Sciencemadness Discussion Board - Exotic Primaries - Complex Salts

Exotic Primaries - Complex Salts

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Microtek - 28-1-2025 at 08:02

In fact, they reference Sciencemadness explicitly further down.

Nemo_Tenetur - 28-1-2025 at 09:58

LOL!

Sciencemadness cited together with Klapötke, Stierstorfer et. al.

This is a kind of knighthood/accolade, isn´t it?

I hadn´t time enough for a thorough reading, but I ´ ll do that soon.

But I contest that all or even most of us are doing illegal research with criminal intent! Most of us are just fascinated and would never ever want to hurt, harm, destroy or even bother other people.

Axt - 28-1-2025 at 10:36

Of all things it the persulphates that cop a reference.

I've seen Sciencemadness referenced at least three times previously in journals.

Attachment: tetraamine copper persulphate.mp4 (4.9MB)
This file has been downloaded 197 times

Laboratory of Liptakov - 28-1-2025 at 12:32

How said Nemo Tenetur (se ipsum accusare)
Essentially all the discussants are digging into exotic compounds to achieve safe and reliable initiation. Which are contradictory requirements. Only occasionally does someone examine secondary substances. And only exceptionally does someone ask about the construction or effects of a large charge.

Microtek - 28-1-2025 at 23:59

It seems that my idea for making iron(III)perchlorate doesn't work as expected. When I weigh the filtered off precipitate (presumed NaCl), only about one third of the expected amount was found.
Another idea is to go through BaCO3 + 2HClO4 --> Ba(ClO4)2, 3Ba(ClO4)2 + 2Fe2(SO4)3 --> 3BaSO4 + 2Fe(ClO4)3 and filter off the BaSO4.

MineMan - 29-1-2025 at 18:30

Quote: Originally posted by Microtek

@Mineman:
The modified CoCP+ was considerably less sensitive than any NAP batch I have tried, and as such was quite promising. However, there are two problems with it: Reproducibility and toxicity. The complexes react when they come into wet contact with something that is able to act as a ligand, and some of the ligands (carbohydrazide) in the CoCP are probably exchanged for NT, or maybe some of the perchlorate ions are. Maybe polymeric complexes are formed. The point is that it is difficult to achieve the same properties every time. I don't quite remember the Chinese paper (was it maybe ICM-something?), but at any rate I haven't tried it.

@Axt:
I wonder about the quoted minimum charge to initiate PETN. They do state a minimum of about 200mg, but only describe testing 200 and 300 mg charges. I haven't yet tried [Fe(4-ATRI)n](ClO4)3 complex using iron(III)perchlorate. I just dissolved the calculated amount of FeCl3 and NaClO4 in ethanol and made another soln of 4-ATRI also in ethanol. On adding the first to the second (dropwise), a precipitate was formed. It changed character from a dull brown to blood red over time, and I let it stir for about another hour after addition. It dried to a nice brick red free flowing powder. The sensitivity is not very high and it behaves much like NHN. It is quite soluble in water, so I need to try it with Fe(ClO4)3 to avoid the NaCl impurity.

I think it is ICM something yes. How does NAP sensitivity compare to urazine perchlorate?

Microtek - 30-1-2025 at 00:08

I didn't systematically test the sensitivity of UZP, but it was quite sensitive. IIRC, a little more sensitive than PETN, though the nature of its reaction when it goes could make it seem more sensitive in my minds eye. I could have worked around it if it wasn't for the hygroscopicity and also the problematic preparation due to the combination of low basicity and low solubility of urazine.

MineMan - 31-1-2025 at 17:51

Quote: Originally posted by Microtek

I didn't systematically test the sensitivity of UZP, but it was quite sensitive. IIRC, a little more sensitive than PETN, though the nature of its reaction when it goes could make it seem more sensitive in my minds eye. I could have worked around it if it wasn't for the hygroscopicity and also the problematic preparation due to the combination of low basicity and low solubility of urazine.

I see, isn’t it worth it if it is the most powerful energetic? There are ways around the hydroscopic nature

. I do recall your experiment of HMX with triaminoguanadine produced higher det pressures… but I also recall the UP, despite its sensitivity had issues with critical diameter, limiting its brisance which should be explored further. Have you come across any new promising energetics that can compete against those two?

