Sciencemadness Discussion Board

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  
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).


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.
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