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)
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