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Author: Subject: New Energetic Materials - Current Research
MineMan
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[*] posted on 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
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[*] posted on 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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[*] posted on 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…
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[*] posted on 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?
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[*] posted on 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.
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[*] posted on 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.
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[*] posted on 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?
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[*] posted on 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.
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[*] posted on 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
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[*] posted on 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.
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[*] posted on 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?
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[*] posted on 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.
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[*] posted on 23-5-2022 at 01:58


Microtek any updates? Why not try H-7 with K6… easier and more powerful than HMx
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[*] posted on 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.
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[*] posted on 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!
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