Sciencemadness Discussion Board - New Energetic Materials - Current Research

New Energetic Materials - Current Research

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MineMan - 27-4-2022 at 13:44

Alright. Very interesting. Everyday I check to see an update from you. I hope you can post more frequently because your updates are a treat

Microtek - 1-5-2022 at 22:48

So, I found another chinese paper (attached). It's about modifying HMX by dissolving it in DMSO along with triaminoguanidine nitrate, and then in situ polymerizing the TAGN with glyoxal (this polymeric material is named TAGP in the paper). Supposedly, this traps the HMX molecules between layers of the high nitrogen 2D polymer. Because of the pi-interactions between the TAGP layers, the HMX is forced into a less favoured conformation, thereby introducing strain in the molecule, and also increasing the density.
The HMX to TAGP ratio can be adjusted via the amounts of TAGN and glyoxal. I aimed for the one they call HT-4 in the paper. The authors measured the crystal density to be 2.04 g/cc for this variant. The synthesis proceeded as described in the SI, except that I would describe the colour as tan rather than grey. This may simply be a translational error, since the colour of my material closely matches the pictures in the paper.
I then pressed the material at high pressure (about 50 MPa), which gave me a very hard and tough pellet of about 2.0 g/cc. In my first attempt, the casing deformed from the pressure, so I had to remove the material from the casing. The pressed material is mechanically similar to hard candy, and can be (carefully) machined if required.
In my standard plate dent test it gave 4.52 mm, corresponding to 104.8% of HMX(95)/viton(5).

Attachment: HMX-TAGP.pdf (1.2MB)
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Attachment: HMX-TAGP_SI.pdf (4.6MB)
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MineMan - 2-5-2022 at 02:26

Quote: Originally posted by Microtek

So, I found another chinese paper (attached). It's about modifying HMX by dissolving it in DMSO along with triaminoguanidine nitrate, and then in situ polymerizing the TAGN with glyoxal (this polymeric material is named TAGP in the paper). Supposedly, this traps the HMX molecules between layers of the high nitrogen 2D polymer. Because of the pi-interactions between the TAGP layers, the HMX is forced into a less favoured conformation, thereby introducing strain in the molecule, and also increasing the density.
The HMX to TAGP ratio can be adjusted via the amounts of TAGN and glyoxal. I aimed for the one they call HT-4 in the paper. The authors measured the crystal density to be 2.04 g/cc for this variant. The synthesis proceeded as described in the SI, except that I would describe the colour as tan rather than grey. This may simply be a translational error, since the colour of my material closely matches the pictures in the paper.
I then pressed the material at high pressure (about 50 MPa), which gave me a very hard and tough pellet of about 2.0 g/cc. In my first attempt, the casing deformed from the pressure, so I had to remove the material from the casing. The pressed material is mechanically similar to hard candy, and can be (carefully) machined if required.
In my standard plate dent test it gave 4.52 mm, corresponding to 104.8% of HMX(95)/viton(5).

I read that paper as well and was very excited about it… however I thought there was so issues so as large inconsistency’s that precluded it from being practical. You duplicating it obviously gives it a second wind.

My big question, can this be done with UZP or the other perchlorate mentioned earlier in this threat with a VOD of 9500m/s and a density of 2.0. If it can be done with UZP
We are looking at 2.3 density.

I can’t remember the name of that other promising perchlorate you linked the paper too, but it was less sensitive than UZP
With a VOD of 9500m/s

Well done! Impressive! Still crazy the UZP has a larger dent…

MineMan - 2-5-2022 at 02:29

Quote: Originally posted by Microtek

How did you prepare and cure the HMX Viton? I have searched for uncured viton but have not been able to find any… there are many many grades of fluroelastomers and viton… which one did you use?

Microtek - 2-5-2022 at 11:08

A kind member on this forum had obtained a large amount of unvulcanized Viton and donated some to me. It is very easy to use since it is quite soluble in acetone, so I just added 5 parts Viton and 95 parts HMX to enough acetone to dissolve the Viton. Then evaporated the solvent while stirring. When it contains just a trace of acetone, it presses very well.

Microtek - 4-5-2022 at 01:54

Regarding the idea of using the TAGP (triaminoguanidine polymer) to modify UZP, I did consider it, and this is what I have come up with:

If UZP is sufficiently soluble in DMSO, then we have to find an anti-solvent which can precipitate the UZP-TAGP material. In the chinese paper they use water, but that won't work with UZP. Maybe an alcohol or a non-polar solvent such as gasoline could work.

If it can be made to work, the question remains what effect it will have on the properties of UZP. UZP is inherently different from HMX in that it is a salt, and I am not sure what that will do in this system. The reason that the density of HMX is enhanced is that normal HMX is an eight-membered ring which, due to the bond angles in the molecule, can't be packed very closely (the "ring" is kinked). The TAGP layers act by squeezing the molecule, thus flattening it to a degree, which allows it to pack qin more dense crystals (according to the paper).
UZP is a five-membered ring system which is planar, so I don't think we will see much enhancement of the density, but we won't know for sure until we try.
Also, if the TAGP-system can work as an anti-hygroscopic barrier, that would easily be worth it. If the sensitivity is decreased, even more so.

MineMan - 4-5-2022 at 02:59

Quote: Originally posted by Microtek

Regarding the idea of using the TAGP (triaminoguanidine polymer) to modify UZP, I did consider it, and this is what I have come up with:

If UZP is sufficiently soluble in DMSO, then we have to find an anti-solvent which can precipitate the UZP-TAGP material. In the chinese paper they use water, but that won't work with UZP. Maybe an alcohol or a non-polar solvent such as gasoline could work.

If it can be made to work, the question remains what effect it will have on the properties of UZP. UZP is inherently different from HMX in that it is a salt, and I am not sure what that will do in this system. The reason that the density of HMX is enhanced is that normal HMX is an eight-membered ring which, due to the bond angles in the molecule, can't be packed very closely (the "ring" is kinked). The TAGP layers act by squeezing the molecule, thus flattening it to a degree, which allows it to pack qin more dense crystals (according to the paper).
UZP is a five-membered ring system which is planar, so I don't think we will see much enhancement of the density, but we won't know for sure until we try.
Also, if the TAGP-system can work as an anti-hygroscopic barrier, that would easily be worth it. If the sensitivity is decreased, even more so.

I see! Would there be any other way to apply inter molecular pressure to increase the crystal density?

Microtek - 4-5-2022 at 22:01

None that I can think of just now.

Some people have speculated that it might be possible to nest one energetic molecule inside another. This kind of structure can be seen in zeolites, and there was a report of a composite of nanoporous silicon and liquid oxygen some years ago. It was reportedly very powerful, but of course completely impractical. The problem with experimenting with this kind of thing from my perspective, is that I have no access to the required analytical equipment, so I would be shooting in the dark.

MineMan - 6-5-2022 at 17:40

Quote: Originally posted by Microtek

None that I can think of just now.

Some people have speculated that it might be possible to nest one energetic molecule inside another. This kind of structure can be seen in zeolites, and there was a report of a composite of nanoporous silicon and liquid oxygen some years ago. It was reportedly very powerful, but of course completely impractical. The problem with experimenting with this kind of thing from my perspective, is that I have no access to the required analytical equipment, so I would be shooting in the dark.

The silicon and liquid oxygen was a sensational headline in my opinion. Some Russian guy claimed CL-20 type power but… look at the reaction. SiO2 is the product. That does not fit detonation theory of being a good explosive.

Any updates with the UZP or higher concentrations like the H7 with more TAG binder? Microtek man, your one of the only ones keeping this place alive. We love your updates. I do. If you get this, successfully I will build a shrine of you. Ok

Microtek - 9-5-2022 at 12:53

I did some experiments with UZP and DMSO to determine the viability of using in situ synthesized TAG-polymer to improve some of the properties of UZP. It seems that DMSO does dissolve UZP, forming a clear solution. However, when I tried reprecipitating it by adding an antisolvent (isopropanol), only unprotonated urazine was recovered. I also tried detergent gasoline (a mixture of alkanes), but it doesn't mix with DMSO. The possibility remains that the presence of TAGP might change this behavior, but I'm not very hopeful.

I also think it likely that the glyoxal might react with the amino group of urazine which would alter the composition of the polymer. This could be a good or a bad thing.

MineMan - 9-5-2022 at 15:26

Quote: Originally posted by Microtek

I did some experiments with UZP and DMSO to determine the viability of using in situ synthesized TAG-polymer to improve some of the properties of UZP. It seems that DMSO does dissolve UZP, forming a clear solution. However, when I tried reprecipitating it by adding an antisolvent (isopropanol), only unprotonated urazine was recovered. I also tried detergent gasoline (a mixture of alkanes), but it doesn't mix with DMSO. The possibility remains that the presence of TAGP might change this behavior, but I'm not very hopeful.

