com/file/7077815

http://mihd.net/vp6tjn


If you wan to try to open the file attached below , try this
1. download and save to your computer
2. delete the - .zip - extension
3. click the file and select the utility to open it from the popup dialog box
4. drag the file you see inside to the desktop and click that to open it
5. again, repeat step 3
6. you should now see the contained .mht files and be able
to extract or view them directly in your browser.


[Edited on 11-1-2008 by franklyn]

Attachment: New Energetic Materials.zip (530kB)
This file has been downloaded 2149 times


Axt - 28-12-2007 at 18:48

The majority of that site, up the the plasticisers is directly copied from Thermochimica Acta 384 (2002) 187–204. I cant find the article for the plasticiser ect. portion but it has been available as pdf at some time here.

Attachment: a review of energetic materials synthesis.pdf (278kB)
This file has been downloaded 5022 times


Energetic high Nitrogen Heterocyclic compounds

franklyn - 28-12-2007 at 21:56

Quote:
@ Axt
Funny I had that since early September
didn't make the connection though

US patents of interest with preparations

7119179 - Prep of high Nitrogen compounds ( many types )
6657059 - 3,6bis(1H-1,2,3,4-Tetrazol-5-ylamino)-1,2,4,5-Tetrazine
6570022 - bis-(1(2)H-Tetrazol-5-yl)- Amine
6552201 - 3,3'-Diamino-4,4'-Azo Furazan
6458227 - 3,6-bis(1H-1,2,3,4-Tetrazol-5-ylamino)-1,2,4,5-Tetrazine
6388087 - 3,3'-Dinitro-4,4'-Hydrazo Furazan
6358339 - 3,3'-Diamino-4,4'-Azoxy Furazan
6342589 - 3,3'-Azo(bis)(6-Amino-1,2,4,5-Tetrazine)
6312537 - Tetrazoles

U P D A T E
Paper with preparations of insesitive aza-heterocyclic nitramine ureas
http://my-lair.narod.ru/v26pp63-68.pdf
* N O T E *
You must copy this url and paste it into the address bar of your browser to download

[Edited on 11-1-2008 by franklyn]

TNPDU

franklyn - 27-2-2008 at 07:26

Quote:
U P D A T E
Paper with preparations of insesitive aza-heterocyclic nitramine ureas
http://my-lair.narod.ru/v26pp63-68.pdf

Edit option lapsed so item of dead link above is now available here
http://www.sciencemadness.org/talk/viewthread.php?tid=7518&a...
Synthesis, Characterization and Thermal Behaviour of
(TNPDU) 2,4,6,8-Tetranitro-2,4,6,8-Tetraazabicyclo[3.3.1]Nonane-3,7-Dione
and one of its Methylene Analogues

A. K. Sikder, G. M. Bhokare, D. B. Sarwade, J. P. Agrawal
Propellants, Explosives, Pyrotechnics 26, 63 - 68 (2001)


On N-Cl substitutions
http://www.sciencemadness.org/talk/viewthread.php?tid=4282&a...

.

Ritter - 2-8-2008 at 14:08

Quote:
Originally posted by chemoleo
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?



You have the structure correct. It is 1,5-dinitrobiuret, aka DNB.

There is not much literature on this, which is surprising when you consider thae fact that it was first made in Germany in 1898! It was resynthesized in Germany in 2004.

Heating nitrourea to decomposition just gives you NOx. They use a 2-step nitration of biuret: first with mixed acids to get 1-nitrobiuret, then with fuming HNO3 at ice temperatures to get the DNB.

The Thiele prep is attached.

[Edited on 2-8-2008 by Ritter]

DNB.jpg - 14kB

Ritter - 2-8-2008 at 14:12

Here is the original article abstract.

1,5-Dinitrobiuret.jpg - 52kB

Formatik - 2-8-2008 at 14:56

"nitrobiuret ... prepared by adding biuret in small portions to a mixture of concentrated nitric and sulphuric acids, separates from water as a white, crystalline powder"

100g biuret is added under stirring into an ice cooled mixture of HNO3 (66 ccm, D = 1.4) and conc. H2SO4 (250 ccm), after the end of the reaction (2 hours) it is poured onto ice, and the nitrobiuret is washed with water and alcohol. The remaining nitrobiuret in the mother liquor is obtained by precipitating with mercury nitrate.