MineMan - 31-1-2025 at 18:43

Back in 2022 I discussed this with microtek. Has anyone explored this or does anyone like Axt have any thoughts? Seems like it would be the ideal primary explosive.

Primary explosive with a sensitivity of 10J impact and 120N Friction. Also thermally stable to 350C

It’s basically a primary explosive with less sensitivity than RDX!

https://onlinelibrary.wiley.com/doi/abs/10.1002/prep.2022000...

I don’t have access to these papers, since scihub was shut down and I am no longer with the university, does anyone have a way to access these?

[Edited on 1-2-2025 by MineMan]

Axt - 31-1-2025 at 20:54

It's a salt of "Tz-FOX", essentially FOX-7 with a tetrazole moiety replacing one of the nitro's. It's not a trivial preparation; you will find its potassium salt in older literature that is accessible through sci hub. If you track it back the starting compound is 4,6-Dichloro-5-nitropyrimidine bought commercially ($500 for 25g).

Nemo_Tenetur - 1-2-2025 at 01:21

Quote: Originally posted by Axt

It's a salt of "Tz-FOX", essentially FOX-7 with a tetrazole moiety replacing one of the nitro's. It's not a trivial preparation; you will find its potassium salt in older literature that is accessible through sci hub. If you track it back the starting compound is 4,6-Dichloro-5-nitropyrimidine bought commercially ($500 for 25g).

Thank you for this Information. 20 Dollar per gram precursor, final product probably expensive as gold, that"s out of my financial possibilities.

Microtek - 1-2-2025 at 08:32

I recently read a paper about a promising primary that was easy to prepare from "inexpensive commercially available materials". When I looked the precursor up it was priced at right around 1000 euro for 25g, even in China or India.

@MineMan:
It turned out the critical diameter issue was a function of crystal size. Due to the way I made the UZP (heating equivalent amounts of urazine and perchloric acid to dryness), fairly large crystals were formed. I tested the mechanical sensitivity of UZP when wet with gasoline, and deemed it reasonably safe to grind like this in small portions (0.1 g at a time). When I tested the ground material, it worked just fine in 7 mm coloumns.
If you have ideas to get around the hygroscopicity, I would love to hear them. I tried a number of solutions myself, but didn't find anything that worked.

MineMan - 1-2-2025 at 16:22

Quote: Originally posted by Microtek

I recently read a paper about a promising primary that was easy to prepare from "inexpensive commercially available materials". When I looked the precursor up it was priced at right around 1000 euro for 25g, even in China or India.

@MineMan:
It turned out the critical diameter issue was a function of crystal size. Due to the way I made the UZP (heating equivalent amounts of urazine and perchloric acid to dryness), fairly large crystals were formed. I tested the mechanical sensitivity of UZP when wet with gasoline, and deemed it reasonably safe to grind like this in small portions (0.1 g at a time). When I tested the ground material, it worked just fine in 7 mm coloumns.
If you have ideas to get around the hygroscopicity, I would love to hear them. I tried a number of solutions myself, but didn't find anything that worked.

Wow! That is expensive! I suppose for the FOX primary, if only 25mg is needed to set of a secondary and it is completely safe then it is worth it. But NAP is also very safe as well.

Yes, I reread your thread last night and I do have some ideas. The first is 3 percent wax, but I am assuming you have tried this. The second would be, binding it to 5 percent Viton. I don’t know if it de pronates in acetone… if so can DMSO dissolve viton… it seems it only swells non crosslinked viton because of its polarity. THF dissolves viton quite well, could that be used to dissolve the UP and crosslink the viton into it?

Or even 3-5 percent petroleum jelly mixed with UP should do the trick.

[Edited on 2-2-2025 by MineMan]

[Edited on 2-2-2025 by MineMan]

[Edited on 2-2-2025 by MineMan]

Alkoholvergiftung - 2-2-2025 at 12:42

Found in the Book Escales "Die Initialsprengstoffe" something interesting the Copper salt of Ammoniumthiocyanat (made by the reaction of an ammoniak containing Ammoniumthiocyanat solution and Coppersulfate)mixed with Potassiumchlorate after filling it in an blasting cap it only burns or flashes out except 3 drops of Ethanol or Aceton are added and dryed. Sounds interesting for this who have easy access to ammoniumthiocyanat.Somer other compounds are mentionetd Persulfocyancopper CuC2S3N2 and persulfocyanlead PbC2S3N2.
Isodithiocyanacid H2C2N2S2 and there copper and lead salts. And Pseudosulfurcyan HC3N3S3 .All heavy metall salts can be mixed wiht 2,5 to 3 parts KClO3.