I also think it likely that the glyoxal might react with the amino group of urazine which would alter the composition of the polymer. This could be a good or a bad thing.

Ahh. Darn!

Would you be willing to try a debt test on the H-7… the one that contains more TAGP?

Microtek - 9-5-2022 at 22:47

Yes, I plan on doing that at some point. I may need to prepare some more HMX first though.

MineMan - 23-5-2022 at 01:58

Microtek any updates? Why not try H-7 with K6… easier and more powerful than HMx

Microtek - 24-5-2022 at 12:55

I am exploring some ideas with the TAGP system. I tried preparing a TAGP-UZP material using an aqueous system and the simply heating to drive the water off. It seemed to work, but of course, I don't know if the same kind of intercalated compound was formed. The product was much less sensitive to impact, but unfortunately still quite hygroscopic. I didn't test energetic properties, and now I've run out of urazine. In the mean time, I'm working on something else which may have some potential. I will reveal more when I have something to report.

MineMan - 24-5-2022 at 16:56

Quote: Originally posted by Microtek

I am exploring some ideas with the TAGP system. I tried preparing a TAGP-UZP material using an aqueous system and the simply heating to drive the water off. It seemed to work, but of course, I don't know if the same kind of intercalated compound was formed. The product was much less sensitive to impact, but unfortunately still quite hygroscopic. I didn't test energetic properties, and now I've run out of urazine. In the mean time, I'm working on something else which may have some potential. I will reveal more when I have something to report.

Ok microtek. Amazing it worked with the UZP. Any ideas on density? I am curious what your current project is!

katyushaslab - 30-5-2022 at 02:57

Previously in the thread, during discussions of semicarbazide/carbohydrazide as routes to urazine, I came across an old post by Microtek about NTO (nitrotriazolone), made by nitrating triazolone (formed by the condensation of semicarbazide hydrochloride and formic acid) on another, now defunct forum.

Yesterday I started pulling that thread again, and came up with a few things of note that I will just leave here.

While looking up some papers, I came across [1].

This paper is the source of the condensation of semicarbazide and formic acid route to triazolone, and also mentions that the best yields for NTO seems to be with nitric acid of around 65% - noting that fuming mineral acids cause carbonization of the starting material, which seems delicate. This is rather interesting, as azeotropic nitric acid is a lot less expensive to produce.

NTO itself is an insensitive high explosive, but practical applications suffer somewhat due to being water soluble.

The patent [2] mentions that crystal/particle size has an impact on critical diameter and sensitivity of the material. A further paper, [3], mentions that it forms hydrates - and that water can make the material more sensitive.

Its performance seems to be in the 7-8km/s range of velocity of detonation,

Notable things from this paper [1] include:

- Nitrotriazolone is water soluble and is also a relatively strong acid, forming salts. A potassium, and a mercury salt are mentioned - but their energetic properties aren't really explored. Potentially an avenue for research? Apparently the sodium and potassium salts are sparingly soluble, but the lithium salt is soluble. Barium and Silver salts are mentioned. I'd guess a lead or copper salt is possible also.

- There are two forms of aminotriazolone, one of which can be formed by melting together aminoguanidine hydrochloride and urea, the other is formed by reduction (HCl/Zn) of nitrotriazolone.

- Both forms of aminotriazolone can be isolated as picrates, and both form salts with silver with different properties - one is a red, the other is a white colour. Nothing is mentioned about their energetic properties either. Other salts are likely to be possible.

I need to chase down more references on this, but this could be a potentially promising thread to pull on to find interesting materials to explore. Especially given semicarbazide and aminoguanidine are already well-trodden areas of research for the SM community.

Edit:
A search lead me to more angles on this, see the thread/post in [4], pointing at patent [5], referring to hydrazine and aminoguanidine salts of nitrotriazolone, among other things. Some properties are elaborated upon in the patent, but as with all patents, take with a pinch of salt.

[1]: https://sci-hub.se/https://doi.org/10.1007/BF00955602
[2]: https://patents.google.com/patent/WO1994006779A1/en
[3]: https://sci-hub.se/https://doi.org/10.1016/j.molliq.2021.116...
[4]: https://www.sciencemadness.org/whisper/viewthread.php?tid=10...
[5]: https://patents.google.com/patent/US5256792

[Edited on 30-5-2022 by katyushaslab]

Microtek - 30-5-2022 at 22:55

Interesting. I haven't done very much experimentation with NTO due to the critical diameter. At the time, I felt that it would require too large charges for my experimental scale. It is certainly interesting if a particle size reduction can lower the critical diameter similarly to UZP. Also, I would think a hydroxylammonium salt might be worth exploring.

Microtek - 23-6-2022 at 23:10

Alright, I have been extremely busy at work, but now I have a little time to report some of my findings:

I explored an ETN/TAGP compound produced similarly to the HMX/TAGP reported earlier. My thinking was that if ETN could be flattened between sheets of TAGP as with HMX, some strain must be induced in the molecule (otherwise the "un-flattened" conformation would not represent an energetically stable minimum). This would lead to a higher heat of formation and if the density was also increased, performance would almost have to improve also.

I prepared the compound in a similar manner to HMX/TAGP since the ETN molecule is almost the same mass as HMX. The preparation was uncomplicated, and the density was measured to about 1.85 g/cc (at room temp). Diverging values of ETN density are found online (1.72 and also 1.83). As far as I can tell the higher value is measured at cryogenic temperatures, so if that is true, it seems that the density is indeed improved. I tested the brisance of the compound and found a dent depth of 4.60 mm (HMX95/viton5 4.31, UZP 4.64).

I then thought about PETN, which should also have a lot of potential for flattening. PETN/TAGP gave a dent of 4.70 mm, though the density didn't increase noticeably. Then I tested unmodified PETN for comparison, and got exactly the same dent 4.70 mm. I don't have enough ETN to test that unmodified just now.
My preliminary conclusion is that the sensitive nitric esters are quite hard to beat at the very small scale, at least in this kind of test. I may have to look into CNC machining SC liners to see if the faster energetics are better in those applications at the ~1 g scale.

dettoo456 - 30-11-2022 at 11:00

I’m guessing that brisance levels (although there’s no real defined measurement calc for it) and by-proxy, critical diameter, relate more at the <1g scale. I don’t think that det pressure necessarily takes into effect for the munroe effect but as a product of propagation and density-packing of the material as it’s initiated, the rate at which the EM ‘gets going’ is more important at low masses. Also, I haven’t been able to test it yet but incorporating plane wave lenses into the shape charge design may help to boost performance aswell.

Microtek - 2-12-2022 at 09:28

I have used lenses in my SCs in the past, and they do indeed help with the performance at the very small scale as well. However, my reason for considering SCs in this context is not to get as much performance as possible, but simply to compare the performance of different HEs. The idea is to device tests that are on the one hand standardized at the scale I work at, and on the other hand simulates some of the applications of such materials. VOD and Pcj is only indirectly interesting to me; it is the ability of the energetic to do useful work that I find to be the real criterion.

MineMan - 2-12-2022 at 14:20

Any update on UZP microtek?

Microtek - 16-12-2022 at 05:51

No, I haven't worked on UZP since I ran out of urazine. However, I came across some papers on derivatives of 5,5'-Diamino-3,3'-bis-1,2,4-triazole. The parent heterocycle is produced very simply and in decent yield by the reaction of aminoguanidine*HCO3 with oxalic acid. The product can then be treated with nitrous acid and ionic nitrite to give the dinitro derivative, or nitrated with mixed acid to give the dinitramine. Both can form salts with anions such as hydrazine, ammonia, diaminourea, hydroxylamine and others. Many of the seem to have promising properties, such as high density and VOD, low sensitivity and high thermal stability.
The reactants and apparatus requirements seem to be within reach, although the dinitro derivative requires a LOT of nitrite. I think I may try some of these reactions when I am done with the guanazole derivatives I am working on at present.

[Edited on 16-12-2022 by Microtek]

MineMan - 17-12-2022 at 22:11

Quote: Originally posted by Microtek

No, I haven't worked on UZP since I ran out of urazine. However, I came across some papers on derivatives of 5,5'-Diamino-3,3'-bis-1,2,4-triazole. The parent heterocycle is produced very simply and in decent yield by the reaction of aminoguanidine*HCO3 with oxalic acid. The product can then be treated with nitrous acid and ionic nitrite to give the dinitro derivative, or nitrated with mixed acid to give the dinitramine. Both can form salts with anions such as hydrazine, ammonia, diaminourea, hydroxylamine and others. Many of the seem to have promising properties, such as high density and VOD, low sensitivity and high thermal stability.
The reactants and apparatus requirements seem to be within reach, although the dinitro derivative requires a LOT of nitrite. I think I may try some of these reactions when I am done with the guanazole derivatives I am working on at present.