"produced when the finely divided nitro-deriative is added to fuming nitric acid cooled with a freezing mixture".... The solution is then evaporated in a vacuum in the dark over "Natronkalk" (Ca(OH)2 plus NaOH), and H2SO4. The nitric acid is 100% pure.

The German references say it just deflagrates at 124 deg. The potassium salt (K2C2HO6N5) also deflagrates when heated.

[Edited on 2-8-2008 by Schockwave]

Ritter - 2-8-2008 at 17:18

If DNB is such great stuff, why isn't there a lot of literature on it? There are only half a dozen U.S. patents that mention its use in coatings & a 1960 patent with a brief mention of its use in a diazo reprographic system. Note the different decomposition temperature given.

[Edited on 2-8-2008 by Ritter]

US3453112.jpg - 10kB

Formatik - 2-8-2008 at 22:40

Quote:
Originally posted by Ritter
If DNB is such great stuff, why isn't there a lot of literature on it? There are only half a dozen U.S. patents that mention its use in coatings & a 1960 patent with a brief mention of its use in a diazo reprographic system.


The material has been rediscovered, interest may grow. A blast from the past. Back from the dead. If the lower decomposition temperature is correct, then it has for the purposes of commercial application the draw back of a low decomposition point. Another thing is that it forms salts, so may be incompatible with metals. Despite those it has good chemical stability, and is up there with the greats PETN, HMX, RDX, etc. in terms of energy output.

Quote:
Note the different decomposition temperature given.


Whatever its decomposition temperature really is, I usually tend to take patent values secondary to periodicals. But at least we know the range. That is at least until someone else whips out another figure.

Ritter - 6-8-2008 at 05:20

Quote:
Next-generation Explosives: More Power And Safety Without The Pollution
ScienceDaily (May 27, 2008) — Scientists in Germany are reporting development of a new generation of explosives that is more powerful than TNT and other existing explosives, less apt to detonate accidentally, and produce fewer toxic byproducts.

Their study of these more environmentally friendly explosives is scheduled for the June 24 issue of ACS’ Chemistry of Materials, a bi-weekly journal.

In the new study, Thomas M. Klapötke and Carles Miró Sabate point out that conventional explosives such as TNT, RDX and HMX, widely-used in military weapons, are rich in carbon and tend to produce toxic gases upon ignition.

In addition to polluting the environment, these materials are also highly sensitive to physical shock, such as hard impacts and electric sparks, making their handling extremely dangerous. Greener, safer explosives are needed, the researchers say.

To meet this need, Klapötke and Sabate turned to a recently explored class of materials called tetrazoles, which derive most of their explosive energy from nitrogen instead of carbon. They identified two promising tetrazoles: HBT and G2ZT. The researchers developed tiny “bombs” out of these materials and detonated them in the laboratory. The materials showed less sensitivity to shock than conventional explosives and produced fewer toxic products when burned, the researchers say.


--------------------------------------------------------------------------------

Journal reference:

Klapötke, Thomas M. and Sabaté, Carles Miró. Bistetrazoles: Nitrogen-Rich, High-Performing, Insensitive Energetic Compounds. Chem. Mater., 2008 doi: 10.1021/cm703657k


Here is HBT:

http://en.wikipedia.org/wiki/HBT_(explosive)

and here is G2ZT:

http://en.wikipedia.org/wiki/G2ZT

There is no structure in the Wiki article.








[Edited on 6-8-2008 by Ritter]

sparkgap - 6-8-2008 at 06:01

"Bis(3,4,5-triamino-1,2,4-triazolium)-5,5'-azotetrazolate."

Looks dodgy, unless "1,3,5-triamino-1,2,4-triazolium" was what was intended.

sparky (~_~)

Ritter - 6-8-2008 at 06:18

Quote:
Originally posted by sparkgap
"Bis(3,4,5-triamino-1,2,4-triazolium)-5,5'-azotetrazolate."

Looks dodgy, unless "1,3,5-triamino-1,2,4-triazolium" was what was intended.

sparky (~_~)


I think you are correct that he has prepared a salt. Here is a snippet from the Web on the makeup of G2ZT:

Quote:
3,4,5-triamino-1,2,4-triazolium cation similar ..... “Salts of 5,5’-Azotetrazolate” Eur. J. Inorg. Chem. 2002, 834


There is discussion of these salts in this thread: http://www.sciencemadness.org/talk/viewthread.php?tid=8144&a....