[Edited on 2-2-2025 by Alkoholvergiftung]

[Edited on 3-2-2025 by Alkoholvergiftung]

Alkoholvergiftung - 3-2-2025 at 11:34

More research on the first explosive. It was made by reaktion of Ammoniumthiocyanat in ammonia containing solution and Coppersulfate.
the Copperammonimthiocyanat was mixed 2,1 part to 4,9 parts Potassiumchlorate. Its descripet that 0,2gramm of that stuff can detonate Dynamite.

Laboratory of Liptakov - 3-2-2025 at 13:10

Alkoholvergiftung.......Have you tried making anything yet? Or is it just theorizing about ammonium thiocyanate?..... :cool:

Alkoholvergiftung - 4-2-2025 at 05:49

Not made yet. Ammoniumthiocyanat is ordered

. It isnt only theory it seems they used it in some blasting caps bevore ww1.The other sulfo compounds would be better but heavier to make.Storage stable up to 100C. Persulfocyan wold be the simpelst and it was used as an yellow colour name Kanarin maybe it is somewhere aviable.

Laboratory of Liptakov - 4-2-2025 at 07:12

I am curious for first resuts....

...Beware on 10 fingers,,,,,

Silver styphnate?

Nemo_Tenetur - 7-2-2025 at 12:36

Cited from the recent publication in "molecules 29-05588-v2", page 10:

" Silver styphnate has favorable explosive properties
and is a promising primary explosive. However, its cost limits its applications [11,85]"

The cited reference 11 is the book "primary explosives" from Matyas and Pachman. In this book is stated " ... Information about silver and cupric salts is sparse" .

Reference 85 is a 90 year old patent where silver styphnate is used together with other common ingredients as a primer mixture.

I was unable to find any information about the "favorable" properties of this "promising" primary explosive. Does anybody know about impact sensitivity, friction sensitivity, initiation efficiency, ESD sensitivity etc.?

MineMan - 17-2-2025 at 19:46

Has anyone investigated #2 from this paper. Very promising for a low sensitivity primary. Chemicals don’t look too exotic. I don’t know how to separate 2 from 6 tho.

https://pubs.rsc.org/en/content/articlehtml/2024/ma/d4ma0043...

Axt - 18-2-2025 at 03:22

This threads getting off track, it's meant to be specific to complex salts. That bi-imidazole is worthy of its own thread, its downside is its pathetic yield.

Microtek - 18-2-2025 at 12:20

I think I've got everything required, although my glyoxal may require reviving. As far as I could see in the papers and patents, the yield seemed OK-ish. If I find anything interesting I'll start a new thread (unless someone beats me to it...)

MineMan - 18-2-2025 at 21:02

Quote: Originally posted by Axt

This threads getting off track, it's meant to be specific to complex salts. That bi-imidazole is worthy of its own thread, its downside is its pathetic yield.

Ok Axt, you’re right. Your a non metal primary.

Axt - 22-3-2025 at 07:20

Gallium DMSO Perchlorate is more vehemic than the iron salt analogue, flashes quite violently on ignition almost resembling NHN. Made the same way, Ga(ClO4)3 precipitated from acetone solution with DMSO.

I ignited it on Al foil to see if it affected it, it didn't seem to.

[Edited on 22-3-2025 by Axt]

Alkoholvergiftung - 22-3-2025 at 10:30

The patent with the Ammoniumthiocyanat and Coppersulfate doesnt work i couldnt isolate any Copperammoniumthocyanat. It should form blass blue needles. I got only crystals like from tetrammoniumcoppersulfate. I tried purification with EtOH no sucess. If you dont use ammoniusolution and react ammoniumthiocyanat directly with Coppersulfate it forms metallic copper powder.

dettoo456 - 23-4-2025 at 05:45

I don’t know if it’s been mentioned already, but here’s an interesting paper from LMU: 4 AgNTZ molecules are able to complex to NH3 (one of the Ag’s itself actually does) to produce a comparably safer primary. I know some here have tried to recrystallize AgNTZ from aq NH3, they might inadvertently form this in the process.