[Edited on 16-12-2022 by Microtek]

Any of them with VODs above 9500m/s? Or that outperform ANQN?

Can you link the paper?

Microtek - 18-12-2022 at 03:47

I don't think any of them outperform ANQN (on paper at least), but in my opinion, high performance coupled with low stability is not that valuable. For performance, you could just nitrate 5-aminotetrazole to get nitraminotetrazole. The product has density 2.06 g/cc, Pcj of 48.5 GPa and a VOD above 10 km/s according to one of the attached papers. Nevertheless, I would prefer reacting it with an organic high-nitrogen base to improve stability and lower the sensitivity.

Attachment: Energetic Salts of 3-Nitro-1,2,4-triazole-5-one and 5-Nitroaminotetrazole.pdf (166kB)
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Attachment: Bis(nitrimino-1,2,4-triazole)salts.pdf (111kB)
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Attachment: phpzaBYwu (909kB)
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MineMan - 18-12-2022 at 18:44

Quote: Originally posted by Microtek

I don't think any of them outperform ANQN (on paper at least), but in my opinion, high performance coupled with low stability is not that valuable. For performance, you could just nitrate 5-aminotetrazole to get nitraminotetrazole. The product has density 2.06 g/cc, Pcj of 48.5 GPa and a VOD above 10 km/s according to one of the attached papers. Nevertheless, I would prefer reacting it with an organic high-nitrogen base to improve stability and lower the sensitivity.

Thank you microtek!!

Microtek - 20-12-2022 at 00:15

Another interesting paper on nitrating amino-substituted azoles to nitramines using a simple KNO3-H2SO4 system at 0C. Apparently, this system gives better yields than HNO3-Ac2O-TFAA or other exotic mixtures. In the paper they work on assorted difficult-to-nitrate pyrazoles and triazoles, but I don't see a reason it wouldn't work on more accessible aminotetrazole or guanazole.

Attachment: KNO3-H2SO4 nitration of amino groups on azoles.pdf (830kB)
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Attachment: KNO3-H2SO4 nitration of amino groups on azoles_SI.pdf (1.6MB)
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dettoo456 - 16-3-2023 at 15:35

By any chance has anyone attempted nitration of 4-substituted imidazoles or 3-substituted triazoles before? I was thinking about 4-methyl-2,5-dinitroimidazole as a simple, cheap melt cast EM (it’s relative 2-methyl-4,5-DNI has melt cast potential). The easiest route being Acetone —SeO2–> Methylglyoxal —Hexamine+NH4OAc+AcOH—> 4-Methylimidazole —HNO3+H2SO4/SO3–> 4-M-2,5-DNI.

Microtek - 17-3-2023 at 14:20

According to this abstract:

https://www.researchgate.net/publication/261528645_2-Methyl-...

2-methyl-4,5-DNI has a melting point of more than 200 C. That's a little high for a melt cast I think.

dettoo456 - 17-3-2023 at 21:37

@Microtek My bad, I must have been thinking of something else. Apparently the N-methyl-2,4,5-TNI has a melting point of 105C though - although its amateur accessibility level is quite lower. Alkylated amines in heterocycles do seem to trend towards lower MPs but it’s weird that a trinitro product would have a lower MP than it’s dinitro analogue. Cited from DOI: 10.1002/prep.201100047

Microtek, is your UZP any farther along by the way? I don’t know what to do with my hydrazine and I was think of either going the TAGN or the carbohydrazide -> urazine route. Maybe nitrourazine (4-nitramino-1,2,4-triazole-3,5-dione) could be interesting although I haven’t seen anybody attempt nitration of urazine - it seems like it’d take really harsh conditions to do so.

Microtek - 18-3-2023 at 14:30

Yes, I also feel like the arrangement with three nitrogens in a row, with one of them being in a nitro group is probably too unstable. Still, on a sufficiently small scale it could be interesting (but not excessively interesting) to try. I'm thinking of trying an N-nitration of guanazole (3,5-diamino-1,2,4-triazole) when I have time. Guanazole is not too difficult to make.

dettoo456 - 18-4-2023 at 15:24

Bronopol (2-Bromo-2-Nitropropane-1,3-diol) is used fairly commonly in cleaning and preservatives of industrial products (see wiki https://en.m.wikipedia.org/wiki/Bronopol ). Could this be used practically if found cheap enough? I was thinking a simple nitration followed by Azide metathesis to furnish the gem-azidonitro (although I don’t know much about gem-halonitro reactions) or just nitration to the 2-bromo-2-nitropropane-1,3-diol dinitrate. Both would probably be sufficiently powerful (estimated VOD around mid 7km/s) and available. I’m sure Chinese vendors can offer it less than or equal to $25/kg, although I’d need to check.

Σldritch - 12-12-2023 at 01:31

Found this very nitrogen-rich cation [N(NNH3)4]+1 that looks suprisingly robust. Especially if stabilized as an adduct with two (thio)urea molecules. Paired with an appropriate anion it should make a very powerful explosive. No idea how to synthesize it though but there is a lot of symmetry to exploit so it has that going for it.

Microtek - 13-12-2023 at 00:29

Is there reason to think that this is anything other than a purely theoretical molecular structure? It looks... unstable to me.

Nemo_Tenetur - 13-12-2023 at 07:28

Hello!

This is my first post in this forum, I´m not a native english speaker, so forgive me misunderstandings and typo please.

Last week I found this very interesting article about a new primary called DPPE-1 with a so-called double
perovskite framework, published last month in nature communications (14, article number 7765 (2023), published 27th november 2023) :

https://www.nature.com/articles/s41467-023-43320-0

This is also the reason why I´ve decided to create an account here: I´ve read a lot here within the last months, got a pile of useful information and now I´d like to give a little back to the community.

The synthesis is very easy (pour together aqueous solutions of sodium periodate, ammonium chloride and DABCO-dihydrochloride at room temperature, filter off the crystalline precipitate, dry it, ready) with a good yield.

This primary is claimed to have superior initiation capabilities (five milligram enough to initiate RDX - wow), the impact sensitivity is acceptable, the friction sensitivity high (but not as high as silver oder lead azide) and the thermal stability seems sufficient for many applications.

Unfortunately, the ESD value is not reported by the researcher group. This is a severe gap in this publication, as accidental ignition by electrostatic discharge is a major issue and has caused so much trouble in the past.

I also miss some solubility data, behaviour against acids and bases and compatibility tests (i.e. copper, brass and aluminum casings, sulfur from time fuse, fuel oil from ANFO mixtures etc.).

Further research in this area with appropriate precautions seems necessary. A "fine-tuning" with other building blocks could reveal yet unknown primaries with even better performance. This is "terra incognita" for the scientific community.

Kind regards,

Nemo_Tenetur

dettoo456 - 13-12-2023 at 09:30

The perovskites and MOFs seem to be all the rage for new energetics - this one could be promising though. The only issues seem to be thermal stability and mechanical but those could maybe be tuned by substituting a bulkier amine like hexamine or some other polycyclic amine. Perbromate, although difficult to obtain, could maybe be used in place of the periodate and maybe cesium swapped for sodium.

Energeticheretic did some work with piperazine perchlorate perovskites and they seemed very promising but I don’t think he is active anywhere… he might be in jail sadly.

Σldritch - 13-12-2023 at 13:05

Quote: Originally posted by Microtek

Is there reason to think that this is anything other than a purely theoretical molecular structure? It looks... unstable to me.

Well the model I linked is sure not very accurate but this tautomer does feature strong-ish nitrogen-nitrogen bonds. The other tautomers not so much but again this model is crude. Of course anything with this much nitrogen looks unstable but do you have a specific fragment in mind?

I think the main decomposition pathway besides tautomeriazation would be formation of [N(NNH3)3]+2 dication isoelectronic with the triaminoguanidinium cation and a [NNH3]-1 hydrazide anion. Not very favorable. Then, looking at the tautomer, who knows? My intuition says it is moderately stable. That does not mean it forms easily. Does that make it purely theoretical? You be the judge. Personally I think the energetics design field is not very serious in its research just looking for minor improvements mostly so something like this is where it is at.

Microtek - 17-12-2023 at 03:15

What I meant was, is there any data that suggest it may have been synthesized at some point? All I see in the link is things I would expect from a theoretical study on a hypothetical molecule. How did you find out about it?

Σldritch - 18-12-2023 at 01:29

Quote: Originally posted by Microtek

What I meant was, is there any data that suggest it may have been synthesized at some point? All I see in the link is things I would expect from a theoretical study on a hypothetical molecule. How did you find out about it?