I just sent an email request to Herr Prof. Dr. Klapoetke for a pdf or a graphics file to get the correct structure & prep. If I receive anything back I'll post it here. In the meantime here is my revised version the composition of G2ZT:

And here is a Google Book reference of the 5,5'-azotetrazolate dianion: http://tinyurl.com/5uf4np












[Edited on 6-8-2008 by Ritter]

G2ZT.gif - 6kB

The_Davster - 6-8-2008 at 07:21

Can't get this as a pdf for some reason, it just will not load. Odd. Here is some c/p from the HTML article.

Preps:
Synthesis of 5,5′-Hydrazinebistetrazole (HBT). Sodium 5,5′-azotetrazolate pentahydrate (50.00 g, 166.63 mmol) was dissolved in 1.4 L of water before an excess of magnesium powder (28.71 g, 1.18 mol) was added to the yellow solution. The reaction mixture was refluxed for 6 h and left to cool to room temperature under a stream of nitrogen. The excess magnesium powder was filtered along with some magnesium hydroxide, which precipitated on cooling (this operation has to be carried out quickly in order to prevent oxidation of sodium 5,5′-hydrazinobistetrazolate) into a sidearm flask containing 160 (1.58 mol) mL of 6 M HCl (once the filtrate came into contact with the HCl no oxidation of the hydrazino-bridged compound was observed). A white solid immediately formed and the sidearm flask was shaken thoroughly to favor the precipitation of the product. The slightly yellow powder was filtered off and washed thoroughly with water and with acetone, yielding the desired product as a white powder (26.64 g, 95.2%). Crystals of the compound suitable for structure determination were grown by dissolving a small amount of the solid in boiling water and letting to cool slowly. C2H4N10 (calcd/found, %): C, 14.29/14.27; H, 2.40/2.58; N, 83.31/82.68. Mp (Büchi B-540, uncorrected): 206.9–208.2 °C (decomposition). 1H NMR (DMSO-d6, 400.18 MHz, 25 °C, TMS): δ 9.66 (4H, s, NH). 13C{1H} NMR (DMSO-d6, 100.63 MHz, 25 °C, TMS): δ 159.68 (s, CN3); Decomposition Experiments. MS (EI): m/z = 12 (0.1, C+), 14 (0.6, N+), 16 (1.2, NH2+), 17 (3.6, NH3.+), 26 (3.2, CN+), 27 (20.4, HCN.+) and 28 (100.0, N2.+). IR (Gas): Δν (cm−1) 3332 (w, NH3), 3336 (s, HCN), 3282 (s, HCN), 2168 (w, HCN), 2102 (w, HCN), 1621 (m, NH3), 1431 (w, HCN), 1380 (w, HCN), 965 (vs, NH3), 926 (vs, NH3), 732 (s, HCN), 710 (vs, HCN), 679 (s, HCN).

Synthesis of Bis(3,4,5-triamino-1,2,4-triazolium) 5,5′-Azotetrazolate (G2ZT). To an aqueous solution of sodium azotetrazolate pentahydrate (31.01 g, 103.25 mmol) in 150 mL of hot water was added 3,4,5-triamino-1,2,4-triazolium bromide (40.185 g, 206.50 mmol) in 100 mL of hot water. The mixture was stirred and boiled for 3 h and the title compound, only slightly soluble in hot water, started to precipitate. After slow cooling to room temperature, the yellow solid was filtered, washed with a small amount of cold water and methanol, and air-dried (37.24 g, 91.6%). Crystals suitable for X-ray analysis were obtained by recrystallization from water of a small amount of the compound. C6H14N22 (calcd/found, %): C, 18.28/18.22; H, 3.58/3.68; N, 78.15/77.95. Mp (Büchi B-540, uncorrected): 211.3–212.4 °C (decomposition), 1H NMR (DMSO-d6, 400.18 MHz, 25 °C, TMS): δ 6.60 (4H, s, C-NH2), 5.58 (2H, s, N-NH2). 13C{1H} NMR (DMSO-d6, 100.63 MHz, 25 °C, TMS): δ 173.24 (2C, [C2N10]2−;), 150.31 (2C, C-NH2); Decomposition Experiments. MS (EI): m/z = 12 (0.6, C4+), 13 (0.3, CH3+), 14 (3.4, CH22+, N+), 15 (0.4, CH3+), 16 (10.0, CH4.+, NH2+), 17 (13.6, NH3.+), 26 (5.8, CN+), 27 (38.0, HCN.+), 28 (100.0, N2.+), 31 (0.1, NH2NH+), 32 (0.2, NH2NH2.+), 38 (0.0, CCN3+), 39 (0.0, CHCN2+), 40 (0.1, CH2CN+), 41 (0.2, CH3CN.+). IR (Gas): Δν (cm−1) 3450 (w, NH3), 3333 (s, HCN), 3285 (m, HCN), 2166 (w, HCN), 2102 (w, HCN), 1623 (s, NH3), 1431 (w, HCN), 1382 (w, HCN), 964 (vs, NH3), 925 (vs, NH3), 731 (m, HCN), 714 (vs, HCN), 681 (m, HCN), 667 (w, NH3), 624 (vw, NH3).