dettoo456 - 23-4-2025 at 05:49

I’m not able to edit the previous post for some reason, so here’s the link to the article:

https://onlinelibrary.wiley.com/doi/epdf/10.1002/prep.12013

Etanol - 2-5-2025 at 04:49

Quote: Originally posted by Etanol

Co(ClO4)2+NH4ClO4+NH3(excess)+H2O2=>[Co(NH3)6](ClO4)3 red solution
[Co(NH3)6](ClO4)3+3 (4-ATrz)=(boiling?)=>[Co(4-ATRz)3](ClO4)3

The subs is a dark-red resin or red-brown grains that easily melt into red resin. When cooling, the resin turns into a red vitreous mass. The substance is poorly soluble in cold water and insoluble in isopropyl alcohol.
It is difficult to ignite. Unconfined, it melts first, then burns with flashes and burns out. The melting temperature is lower than the decomposition temperature.
Unconfined, being heated on a metal foil, it melts, then burns with a flash.
Approximately 20-30 mg, confined into aluminum foil, strong detonate when heated.
In my opinion, this is powerful, but unsuitable subs.

Quote: Originally posted by Etanol

[ [Co(NH3)6](ClO4)3 and Co(NH3)6](NO3)3 are more stable

I apologize. My failure was caused by the fact that I could not correctly oxidize cobalt(II) in cobalt(III), because I used a false manual without a catalyst. The properties of the substance will be double-checked.
The cobalt(III) complexes are very very stable really. If you received it, then it is almost impossible to destroy it either with boiling or acid. However, it is important to prepare them correctly and clean in front of the next stages.

[Edited on 2-5-2025 by Etanol]

Axt - 18-5-2025 at 23:41

I neutralised formic acid with a slight excess of hydrazine then heated the hydrazine formate to 180-190C for 5hrs in an oil bath. After cooling the solid was recrystalised from ethanol/ether gave what I'm assuming to be 4-aminotriazole as a white crystalline precipitate, the melting point of about 80C seems correct.

I mixed the stoichiometric quantities of basic copper carbonate, perchloric acid and 4-aminotriazole to give {[Cu(C2H4N4)3](ClO4)2}n. A light blue precipitate forms immediately, it was stirred for an hour and filtered.

CuCO₃·Cu(OH)₂ 0.553 g
70% HClO₄ 1.435 g
4-Aminotriazole 1.262 g

Now actually reading the literature (main discussion on pg. 28) they use a considerable excess of copper perchlorate to give the tris-ligand instead of the tetrakis-ligand. I presumably have Cu(C2H4N4)4(ClO4)2. It flares off like blackpowder on ignition but only as a powder, if the caked lumps are ignited it flashes in a blue jet of flame, scoots away and deflagration does not propagate.

Does anyone have experience with Cu(C2H4N4)3(ClO4)2 or Cu(C2H4N4)4(ClO4)2? What are their "vehemic" properties?

Etanol - 19-5-2025 at 09:15

Quote: Originally posted by Axt

Does anyone have experience with Cu(C2H4N4)3(ClO4)2 or Cu(C2H4N4)4(ClO4)2? What are their "vehemic" properties?

I prepared Cu(C2H4N4)2(ClO4)2, Cu(C2H4N4)3(ClO4)2 and Cu(C2H4N4)4(ClO4)2 but I have not used it in detonators so far.
If you use an excess of copper perchlorate, you will get a hygroscopic Cu(C2H4N4)2(ClO4)2*nH2O.
Apparently, to prepare Cu(C2H4N4)3(ClO4)2, it is important not only to mix reagents 1:3, but to get a hot saturated solution without solid sediment. It is not necessary to stirring it for an hour. Only then can you cool it in a mixture of the ice and water to 0C. At the same time, the entire subs is crystallized. The substance is very poorly soluble in ice water.
Try to enclose 20-30mg in aluminum foil and heat. It will be very loud.

Axt - 19-5-2025 at 20:15

I see.

So, there is two reported procedures, one used stoichiometric quantities (3:1) https://www.sciencemadness.org/whisper/files.php?pid=698661&... . The other used an excess of copper perchlorate (1:1) https://www.sciencemadness.org/whisper/files.php?pid=698664&... . I notice these are the same authors and the 3:1 is the later published.