I thought I made it clear: I came up with it. No studies. No data. Just intuition and playing around in Molcalc, but, if you have a guess what someone might call this molecule, then, perhaps data can be found. I would expect any studies on this molecule to be military secrets, though, if it has potential at all. I guess that also explains why I get the impression that the energetics research community just does minor optimization: the paradigm-shifting research is secret, and so we don't see it.

Microtek - 18-12-2023 at 02:04

Well, Klapötke et al (among others) have done quite a lot of work on high nitrogen compounds. This kind of thing with long chains or networks of single-ish bonded nitrogen is usually either unstable or horrendously sensitive or both.
You can obviously play around with molecule building kits, digital or otherwise, all you like, but there is a huge step up from building a model and synthesizing the molecule in reality.

Σldritch - 18-12-2023 at 03:33

I am just saying that don't judge what works and what does not too much on published research. There are design rules of course which you can learn from, and I have, but if and when the perfect chemical explosive is found all these people are out of a job, and, that is if it is published at all. I would know because I have not published my best ideas, here, either! Then there is the issue of chemists using a very simplified model of physics and of thermodynamics especially which limits creativity, as well, not to mention the funding issue.

Regarding synthesis there may be ways of synthesizing amazingly complex molecules very simply but to my knowledge no research has been carried out in that direction, for better or worse, so there is that (I've been doing a deep dive into obscure physics lately). So there very much is an argument to be made that what the (published) energetics research community at large is doing is little better than the playing around with molecule building kits I am doing.

[Edited on 18-12-2023 by Σldritch]

Microtek - 19-12-2023 at 01:58

I completely disagree. Both on the implied existence of a conspiracy in the energetics community, and on your "observations" on simplistic chemical/physical models. Tons of research have been done on synthesizing complex molecules in a simple manner - you might say that is what all synthetic chemical research is about.

I dare you to share some of those amazing insights you have developed (beyond just hypothetical molecules; anyone can do that). If you won't, well then you are the conspiracy (or maybe just a troll).

dettoo456 - 19-12-2023 at 12:48

@Microtek I personally agree with Σldritch in the sentiment that the current EM research community isn’t exactly full of innovators as it relates to new molecule prep. I mean, look at most papers that come out of PEP nowadays; they’re mostly about modifications to old energetics like RDX, Cl-20 (not old but technically 20th century), and more physics or physical chemistry related topics. Klapotke and some of the less-trustworthy Chinese contributors are the only ones really pushing new molecules, and even then, it’s mainly just “addition of azide group here or nitro here or azo bridge there, etc”. Klapotke’s Si-PETN info was actually interesting, just as some of his N-B heterocyclic stuff but that never seemed to go anywhere.

Though, especially since some of the key motivators in EM chemistry are cost-benefit analysis and scale-up engineering, radical changes to explosives and propellants aren’t likely to even see the light of day (or less likely to make it to large scale applications).

TKX-50 is great but it’s way too expensive to make and not enough has been done to improve synth routes. Even ADN likely won’t go very far into commercial or military use.

Theoretical molecules won’t help matters though - and molbase is practically useless.

dettoo456 - 19-12-2023 at 12:56

@ Σldritch, idk what your personal insights are, but I’d say most people here are just invested in making EM’s safer, more attainable, and cleaner (the green shit is actually a worthwhile pursuit imo). As much as a fancy 3D cube or C2N14-like material is cool to look at, it simply isn’t realistic.

[Edited on 19-12-2023 by dettoo456]

Σldritch - 19-12-2023 at 13:53

Quote: Originally posted by Microtek

I completely disagree. Both on the implied existence of a conspiracy in the energetics community, and on your "observations" on simplistic chemical/physical models...

I implied no such thing. I just expect military contractors to keep military secrets.

As for models chemical explosives are now treated as closed systems. There are no closed systems in the universe or we would be unable to study them experimentally. Hence energy can be collected from the environment and be used to boost chemical explosives. One could argue that is what a (thermo)nuclear weapon is. Where this energy comes from is not always clear, though, so saying it is 'free' energy is convenient. If you do not believe in such a concept I would recommend a long and reflective look at the Sun, with emphasis on reflective, lest you burn out your retinas with all that limitless free energy.

What comes to mind first and foremost, though, as a way to amplify chemical explosives is this link.

But as discussed a chemical explosive is only as good as the industrial process producing it, though, there may be ways around that but it is pretty far out. You'd never believe it possible if I told you, and, while I know it is possible in principle myself I am not sure it can be practical without opening pandoras box...

Of course I share the goals of many other explosives enthusiasts here but I also kind of felt this was among the more speculative threads fitting for my idea which did not really deserve its own thread.

dettoo456 - 19-12-2023 at 16:01

Sounds like ideas better suited to a think-tank rather than an amateur forum then.

Defense companies may have an incentive to push for compounds like Cl-20 or LLM-105, or BTTN, etc, but I believe they’d do that to simply make more profit, not to keep jobs. For example, BAE can use their lobbyists to talk to generals about fancy 3D ultra-powerful explosives and the generals will sign whatever check BAE gives them because the generals (government) literally control one of the largest wealth collectives in all time; the US defense budget. The government doesn’t care how much an explosive will cost or how great it’ll be in reality, they care about what the defense companies or lobbyists tell them (or secret backroom deals they make). So even if a new EM came out that was fantastic, if BAE or Northrop Grumman didn’t have any interest in it for whatever reason, it wouldn’t leave the research lab. And that happens constantly. That doesn’t mean people would be discouraged from doing PEP research though, it just means that you need to be a great negotiator with defense companies.

Microtek - 20-12-2023 at 00:54

Quote:

There are no closed systems in the universe or we would be unable to study them experimentally. Hence energy can be collected from the environment and be used to boost chemical explosives. One could argue that is what a (thermo)nuclear weapon is. Where this energy comes from is not always clear, though, so saying it is 'free' energy is convenient. If you do not believe in such a concept I would recommend a long and reflective look at the Sun, with emphasis on reflective, lest you burn out your retinas with all that limitless free energy.

This is so chock-full of logical fallacy, pseudo science, and plain old misconceptions, that I hardly know where to begin. The link you provided is to a pseudo science conspiracy nut who practices alchemy. I think it is now firmly established that you are just trolling here. I will stop responding to your posts now.

EF2000 - 20-12-2023 at 03:10

There's obviously a conspiracy between the military and scientists.
I once had a chance to look into one certain hangar on a certain base (obviously I can't say where). What have I seen...
Giant robots for combat in space, giant bio-robots with souls of pilots' mothers inside, tanks huge as fortresses, fighter jets with thermonuclear engines, alien life progenitor impaled with super weapon, and more. I had to fight for my life with nanomachines-infused US senator, so I couldn't look into other hangars, maybe there were those secret explosive formulas
As I'm typing this, their agents may be already on my doorstep, I'm not as trained in gorilla warfare, so farewell my friends

Σldritch - 29-12-2023 at 02:13

Here is something more creative: the synthesis of ground-state diatomic carbon at room-temperature (link).

Diatomic carbon is interesting from an energetics POV, not primarly because it would make a good explosive, I think, but because it would make a good propellant enhancer. The ground state of diatomic carbon contains about as much energy as the combustion of the same amount of carbon to the dioxide releases. Better yet, it may not even be explosive! This is because, if pure, it should not contain enough energy to boil itself, greatly increasing safety during handling. Not only that, it may be pourable cryogenic liquid, easing handling even further, in comparison to, say; metal(hydrides), which it also has the advantage over of not producing any ash, besides not containing any rare or toxic elements. But there is more! Producing diatomic carbon in the ground-state seems to pull energy out of nowhere.

Here is Henry Rezpa clowning himself by implying diatomic carbon could not have been produced in the paper above because it would break 'the laws of thermodynamics' when there is in fact no such law of thermodynamics (link). It seems he is wisely realizing the limitations of his model here, though, as he claims the source of this energy is unknown, but it is not! For a long time it has been known energy can be pulled out of the vacuum/time domain. Tesla new it! There is no mystery here.

In conclusion, because the ideal energetic is as much a chemical process as it is the final product of that same chemical process producing it, that chemical process should extract energy from the environment. It seems entropy driven irreversible reactions is the way to do it, which should not suprise anyone, because irreversible obviously means non-equilibrium conditions where of course the infamous second law of thermodynamics does not necessarily apply.

[Edited on 29-12-2023 by Σldritch]

MineMan - 30-12-2023 at 17:58

Quote: Originally posted by Σldritch

Here is something more creative: the synthesis of ground-state diatomic carbon at room-temperature (link).