Product:

g2zt.JPG - 11kB

Ritter - 6-8-2008 at 08:57

Quote:
Originally posted by The_Davster
Can't get this as a pdf for some reason, it just will not load.


I just received this from the author.

Attachment: 403.pdf (956kB)
This file has been downloaded 3972 times


The_Davster - 6-8-2008 at 09:20

A recent article on the use of some of these high nitrogen compounds in pyrotechnics.

From the usual group which seems behind all these nifty compounds

Attachment: green pyro.pdf (1.2MB)
This file has been downloaded 3747 times


New energetic from Prof Dr Klapötke

Ritter - 6-8-2008 at 12:30

Quote:
Phys Chem Chem Phys. 2008 Aug 7;10(29):4340-6. Epub 2008 Jun 9.

Triaminoguanidinium dinitramide-calculations, synthesis and characterization of a promising energetic compound.

Klapötke TM, Stierstorfer J.

Energetic Materials Research, Department of Chemistry and Biochemistry, University of Munich (LMU), Butenandtstr. 5-13, D-81377, Germany. tmk@cup.uni-muenchen.de.

The highly energetic compound 1,3,5-triaminoguanidinium dinitramide was prepared in high yield (82%) according to a new synthesis by the reaction of potassium dinitramide and triaminoguanidinium perchlorate. The heat of formation was calculated in an extensive computational study (CBS-4M). With this the detonation parameters of compound were computed using the EXPLO5 software: D = 8796 m s(-1), p = 299 kbar. In addition, a full characterization of the chemical properties (single X-ray diffraction, IR and Raman spectroscopy, multinuclear NMR spectroscopy, mass spectrometry and elemental analysis) as well as of the energetic characteristics (differential scanning calorimetry, thermal safety calorimetry, impact, friction and electrostatic tests) is given in this work. Due to the high impact (2 J) and friction sensitivity (24 N) several attempts to reduce these sensitivities were performed by the addition of wax. The performance of was tested applying a "Koenen" steel sleeve test resulting in a critical diameter of >/=10 mm.



Triaminoguanidinium dinitramide.jpg - 75kB

BPTAP

Ritter - 3-9-2008 at 11:01

Thermally-stable inner salt compounds have been known for some time. Los Alamos recently had a U.S. Patent Application published that describes the preparation of the new secondary explosive BPTAP: http://v3.espacenet.com/origdoc?DB=EPODOC&IDX=US20081850...

Additional info on BPTAP & other recent developments in explosives is found here: http://www.pnas.org/content/103/27/10322.full

The process flow & final structure are shown here:

[Edited on 3-9-2008 by Ritter]

BPTAP.gif - 33kB

hissingnoise - 17-11-2008 at 07:00

Does anyone have synth., or other info on the new energetic developed in LANL by D Chavez?
Six carbons, two nitro and four nitrate groups would make for good O.B and its density, too, is quite high.
That and the low m.p. makes it sound particularly interesting.


[Edited on 25-12-08 by The_Davster]

497 - 17-11-2008 at 20:41

It looks like a very interesting little compound.

Here it is:

[Edited on 25-12-08 by The_Davster]

Attachment: Synthesis of an Energetic Nitrate Ester.pdf (376kB)
This file has been downloaded 4365 times


hissingnoise - 18-11-2008 at 07:42

Many thanks, 497; it's great to have a detailed synthesis at hand.
The OB at zero makes it as powerful as nitroglycol and predicted brisance is higher(high density), so we'll hear a lot more of this explosive.
ETN looks pedestrian, by comparison.
What still commends ETN, though, is its simplicity.
After experience of HMTD, cyclonite, NGL and methyl nitrate, ETN's next on the list.


[Edited on 25-12-08 by The_Davster]

Mr. Wizard - 18-11-2008 at 10:21

"BTW, the unfair "redneck" reference to Mega's site was a stupid response to the anti-Obama vitriol I saw there.
I hope it didn't offend."
To your credit you did say it was unfair, but then you try to rationalize it. If it was an ant-Bush diatribe, would you feel the need to interpret the politics of the site for us?