Diatomic carbon is interesting from an energetics POV, not primarly because it would make a good explosive, I think, but because it would make a good propellant enhancer. The ground state of diatomic carbon contains about as much energy as the combustion of the same amount of carbon to the dioxide releases. Better yet, it may not even be explosive! This is because, if pure, it should not contain enough energy to boil itself, greatly increasing safety during handling. Not only that, it may be pourable cryogenic liquid, easing handling even further, in comparison to, say; metal(hydrides), which it also has the advantage over of not producing any ash, besides not containing any rare or toxic elements. But there is more! Producing diatomic carbon in the ground-state seems to pull energy out of nowhere.

Here is Henry Rezpa clowning himself by implying diatomic carbon could not have been produced in the paper above because it would break 'the laws of thermodynamics' when there is in fact no such law of thermodynamics (link). It seems he is wisely realizing the limitations of his model here, though, as he claims the source of this energy is unknown, but it is not! For a long time it has been known energy can be pulled out of the vacuum/time domain. Tesla new it! There is no mystery here.

In conclusion, because the ideal energetic is as much a chemical process as it is the final product of that same chemical process producing it, that chemical process should extract energy from the environment. It seems entropy driven irreversible reactions is the way to do it, which should not suprise anyone, because irreversible obviously means non-equilibrium conditions where of course the infamous second law of thermodynamics does not necessarily apply.

[Edited on 29-12-2023 by Σldritch]

What is the synth like?

Σldritch - 31-12-2023 at 02:25

Quote: Originally posted by MineMan

What is the synth like?

I presume your point is that I should not post about something I have not tried myself nor that which is not do-able in an amateur setting as I already provided the link to the synthesis but while this is beyond my ability currently (unless some kind soul would like to make a sizeable donation for my lab) it may not be beyond the resourceful amateur at all.

Acetylides are explosive for a reason after all... Heating Cu₂C₂•H₂O under vacuum is supposedly non-explosve and deposits carbyne on the vessel wall. Why does it do that? Perhaps diatomic carbon is produced and traces of volatilized copper catalyzes the production of carbyne. Then, suppose we replace the copper with, say, mercury (Hg_nC₂) which perhaps does not catalyze that transformation and also ensures a lower temperature of decomposition as the mercury absorbs heat as it boils perhaps you would be able to trap some diatomic carbon if you are clever.

Maybe the hardest thing with its isolation would be its sensitivity to air/light and that it ought to have a boiling-point lower than that of nitrogen (considering its mass). It does not seem impossible to work around though.

Edit: having written this perhaps you were asking how the idea I concluded with would be inplemented in practice. Well, besides this idea of using diatomic carbon as an energetic I have one other idea employing these same principles of using an irreversible strongly entropy driven reaction to efficiently synthesize a very energetic compound. It is my secret, though, as I need to eat too, and, as I have grown older I am not too keen to introduce another weapon into the world. Especially as we stand on the brink of WWIII.

[Edited on 31-12-2023 by Σldritch]

dettoo456 - 1-1-2024 at 11:43

High modulus, pyrolized polyacrylonitrile (carbon fiber) can be used to drastically enhance CMDB (and likely other types of) propellant burning rates. And carbon black is slightly energetic on its own - coal fires. Other than that, metal fuels are the closest thing to an elemental EM you’ll find.

Carbon fiber propellant catalyst pdf:
https://patentimages.storage.googleapis.com/4b/c9/f1/f77511a...

Ag2BTA

Nemo_Tenetur - 11-2-2024 at 11:06

Anyone here with information about the disilver salt of bistetrazolylamine? I found this substance mentioned in "laser ignition of energetic materials" by S Rafi Ahmad and Michael Cartwright 10 years ago:

The copper and silver salt of bis tetrazolyl amine CuBTA (46) and Ag2BTA (47) have been trialled as primary explosives (...) the performance of these materials is a little unpredictable, and they should be treated with extreme care - particulary the silver bistetrazolamine. There is insufficient data in the literature to fully characterize their properties as primer compositions."

[Edited on 11-2-2024 by Nemo_Tenetur]

dettoo456 - 11-2-2024 at 20:09

I couldn’t find any info on the silver salt, but the 5,5’-bis(tetrazolyl)amine is light sensitive on its own (much less energetic as compared to a detonation).

https://doi.org/10.1016/j.chemosphere.2019.125008

Laser sensitive EMs are pretty common though, laser initiation systems far less so.

EP 2 679 567 A2

Nemo_Tenetur - 12-2-2024 at 01:46

There is an european patent filed in 2012, but the information is pretty sparse.

Impact sensitivity greater than one Joule, friction sensitivity greater than 20 Newton, decomposition temperature 360 degree centigrade (sic!)
Detonation was observed with 200 mW @ 532 nm wavelenght.
The chromium (III) salt is even more thermally stable, but deflagrates only.

The synthesis is also described and easy, so I´ll give it a try next time.

Attachment: EP2679567A2 BTA.pdf (141kB)
This file has been downloaded 501 times

Mush - 16-10-2025 at 14:59

Recent Progress on Synthesis, Characterization, and Performance of Energetic Cocrystals: A Review

Molecules 2022, 27(15), 4775; https://doi.org/10.3390/molecules27154775

Abstract
In the niche area of energetic materials, a balance between energy and safety is extremely important. To address this “energy–safety contradiction”, energetic cocrystals have been introduced. The investigation of the synthesis methods, characteristics, and efficacy of energetic cocrystals is of the utmost importance for optimizing their design and development. This review covers (i) various synthesis methods for energetic cocrystals; (ii) discusses their characteristics such as structural properties, detonation performance, sensitivity analysis, thermal properties, and morphology mapping, along with other properties such as oxygen balance, solubility, and fluorescence; and (iii) performance with respect to energy contents (detonation velocity and pressure) and sensitivity. This is followed by concluding remarks together with future perspectives.
Keywords:
energetic materials; cocrystallization; detonation performance; characterizations of ECCs

The Study of Co-Crystallization of Trinitrophenol (TNP) and Ammonium Nitrate (AN) As a Potential Method for Enhanced Stability
DOI: https://doi.org/10.51584/IJRIAS.2025.100500035

Received: 16 April 2025; Accepted: 28 April 2025; Published: 05 June 2025
ABSTRACT

This study explores the co-crystallization of trinitrophenol (TNP) and ammonium nitrate (AN) using a slow solvent evaporation method at a 1:1 molar ratio. The co-crystal formation and its potential for improved explosive stability were investigated. Characterization techniques including Fourier-Transform Infrared Spectroscopy (FTIR), X-ray Diffraction (XRD), and Differential Scanning Calorimetry (DSC) were employed. FTIR analysis revealed new peaks corresponding to functional group interactions between TNP and AN, indicating co-crystal formation. XRD confirmed the presence of new diffraction peaks not observed in the individual components, further supporting co-crystallization. DSC analysis demonstrated a significant shift in thermal behaviour compared to TNP and AN. The co-crystal exhibited a glass transition, melting point, and decomposition temperature distinct from the single components. These observations suggest interactions between TNP’s -OH groups and Ammonium NH4+ ions, leading to the formation of a more stable ammonium picrate co-crystal. The altered thermal profile indicates a potential improvement in the co-crystal’s stability compared to the individual explosives.

Synthesis of environmentally friendly energetic cocrystal derived from commodity
10.1039/d4cc04037f
Abstract

Ammonium nitrate (AN) is a green oxidizer in the field of energetic materials. However, hygroscopicity and phase transitions have prevented AN from being put into practical use. To address these two drawbacks, a cocrystallization technique was applied to AN in this study. An AN/glycine (Gly) cocrystal was newly prepared and characterized; both AN/Gly and AN/sarcosine exhibited decreased hygroscopicity and did not exhibit a phase transition.
chemicals

Enhancement of the burning performance of ammonium nitrate via cocrystallization
Abstract
Ammonium nitrate (AN) is a low-cost oxidizer with a low environmental impact; however, its low burning rate limits its application. In this study, a cocrystallization technique was used to enhance the burning performance of AN. An AN/4- amino-1,2,4-triazole (4ATA) cocrystal (molar ratio = 1:1) was prepared, and its crystal structure was investigated using single-crystal X-ray diffraction. The friction sensitivity test proved to be sufficiently safe for the treatment of the cocrystal. 5-Amino-1H-tetrazole/strontium nitrate was blended with the AN/4ATA cocrystal or with a simple mixture of AN and 4ATA to evaluate the burning behavior using the deflagration test. The test results showed enhanced burning performance for the composition containing the AN/4ATA cocrystal compared to that containing the mixture of AN and 4ATA. The hygroscopicity test revealed that cocrystallization suppressed the hygroscopicity and also resulted in the phase stabilization of AN, as confirmed from sealed cell-differential scanning calorimetry analysis.

"In our previous
studies, we prepared novel cocrystals of 1Htetrazole/
sodium perchlorate (SP), 1,2,4triazole/SP, 3amino1,2,4
triazole/SP, and 4amino1,2,4triazole (4ATA)/SP. All four
cocrystals showed higher burning performances than the
corresponding mixtures of parent materials 13)15). To the
best of our knowledge, the series of studies undertaken by
our research group are the only ones that focus on the effect
of cocrystallization on the burning performance of a
mixture of fuel and oxidizer."

Three Insensitive Energetic Co-crystalsof 1-Nitronaphthalene, with 2,4,6-Trinitrotoluene (TNT),2,4,6-Trinitrophenol (Picric Acid) and D-MannitolHexanitrate (MHN)
Central European Journal of Energetic Materials, 2015, 12(1), 47-62

Abstract: Co-crystallization is proposed as an effective method to alter the physicochemical
properties of energetic materials, e.g. density, sensitivity and solubility.
As reported in this paper, it was found that 1-nitronaphthalene could form cocrystals
with TNT, picric acid and MHN in a 1:1 molecular ratio. The sensitivity
and thermal stability of the 1-nitronaphthalene co-crystals was greatly improved
compared with that of pure TNT, picric acid and MHN. In addition, the melting
points of TNT, picric acid and MHN were lowered through co-crystallization with
1-nitronaphthalene. The electrostatic potential surface of 1-nitronaphthalene,
calculated by the DFT method, showed that the electron-rich 1-nitronaphthalene
has a tendency to be a proton donor and to co-crystallize with other energetic
materials. The structures of the co-crystals of 1-nitronaphthalene with TNT and
picric acid were characterized by single crystal X-ray diffraction (SXRD). The
1-nitronaphthalene/MHN co-crystal was studied by powder X-ray diffraction
(PXRD), differential scanning calorimetry (DSC) and FTIR.

[Edited on 16-10-2025 by Mush]

Microtek - 13-11-2025 at 00:03

Recently I have been looking at furazan derivatives again. There are a number of procedures for diaminofurazan (DAF) from hydroxylamine hydrochloride and glyoxal which does not require a pressure reactor. The dehydration/cyclization step is done either in a high boiling polar solvent such as ethylene glycol, or in concentrated aqueous urea solution with reflux for 12 hours. I have not had much success with the EG processes, but I suspect there is some additive in my EG that is the culprit. The H2O/urea system works fine but I have noticed a fairly large amount of white crystalline sublimate that collects in the condenser.
This compound puzzles me. It is non-flammable, water soluble and does not melt on application of heat from either above or below but rather sublimates. When heated from below on a piece of Al foil this creates a sort of Liedenfrost effect that makes it skate around on the foil without melting.
I initially thought it might be hydroxylamine freebase, maybe as an adduct with water, but that doesn't track with the non-flammability.
Does anyone have an idea as to what it might be?

Axt - 14-11-2025 at 09:34

Quote: Originally posted by Microtek

Does anyone have an idea as to what it might be?

No idea, but you could check its pH in water, then see if it reduced AgNO3 solution. Or just throw it in a nitration bath and see what happens

Is this regarding the dinitramino analogue of DNAF?

Axt - 21-11-2025 at 02:47

Quote: Originally posted by Microtek

Does anyone have an idea as to what it might be?

Just a thought, probably thinking too exotic. Ammonium carbonate would likely act like that.

Microtek - 21-11-2025 at 03:14

Ammonium carbonate is probably the most likely. It is a very substantial amount and may provide insight into why the yield is not so good for these preparations (especially if calculated from hydroxylamine basis).

And, yes, I am considering nitrogen rich salts of furazan derivatives such as dinitraminofurazan or dinitraminoazoxyfurazan. I found a reference to the coupling of DAF to DAAF using just Oxone rather than H2O2/H2SO4 that worked quite well, and since it should be fairly straight forward to nitrate DAAF, it seemed natural to invetigate the salts.

Axt - 21-11-2025 at 04:37

TODO is another possibility. 4H-[1,2,3]triazolo[4,5-c][1,2,5]oxadiazole 5-oxide. d. 1.934 g/cm3, VOD 9250 m/s, DP 43.1 GPa free acid decomposes at 89C though.

Supposedly DAF can be nitrated simply in 70% HNO3, involves a gay solvent extraction, but that's just with ethyl acetate.

From supporting info of ACS Appl. Energy Mater. 2020, 3, 9401−9407.

3,4-Dinitraminofurazan (6)

3,4-Diaminofurazan 5 (1 g, 10 mmol) was added in portions to a vigorously stirred 70% HNO3 (8 g, 5.6 mL, d = 1.42 g cm−3) at 25 °C. After that, the reaction mixture was stirred at ambient temperature for 2 h (as the reaction progressed, 3,4-diaminofurazan was completely dissolved). The solution was poured out into ice water (60 mL) and extracted with ethyl acetate (2 × 60 mL). The combined organic phases were washed with water (2 × 60 mL), dried over magnesium sulfate and concentrated under reduced pressure without heating. The obtained product (1.4 g, 76%) was identical to the 3,4-dinitraminofurazan synthesized by Tang et al.17 and was used without further purification.

Potassium 5-oxido-[1,2,3]triazolo[4,5-c][1,2,5]oxadiazol-4-ide (2a)

3,4-Dinitraminofurazan 6 (1.9 g, 10 mmol) was added in portions to a vigorously stirred and cooled (15 °C) solution of 93% H2SO4 (1050 mg, 10 mmol, d = 1.83 g·cm–3) in Ac2O (20 mL). After that, the reaction mixture was stirred for 30 min at ambient temperature. The solution was poured into
ice water (200 mL) and stirred for 30 min until Ac2O was completely hydrolyzed. Then AcOK (3 g, 30 mmol) was added in portions while stirring. The solution was extracted with ethyl acetate (2 × 200 mL), and the combined organic extracts were washed with H2O (100 mL). Water fractions
S4 were combined, and water was evaporated in vacuo. Acetonitrile (100 ml) was added to the brown residue and the suspension was vigorously stirred for 5 min. Then the precipitate (mainly inorganic salts) was filtered off. The solvent was evaporated in vacuo and the residue was recrystallized from MeOH to give K salt 2a (1.05 g) identical to that described previously.1 The mother liquor was concentrated under reduced pressure and the crude product was purified by flash chromatography (ethyl acetate/methanol, 5:1) to give an additional amount of the K salt as light yellow solid (200 mg). Overall yield: 1.25 g (74%); 13C NMR (125.8 MHz, d6-DMSO): δ = 160.9 (С-3a, C-6a) ppm; 14N NMR (36.1 MHz, d6-DMSO): δ = –3 (N-5, ∆ν1/2 = 15 Hz), –20 (2N, N-1, N-3, ∆ν1/2 = 540 Hz), –129 (2N, N-4, N-6, ∆ν1/2 = 600 Hz) ppm; elemental analysis calcd (%) for C2KN5O2: C 14.55, H 0.00, N 42.41; found C 14.83, H 0.00, N 42.15.

4H-[1,2,3]triazolo[4,5-c][1,2,5]oxadiazole 5-oxide (1)

To a suspension of K salt 2a (0.5 g, 3 mmol) in MeOH (10 mL) ion-exchange resin (Amberlite IR 120, H-form, 1.4 g) was added and the mixture was vigorously stirred for 2 h at room temperature. The ion-exchange resin was filtered off and the solvent was evaporated in vacuo. Diethyl ether (20
mL) was added to the residue. The white solid that formed was filtered off and washed with diethyl ether (5 mL). The filtrate was concentrated under reduced pressure to give pale beige viscous oil that crystallized in a few hours. Yield: 362 mg (95%); light beige solid; m.p. 89 °C (decomp.); 13C
NMR (150.9 MHz, d6-DMSO): δ 160.9 (С-3a, C-6a) ppm; 14N NMR (43.4 MHz, d6-DMSO): δ = –5 (N-5, ∆ν1/2 = 13 Hz), –20 (2N, N-1, N-3, ∆ν1/2 = 275 Hz), –121 (2N, N-4, N-6, ∆ν1/2 = 300 Hz) ppm; 13C NMR (125.8 MHz, d6-acetone): δ = 155.2 (С-3a, C-6a) ppm; 14N NMR (36.1 MHz, d6
acetone): δ = –5 (2N, N-1, N-3, ∆ν1/2 = 615 Hz), –38 (N-5, ∆ν1/2 = 50 Hz), –150 (2N, N-4, N-6, ∆ν1/2 = 600 Hz) ppm; IR (KBr): ν˜ 1092, 1337, 1466, 1500, 3057 cm-1; MS (EI, 70 eV) m/z : 97 [M-NO]+, 83 [M-N2O]+; HRMS (ESI) m/z [M-H]– calcd for C2HN5O2: 126.0047, found: 126.0050; elemental analysis calcd (%) for C2HN5O2: C 18.91, H 0.79, N 55.12; found C 19.17, H 0.73, N 53.41.