Axt - 20-11-2008 at 01:05

Quote:
Originally posted by hissingnoise
Does anyone have synth., or other info on the new energetic developed in LANL by D Chavez?
Six carbons, two nitro and four nitrate groups would make for good O.B and its density, too, is quite high.
That and the low m.p. makes it sound particularly interesting.
RS. (redneck's science?) has a thread on it, but I can't access synth. details.


Very simular structure to that found in US patent 2381406, though without the methylene bridge. Its description (Six carbons, two nitro and four nitrate groups) also fits the nitration product of dinitroinositol I mentioned on the second page of this thread which supposedly also posesses performance simular to HMX.

hissingnoise - 20-11-2008 at 07:23

Axt, your reference to the second page got me thinking I should read the entire longrunning thread, once-and-for-all.
I've gotten through (phew!) a large section, and now I'm poly-nitrogened out. . .
'Think I'll go lie down for a while---say, a week, maybe.

'Seriously, there seems to have been a veritable explosion of new energetics in the last several years.
How many, though, will make it into actual service?

497 - 21-11-2008 at 11:28

Hah! I know how you feel, one time I read almost the whole DPPP thread... Only to be disappointing in the end by finding out it was in fact just AP! :P That's life.

Formatik - 5-1-2009 at 19:08

Here's an energetic that has been under research in rocketry, as it produces high-performance, solid propellants, e.g. for this see EP0959058 Isp of 348.8 for HNF/HTPB/Al mixture (332.9 for AP counterpart). It also burns with smokeless combustion and is not hygrosopic. Some properties below, mainly from Aerospace Propulsion Products B.V.:

Hydrazinium nitroformate
N2H5C(NO2)3 = CH5N5O6
mw: 183.09.
color: orange-yellow
Density: 1.872 g/cc.
Mp. 124 deg.
heat of formation: -17.2 kcal/mol.
Friction sensitivity: 25-36 N (RDX: 120 N).
Impact sensitivity: 2-4 Nm (RDX: 7.5 Nm).
UN test series III, thermal stability
test at 75 deg: passed.
Electrostatic discharge: 3-6 J (RDX: >4.5 J).
toxicity-LD50: 128 mg/kg (RDX: 100 mg/kg).

Though nothing about its explosive properties. Kamlet's method shows at 1.87 an estimate of 8261 m/sec close to as good as the exp. value of FOX-7 (8340m/s) and 36.4 GPa (estimated for FOX-7: 34.0; RDX: 34.6).

[Edited on 5-1-2009 by Formatik]

Taoiseach - 6-1-2009 at 04:09

Nitroformates are salts of trinitromethane. It is explosive by itself and forms explosive metal salts; energetic complexes such as ethylenediamine-copper-nitroformate are also possible.

Definetely an interesting compound, but difficult to make. I searched the forums and didn't find report of a working synthesis :(

Possible routes include

-reacting acetylene with fuming nitric acid in presence of Hg catalyst (nitrate is used comercially)
-react fuming nitric acid with isopropyl alcohol -> very bad yields; 150ml acid give ~10g if I remember correctly
-react silver nitrit with iodoform (I didn't find a detailed description)
-make tetranitromethane from fuming nitric acid and acetic anhydride; this can be reacted with alkali hydroxide to yield the salt of nitroform

Nicodem - 16-3-2009 at 05:31

Coincidently I stumbled upon this paper and thought to post it in case anybody is interested:

Energetic Ethylene- and Propylene-Bridged Bis(nitroiminotetrazolate) Salts
Young-Hyuk Joo, Jean'ne M. Shreeve
Chemistry - A European Journal, 15 (2009) 3198-3203.
DOI: 10.1002/chem.200802326

Attachment: Energetic Ethylene- and Propylene-Bridged Bis(nitroiminotetrazolate) Salts.pdf (247kB)
This file has been downloaded 2080 times


TETS - 10-11-2009 at 18:43

Today i was reading a russian book (via google translate),then i saw a strange composition which was R.D.X/tungsten 50:50.The interesting thing about this stuff is very high value of Plate dent test,which is 8.09(compare with 7.35 for OCTOL).
Also it has very high D:2.9 and just medium VOD of 6500.These figures show that brisance actually related more to density than VOD IMO.
I hope this is right thread for posting that.


hissingnoise - 11-11-2009 at 02:38

Quote: Originally posted by TETS  
Today i was reading a russian book (via google translate),then i saw a strange composition which was R.D.X/tungsten 50:50.