Microtek - 2-12-2025 at 09:22

I found a chinese (!) paper about new methods of preparing DAF (https://www.energetic-materials.org.cn/hnclen/article/abstra...). The full-text is publicly available, but in chinese. Here is an AI-translated excerpt. Beware of potential translation errors:

"2.2.1 Preparation of Supported Solid Base Catalyst

The activated carbon support was boiled in 30% nitric acid at 90 °C for 4 hours, washed with water until neutral, and dried. Then, 100 g of activated carbon was immersed in a potassium hydroxide solution overnight. The moisture was evaporated to dryness using a rotary evaporator. Under nitrogen protection, the sample was dried at 130 °C for 2 hours, then calcined by raising the temperature to 500 °C and holding for 4 hours to obtain the supported solid base catalyst. The KOH loading was 5% (mass fraction).

2.2.2 Synthesis of 3,4-Diaminofurazan Under Supported Solid Base Catalysis

15 g of 3,4-diaminoethanedioxime was dissolved in 187.5 g of distilled water and transferred into an autoclave. Then, 52.5 g of the supported solid base catalyst was added. After purging the air in the system with nitrogen, the autoclave was sealed and heated to 150 °C for 4 hours. The pressure change inside the autoclave was recorded.

After completion of the reaction, the mother liquor was allowed to cool naturally to room temperature, where a white solid precipitated. The solid was filtered and washed with water to obtain the product, with a yield of 91.2%.
m.p.: 179–180 °C.
IR (KBr, cm⁻¹): 3435, 3322 (—NH₂), 1646, 1589 (C—NH—O).
¹H NMR (DMSO): δ 5.8 (4H, NH₂)."

If true, this would be a sufficiently high yield that DAF-based materials could become interesting from more than an academic perspective.

[Edited on 2-12-2025 by Microtek]

Axt - 10-12-2025 at 10:22

I had some DAF from ages ago, so I treated 1 gram with TCCA in acetonitrile (1:2 molar eq. in 50 mL solutions). This is the literature route to the bicyclic "difurazanotetrazocine", so 2 furazan rings joined through two azo bridges. I mistakenly added the TCCA slowly to the DAF whereas as published it should be done the other way around, this may be important.

The lit runs a 2hr soxhlet extraction with hexane, this sounds like a pain in the arse so I just evaporated the acetonitrile and digested the remains with NaOH/water and filtered the orange suspension. It seems to have worked.

You have to be careful with this stuff, it flashes violently on ignition, a fair comparison on the vehemicity scale would liken it to NHN or dinitrobenzenediazonium perchlorate. It detonates easily and strongly under the hammer and when briskly rubbed with the hammer on rusty steel. I wouldn't be surprised if C4N8O2 has initiating properties.

Testing the mp it was way off, lit gives 54C mine kind of beads up a bit at 100C then more major melting at over 200C. This may be the result of adding the TCCA to DAF instead of DAF to TCCA. May also be because I didn't extract it with hexane. I checked the lit for higher oligomers and found the props for the tetramer and its mp was 212C.

Both the dimer and tetramer have similar densities and heats of formation thus would be expected to have similar detonation properties. The tetramer has published values of 8550m/s and 31.9GPa. No sensitivity data for the tetramer but the dimer is 4 cm with 2.5 kg weight where HMX was 25 cm.

[Edited on 10-12-2025 by Axt]

Microtek - 10-12-2025 at 23:57

It might also form polymers and I wouldn't be surprised if the higher homologues were favoured when an excess of DAF was present. Regardless, the potential for a metal free primary is interesting. I might have to look into that. At the moment I'm building a proper pressure reactor to see if I can make the above referenced procedure work. While the reported yields are not that much higher ( ca. 50% vs ca. 70 % total from glyoxal), the major expense is the hydroxylamine which is usually used in large excess such as 10 equivalents when doing the one-pot synthesis.

Another possibility is to perform the dehydration of DAG without solvent (https://revues.imist.ma/index.php/morjchem/article/view/7392). This gives a melt that solidifies on cooling and must then be worked up to remove impurities. Reported yields are around 70 %. I tried it one a 1 gram scale and got around 50%, though I didn't use nearly as much ethyl acetate as the authors. I suppose Soxhlet extraction would be a viable way to conserve solvent.

Axt - 11-12-2025 at 01:31

Have you entertained the thought of the microwave preparation:

One pot synthesis of DAF from glyoxime: An aqueous solution
of sodium hydroxide (100 ml 7.5 M) was added to glyoxime
(17.6 g, 0.2 mol) and mixture was kept under stirring. Subsequently,
hydroxylamine hydrochloride (27.8 g, 0.4 mol) was added, and
the contents were irradiated in the microwave oven at the power of
300 W for 2–3 min. During this period, a break of 30 s was given
when the reaction mixture started boiling. The flask was taken out of
the microwave oven after 3 min when the vigorous reaction started.
The reaction was allowed to subside at room temperature.
The reaction mixture was further irradiated in microwave oven for
30 min with a break of 30 s, whenever required (see above), using a
power of 800 W and was cooled to get a solid product. After washing
with water, DAF (14g, 70 %) was isolated.

It's out of India and half the stuff out of India is retarded but it looks plausible, its written descriptively not vaguely. It's from the paper "Microwave mediated fast synthesis of diaminoglyoxime and 3,4-diaminofurazan: key synthons for the synthesis of high energy density materials". 2005.

I've never tried it. The only "microwave mediated" prep I've tried was sulphanilic acid via microwaving aniline and sulphuric acid which went surprisingly well. I've also tried microwaving ethylene glycol with urea for ethyleneurea but this was a total failure.

Axt - 11-12-2025 at 10:27

Difurazanotetrazocine (DFT), 40 mg in a single layer of foil was negative to DDT, just flashed with a pop.

100 mg of DFT lightly pressed over 600 mg hand pressed PETN was positive with full detonation. Below compares the DFT initiated charge with a commercial #8. The #8 should be around 800 mg PETN with ASA primary and reinforcing cap.

Microtek - 12-12-2025 at 06:41

I tried that exact preparation many years ago but found that once the mixture started boiling, cooling for 30 s at room temp removed so little heat from the mix that it started boiling again in a matter of seconds when replaced in the oven. That means you will have to babysit the reaction for maybe 4-6 hours. Perhaps if more heat can be removed during the cooling intervals such as with a water bath, it might be workable.

DFT seems very interesting, I think I have to experiment with it myself.

Axt - 12-12-2025 at 08:17

Yeh I got to reading the old furazan pre-pub thread https://www.sciencemadness.org/talk/viewthread.php?tid=5813 I don't remember doing any of it, being 18 years old, but I mention the same result of the microwave prep as you. It just boils the instant power is reapplied. I guess you could run it slowly on defrost mode (so auto intermittent mode) and run it to dry and extract the result. I even seem to have had some obsession with DFT back then (I have a fetish for small symmetric molecules, they are pretty) but it was never tried. There was no mention of it being an actual primary explosive.

I think it would be worth trying adding DAF to sodium dichloroisocyanurate in water instead of TCCA in acetonitrile similar to the azotriazole reaction on route to BLG-1. The TCCA reaction is very easy but avoiding the need for acetonitrile would be great.

Microtek - 13-12-2025 at 05:05

Another possibility might be using Oxone for the oxidative coupling, though it might give DAAF instead. I don't know if the azoxy version of DFT would be stable enough to exist, but this might also be a possibility.

Axt - 13-12-2025 at 13:30

Yeh I did stir some DAF in oxone and received a high yield of DAAF, it will respond with a weak snap to a very strong hammer blow. The reduced azo (non-oxy) bridged compound is meant to be just as insensitive. I've been trying to find reference to the sensitivity of the larger azofurazan macrocycles but have not found anything. I'll attach the article on DFT that mentions its sensitivity. I referred to this back in the 19yo thread but mentioned it's too old to be available online, its online now.

"DFT is a dangerous primary explosive with a drop height of approximately 4 cm (2.5 kg. Type 12, HMX=25 cm). We believe the sensitivity is due to the boat configuration as the azo-group's n-electrons are orthogonal to the x-electrons in the furazan rings, and thus no stabilization through delocalization can occur."

They do refer to an attempt at oxidising the DFT to azoxy but received only a low yield of monoazoxy compound and gave up. I have seen reference to oxidation of the tetramer to tetraazoxy yes very dense very powerful but it required oleum/persulphate ie. super Caro's acid.