Hi TETS, yes, it's the right thread, and W/RDX is a strange comp..
Sintered tungsten has been used in S/C liners but RDX already has a low OB and PD tests tell little about explosive power.
Inerts reduce brisance but the hardness of tungsten increases the dent-effect. . .

User - 11-11-2009 at 03:21

Well in that case any hard metal should do the job to some extend.
How should i imagine this kind of composition?
A mean a fine powder mix would result in the metal being burned during detonation , right ?
Also larger particals would form (supersonic) flying bits of metal all over the place, making it a very unpleasant experience to be around.

Someone who can give some clarity ?

hissingnoise - 11-11-2009 at 03:43

Quote: Originally posted by User  

A mean a fine powder mix would result in the metal being burned during detonation , right ?
Also larger particals would form (supersonic) flying bits of metal all over the place, making it a very unpleasant experience to be around.

Larger particles would be pulverised on detonation but not oxidised!
As I said---the OB of RDX is on the low side for such a powerful HE.
Its detonation produces less smoke than, say, TNT, but it's still dark. . .

[Edited on 11-11-2009 by hissingnoise]

User - 11-11-2009 at 03:53

Thanks, I didnt take the oxygen balance in account, I guess i need glasses :)
Well lets suppose it isnt capable of "burning" the metal particals.
Some kind of thermobaric effect would come into play I can imagine.
Due to the incredible heat produces by the detonation the particals probably burn up in the air unless they are big enough.
Does this text say anything about mesh size?

hissingnoise - 11-11-2009 at 04:04

Any thermobaric effect would be very small since RDX, on detonation, produces a quantity of CO at very high temperature. . .

hissingnoise - 11-11-2009 at 04:25

Quote: Originally posted by User  
Well in that case any hard metal should do the job to some extend.

Some metal powders can reduce the thermal stability of RDX; lead, e.g. has a significant effect in this regard. . .

argyrium - 11-11-2009 at 11:53

Quote: Originally posted by TETS  
Today i was reading a russian book (via google translate),then i saw a strange composition which was R.D.X/tungsten 50:50.The interesting thing about this stuff is very high value of Plate dent test,which is 8.09(compare with 7.35 for OCTOL).
Also it has very high D:2.9 and just medium VOD of 6500.These figures show that brisance actually related more to density than VOD IMO.
I hope this is right thread for posting that.



I believe these and similar formulations are also know as Dense Inert Metal Explosives (DIME). Read http://tinyurl.com/y8cojx


hissingnoise - 12-11-2009 at 03:38

Yes, I'd forgotten about them---they were in the news after the Gaza 'adventure', but then, M/A is neccessarily a very nasty business. . .

Microtek - 13-11-2009 at 08:30

I remember reading about this composition (50:50 RDX:W). IIRC, the authors were of the opinion that the abnormally deep dents were due to abrasion. If that is indeed the case, it probably isn't a very useful effect.

-=HeX=- - 10-1-2010 at 12:59

A bit OT but I can safely and confidently tell you that a mix of Hydrazine Azide, Hydrazine Perchlorate and PETN, mixed to OB neutral, makes a VERY good HE for chaped chardes, however it sucks up moisture like mad so it has to be sealed damn well. I left s 2" CSC for 6 months and she still fired, penetrating a 4" RHS plate and punching through the 2" wooden backing - the only target I had on hand at the time. I tamped the SC after sealing it to the target with a cornstarch/water thixotropic mix in a 5gal bucket which was also glued to the target. Ignition was electric, rear-center priming with a CLD (A variant on Microteks design) and a 5g booster of cast PETN:ETN mix ala Rosco Bodine.

I see a beautiful future for N2H4 based material :)

I reckon the plate dent with W added to RDX is doe to the Abrasion as said by Microtek, and due to very dense hot W particles applying a lot of KE to the plate when 'pushed' by the RDX. Or maybe the W burns...

PHILOU Zrealone - 5-3-2010 at 06:31

Quote: Originally posted by -=HeX=-  
A bit OT but I can safely and confidently tell you that a mix of Hydrazine Azide, Hydrazine Perchlorate and PETN, mixed to OB neutral, makes a VERY good HE for chaped chardes, however it sucks up moisture like mad so it has to be sealed damn well. I left s 2" CSC for 6 months and she still fired, penetrating a 4" RHS plate and punching through the 2" wooden backing - the only target I had on hand at the time. I tamped the SC after sealing it to the target with a cornstarch/water thixotropic mix in a 5gal bucket which was also glued to the target. Ignition was electric, rear-center priming with a CLD (A variant on Microteks design) and a 5g booster of cast PETN:ETN mix ala Rosco Bodine.

Hi Hex,
Just a side note about mixing weird and energetic HE stuffs...always think first of possible cross reactions....
1°)NH2-NH2.HN3 + NH2-NH2.HClO4 might free HN3 because NH2-NH2.HClO4 is very hygroscopic and acidic salt.
HN3 is bad news as is HCN (cyanide).
2°) PETN is not advisable in mildly acidic conditions...HP can then favourise hydrolysis and subsequent oxydoreduction, runnaway and explosion. Nitric esters ought to be in neutral media for storage.
3°)Transesterification can be achieved between the alcohol nitrate and the perchloric amine salt.
R-O-NO2 + N2H4.HClO4 <==> R-O-ClO3 + N2H4.HNO3
So in the mix you get little by little some perchloric ester forming...

No need to remind you your last summer mishaps with glycerol triperchlorate and the sensitivity of the PE tetraperchlorate brother....

To my feeling, you should be very cautious with those shaped charges and detonators...they might explode spontaneous or upon the slightest induction after a while.

-=HeX=- - 5-3-2010 at 14:44

Hmmm. I never thought of that... However, I reckon if we keep the water out, it may be 'safe'. Perhaps I will experiment more - but keep the storage tests FAR from people!

Another point - I am working on Hydrazine Nitroformate at the moment - trying to find a method to use. I am starting from Hydrazine Sulphate, and could freebase to the Hydrazine Hydrate... Is this novel material worth my time? Oh, and can anyone tell me the formula of Ammonium Dinitramide - I cannot remember it! My interest at the moment is Zero Carbon Energetics/low Carbon. I will explain why later on - I have this theory you see...

BTW, PHILOU, U2U me with your newest email address - the last one I tried got a wierd automatically generated reply in Dutch...

PHILOU Zrealone - 12-3-2010 at 10:22

Quote: Originally posted by -=HeX=-  

Another point - I am working on Hydrazine Nitroformate at the moment - trying to find a method to use. I am starting from Hydrazine Sulphate, and could freebase to the Hydrazine Hydrate... Is this novel material worth my time? Oh, and can anyone tell me the formula of Ammonium Dinitramide - I cannot remember it! My interest at the moment is Zero Carbon Energetics/low Carbon.

-HNF is not a novel material, it is for sure interesting. But slightly over oxygenated....
2 NH2-NH2.HC(NO2)3 --> 5 N2 + 5 H2O +2 CO2 + 3/2 O2

Ammonium dinitramide is simply NH3.HN(NO2)2

-=HeX=- - 12-3-2010 at 13:57

I was fairly sure it was 'relatively new'.

Still, it is interesting - I have a special love for the N2H4 based materials as they are just so interesting!

ADN is the next stop for my lab I think! It is maybe good for my rocket motors :)

Microtek - 12-3-2010 at 14:22

Then you need effective cooling. I made KDN via the sulfamic acid route some years ago, and the CaCl2/crushed ice cooling that I used was barely adequate even though it got to aroung -55 C.

franklyn - 16-3-2010 at 08:52


@ -=HeX=-

Each mol of the Hydrazine Nitrofrom salt yields 6.75 gas mols

4 { ( N2H4 )•HC(NO2)3 } => 4 CO2 + 10 H2O + 10 N2 + 3 O2

Trinitroethane is acid and should form a nitronate salt with hydazine
one mole of compound will yield 8 gas mols

2 { ( N2H4 )•CH3C(NO2)3 } => CO2 + 3 CO + 7 H2O + 5 N2

Trinitroethane has been known since late in the 19 th century. Originally made from
Methyl Iodide and Silver Nitroform in Acetonitrile. Organic Chemistry of Explosives- Agrawal , page 13

Cheaper reagents that should work as well would be Methyl Bromide and Lithium Nitroform in DMSO

∆Hf = - 26 kcal/mol (s), melting pt. 57 ºC, Boiling pt. 183 ºC , Density ρ = ( mol wt 165 / mol vol 1.0 ) = 1.65 gm/cc

http://www.chemspider.com/Chemical-Structure.11197.html
http://cdb.ics.uci.edu/cgibin/ChemicalDetailWeb.psp?chemical...
http://pubchem.ncbi.nlm.nih.gov/summary/summary.cgi?sid=1549...
http://www.ncbi.nlm.nih.gov/sites/entrez?LinkName=pcsubstanc...