I tried sodium dichlorisocyanurate (1.2 g DAF, 10.2 g SDCIC, 10. g 90% acetic acid / molar ratio 1:4:16) It turns orange instantly but left stirred for an hour then digested with 12 g NaOH whereby the solution turned dark brown. Filtering this leaves the same orange highly sensitive DFT. Its annoyingly fine and difficult to filter, I digested my filter paper with NaOH in the process.

[Edited on 13-12-2025 by Axt]

Attachment: azo, azoxyfurazans and difurazanotetrazocine (TCCA oxidation).pdf (648kB)
This file has been downloaded 44 times

Microtek - 30-12-2025 at 00:44

I tried nitrating DAF as follows:

1.8 g DAF was added in small portions to fuming nitric acid (10 ml double distilled, free of NOx) at 0 C. Stirring was continued at this temp for two hours.

At this point the mix was poured on crushed ice. Nothing precipitated so the soln was extracted with 3 times 8 ml ethyl acetate. The combined extracts were evaporated in an air stream without heating. A small amount of gas evolution was observed during this procedure. I couldn't get the products to crystallize and the mix seemed fairly unstable, so I resolved to form salts directly. I did this by dissolving the product liquid in ethanol and then added this to ethanolic solutions of bases.
I began with simple KOH, the idea being that I could then react this with acid, extract into ethyl acetate and precipitate with other bases as needed. A large amount of orange precipitate was instantly formed when the two solutions were combined, but I had the suspicion that some of the crystals might be KNO3 if some of the nitric acid had been extracted into the ethyl acetate, or if decomposition of the nitrated product had produced HNO3 during evaporation.
To see if there was something other than HNO3, I added some of the product solution to an ethanolic solution of hydrazine hydrate. This also gave an instant precipitate that was slightly darker in colour than the potassium salt.
I also wanted to try the carbohydrazide salt whic I haven't seen mentioned in the litteraure. Carbohydrazide is not soluble in ethanol, but I dissolved some in a small amount of water and then added an equal amount of ethanol. This did not cause the CHZ to crystallize, so I added the purpoted DNAF solution to the CHZ soln, and after about half of the DNAF soln had been added, a large amount of beige precipitate had formed.

All of the salts were isolated and are air drying at time of writing.
On re-reading the "Taming DNAF" paper, I saw that they worry about over-nitrating the DAF substrate by substituting one of the nitramine hydrogens. This substance is obviously much less stable than DNAF. They resolve this problem by using a very small amount of WFNA (2 ml per 1 g of DAF), running the reaction at -10 C and only for 30 minutes.
This means that I likely have made a mixture of di- and tri-nitramines which may explain the instability.

Microtek - 1-2-2026 at 01:13

After working this past month on optimizing the preparation of DAF, I have done a few more runs of DNAF and its salts.

I first suspended 1 g DAF (10 mmol) in H2SO4 (96 %, 5 ml) and then added a mix of HNO3 (62 %, 2.24 g, 22 mmol) and H2SO4 (96 %, 2 ml) dropwise with stirring. I kept temp at 7-8 C using a salt/ice bath. After end of addition, I stirred another 30 minutes. At this point, some foam had formed, but there was no active off-gassing. The mix was poured on ice, and the clear solution was extracted with 3x10 ml ethylacetate. A little of the extract was combined with hydrazine hydrate. No precipitate formed, but after evaporating the solvent and excess hydrazine, a waxy crystalline substance remained. In a flame it melt and then burns with a hissing flame. It may be a hydrate, I will try drying it at some point.
The rest of the extracts were combined with CHZ-nitrate solution. This resulted in an immediate off white precipitate which was isolated.
The dried product puffs off at 198 C without melting. The yield was about 90 % from DAF.
I haven't done any sensitivity or performance tests yet.

I also tried the nitration using acetic anhydride and fuming nitric acid. My nitric had developed some NOx staining, and I think this may have caused some of the DAF to be oxidized (to DAAF probably) based on a marked orange colouring of the reaction. The advantage of not using H2SO4 is that the CHZ soln can be added directly when the mix has been diluted with water. This is problematic with the mixed acid nitration since CHZ-sulfate is only slightly soluble in water (about 25 g/L in hot water), and might compete with the precipitation of the product.
It might not be a big issue since the CHZ-DNAF salt has an extremely low solubility.

Edit: I have done a few tests of CHZ-DNAF. Firstly, I tested impact sensitivity by hammering on a cheap anvil. It required sustained full power strikes, but I was eventually able to set it off in this manner. I would say that it is considerably less sensitive than RDX.
I also compressed 1.000 g into the usual 7 mm ID brass tube with reinforcing block. I used my vice, but wasn't able to get the density to more than 1.70 g/cc. This is not so great, but might be caused by less than ideal crystal morphology. I do not have access to methods to measure crystal density, so it is possible that it is simply not much higher.
Finally, I made a plate dent test (20 mm Al block witness plate using the aforementioned 1.000 g in 7 mm tube at 1.70 g/cc). The dent was 4.2 mm deep placing it at 98 % HMX, 102 % RDX at their respective maximum achievable densities in my setup. This is quite decent at this relatively low density.

[Edited on 2-2-2026 by Microtek]

Axt - 3-2-2026 at 14:34

Are you saying you did receive a precipitate from pouring the water/nitration mixture directly into carbohydrazide solution?

I've tried the prep I posted above, just stirring DAF into 70% HNO3 for 2 hrs at room temp until it dissolved, then poured this yellow solution into a CHZ solution but there was no precipitate. I neutralised it with NH3 but still nothing bar a little sediment that settled out, not enough to bother filtering. I might try again but follow the script to see if it works at all.

What Al grade witness plate are you using?

Interesting though, there's very little that can beat RDX while being less sensitive than it.

Microtek - 3-2-2026 at 23:51

Yes, after nitration in Ac2O/HNO3, the mix was diluted with water and then combined directly with carbohydrazide dissolved in acetic acid. The acetic acid was probably not necessary since the nitration mix contained that in abundance.
The product from the Ac2O nitration is not as thermally stable as that from mixed acids, puffing off at 180 C. I haven't done any experiments to improve the stability, and it is definitely possible that it stems from nitrosamine compounds (or something else entirely) from the dissolved NOx. Maybe boiling for a while could decompose any unstable impurities.

The Al is ordinary extruded AW-6060. I get it in 20x40x2000 mm bars and then saw small blocks off as needed.

[Edited on 4-2-2026 by Microtek]

Axt - 5-2-2026 at 03:14

I tried again, 5 g DAF was stirred in room temp. 68% HNO3 for 2-3 hrs until it dissolved, then either evaporated out directly or poured into 200mL water and extracted with ethyl acetate. The ethyl acetate extract seemed to stay very wet with at least 20 mL water/HNO3 coming over with it I attempted to dry with CaCl2 but it was just too much.

Neither dried to dry crystals rather the ethyl acetate extract stayed slightly waxy, and that evaporated from HNO3 was oily. It dissolved readily in water but neither off these extracts produce precipitates when combined with carbohydrazide (1g extract with 1 molar eq. CHZ in 50 mL water).

The extracts are energetic, deflagrating similar to RDX and responding to the hammer in a similar fashion. Melting point for the obviously impure EA extract was low 60-70C.

EA extract dissolved readily into acetonitrile, there was an initial pale yellow precipitate on addition of 80% hydrazine hydrate for which I accidently added 2x to much (4 molar eq.), but it turned into a yellow solution with small orangish brown oily precip. Currently evaporating out the acetonitrile.

All in all, its pretty ugly.

Microtek - 5-2-2026 at 23:40

I have never isolated the free acid. When I tried evaporating the ethyl acetate extracts the first time I nitrated DAF (and my product was probably contaminated with a lot of the dinitramide derivative) it started bubbling ominously even a room temp, so I stopped concentrating any further and just added the protonated bases in ethanol. Subsequently, I just haven't bothered to evaporate before precipitating the salts. I did find that the CHZ salt doesn't precipitate from ethyl acetate unless the CHZ is protonated first. I have used both CHZ nitrate and acetate which I would dissolve in a small amount of water and then dilute with ethanol.
When this is added to the ethyl acetate extracts (still wet and probably containing some HNO3) with rapid stirring, immediate precipitation is observed. Over the course of a few seconds the precipitate seems to mostly redissolve but as more CHZ-NO3 soln is added, the precipitate persists. The hydrazine salt seems to not precipitate as easily, and I had to evaporate to dryness (room temp airstream) to get the somewhat waxy salt. I did use straight hydrazine hydrate in this case, not a hydrazine salt.

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