.

PHILOU Zrealone - 17-3-2010 at 05:28

@Franklyn,
To be of considerable acidity a nitrocompound must hold an hydrogen atom on the C holding the NO2 group (alfa position)...in CH3-C(NO2)3 there are only H in beta position and thus the acidity will be very much lower than in nitroform.

Do you have pKa datas on 111-trinitroethan to check if an hydrazinium salt might form?

Maybe a mix of hydrazine and TNE might work even if the molecules aren't joined into a salt; but the density will be lower and it is possible both doesn't mix well...

I would better suggest to get a better OB to work on the two following compounds:
1°) Cyanhydrazide nitroformate
N#C-NH-NH2 (cyanhydrazide) + HC(NO2)3 --> N#C-NH-NH3C(NO2)3
C2N6H4O6 --> 2 CO2 + 2 H2O + 3 N2
The introduction of a cyano group increases the energy output because it stocks some energy in the triple link.
2°) Hydrazinium dinitrocyanomethanate (dinitroacetonitrile salt)
NH2-NH2 + HC(NO2)2CN --> NH2-NH3C(NO2)2CN
C2N5H5O4 --> 2 CO + 5/2 N2 + 2 H2O + 1/2 H2

[Edited on 17-3-2010 by PHILOU Zrealone]

franklyn - 20-3-2010 at 11:56

@ PHILOU Zrealone

It does not seem that replacing the lone nitro group of Nitromethane with a
trinitromethyl group would make the methyl group behave much differently ,
if this is viewed as a primary methyl compound , ( ' methyl ' trinitromethane ).
Reduction of Trinitroethane to a dinitro compound is the observed reaction
with bases , adducts have not been documented , so may not form as such.
Your doubts are supported by the stated absense of H-bond doners in the
" Predicted Properties " subpart of the first reference I cited above _
http://www.chemspider.com/Chemical-Structure.11197.html

Organic Chemistry of Explosives - Agrawal , Quoted from page 54
" In Section 1.10.2.3 we observed that a base can react with 1,1,1-trinitromethyl compounds
to either remove an acidic proton or act as a nucleophile to displace a nitro group.
Section 1.10.2.3 , page 41 , ( imaged below )

An interesting azido derivative applying this path is desribed in the attached patent
1,1,1-Azidodinitroethane US patent 4472311

Organic Chemistry of Explosives - Agrawal , References cited on page 13
" synthesis and chemistry of 1,1,1-trinitromethyl compounds has been extensively reviewed "

9. F. G. Borgardt, P. Noble. Jr and W. L. Reed, Chem. Rev., 1964, 64, 19.

114. L. A. Kaplan, in The Chemistry of the Nitro and Nitroso Groups, Part 2, Organic Nitro Chemistry
Series, Ed. H. Feuer, Wiley-Interscience, New York., Chapter 5, 289–328 (1970).

115. (a) Nitro Paraffins (Ed. H. Feuer), Tetrahedron, 1963, 19, Suppl. 1; (b) Nitro Compounds (Ed.
T. Urbanski), Tetrahedron, 1964, 20, Suppl. 1.

.

Attachment: 1,1,1-Azidodinitroethane US4472311.pdf (191kB)
This file has been downloaded 1178 times CH3C(NO2)3 Organic Chemistry of Explosives _ pg.41.gif - 59kB

12332123 - 21-3-2010 at 02:15

Well, with regard to the need for alpha hydrogens, what about 1,1-2,2-tetranitroethane salts? Depending on how acidic it is it could either form (NH3)2 C2(NO2)4 (with one extra oxygen atom per molecule), or 2 NH3-NH2 C2(NO2)4 (deficient by one oxygen atom per molecule), in both cases assuming that the tetranitroethane is doubly deprotonated. Both of these should be somewhat more powerful than hydrazinium nitroformate given their better oxygen balance.

12332123 - 21-3-2010 at 02:20

Or, if one doesn't mind hyperactive sensitivity, aminotetrazolium nitroformate could be synthesised. This has perfect oxygen balance and would likely beat HMX by a fair margin (IIRC the dinitramide salt has a detonation velocity ~9500)
 Pages:  1    3  ..  6