I guess I was after a correlation between the deflagratory properties I gave with others experience. I'm not sure if "unconfined blackpowder" is where this stuff maxes out when ignited in the open.

I'll probably try the 1:1 and see if its properties change. I made a bit more 4-aminotriazole, isopropanol is the better recrystallisation solvent. For 0.3mol formic acid used you'll need about 18g boiling isopropanol to dissolve then cool to 5C and vacuum filter (it's a solid mush).

[Edited on 20-5-2025 by Axt]

Axt - 20-5-2025 at 06:59

Ok, I tried it again.

CuCO₃·Cu(OH)₂ 2.63 g
70% HClO₄ 6.82 g
4-Aminotriazole 5.00 g

This is a 1:2.5 ratio, which wasn't really done on purpose rather I just overestimated how much 4-aminotriazole I had. The basic copper carbonate and perchloric acid were mixed in 100mL of water and brought up to 90C. The 4-aminotriazole was dissolved into 50mL water and poured in in one go turning the solution darker blue. The hotplate and stirrer were turned off and it was allowed to slowly return to room temperature. I was aiming for large crystals here, but it still dropped out quite fine, in quite a desirable free flowing crystalline needle powder.

It may just be the morphology, but this batch was significantly more vehemic than the prior. It thumps off in half-pinch sized quantities reminiscent of NHN. I can see how this would act as an initiatory primary.

copper aminotriazole perchlorate.jpg - 910kB

[Edited on 20-5-2025 by Axt]

Axt - 21-5-2025 at 06:28

The filtrate dropped out slightly more which I filtered and dried, hand pressed in copper det and fired on a thin steel channel. It was about 400mg, no base charge just the Cu(C2H4N4)3(ClO4)2. The matchhead didn't even reach the charge there was an air gap.

This isn't meant to prove much, but I'm confident it is a detonation. 400mg of PETN will do more to that channel but not dramatically more, and its pure detonation not having to DDT.

copper aminotriazole perchlorate det.jpg - 314kB

Axt - 21-5-2025 at 06:52

Attaching the hypochlorite oxidation of 4-aminotriazole to 4,4′-azo-1,2,4-triazole. The complexes of zinc perchlorate and copper nitrate given probably have no practical interest being hydrates but other experimentation may be interesting, being that 4,4′-azobis(1,2,4-triazole) is itself an explosive.

The other which may be more convenient is with sodium dichloroisocyanurate.
Qi, C., Li, S.-H., Li, Y.-C., Wang, Y., Chen, X.-K., & Pang, S.-P. (2011). A novel stable high-nitrogen energetic material: 4,4′-azobis(1,2,4-triazole). Journal of Materials Chemistry, 21(9), 3221. doi:10.1039/c0jm02970j gives explosive props of 4,4′-azo-1,2,4-triazole. (file size too large to attach)

Density = 1.62 g/cm3
VOD = 7520 m/s
Det. pres. = 23.5 GPa
Impact sens. = 14J (about half sensitivity of RDX)
Friction sens. = Slightly more sensitive than RDX
Low static sensitivity.

I have no iodate salts but this is interesting, from the supporting info of J. Phys. Chem. C 2024, 128, 5, 2240–2246.

1.1 Preparation of [M(atrz)(IO3)2]n (M =Mn, Fe, Co, Ni, Cu, and Zn)The preparation of [M(atrz)(IO3)2]n (M = Mn, Fe, Co, Ni, Cu, and Zn) are similar. M(NO3)2 (M = Mn, Fe, Co, Ni, Cu, and Zn), atrz and KIO3 were dissolved by adding appropriate amount of water according to the molar ratio of 1:1:2, and heated to 80 °C for stirring reaction for 6h. After cooling to room temperature, they were filtered and dried to obtain [M(atrz)(IO3)2]n (M =Mn, Fe, Co, Ni, Cu, and Zn) powder sample, yield of 62-84%

[Edited on 21-5-2025 by Axt]

Attachment: 4-aminotriazole oxidation to azo.pdf (639kB)
This file has been downloaded 58 times

Axt - 22-5-2025 at 07:23

Just a bit more info. These are recent so it's again a copy and paste from the supporting info.

The iodate complexes seem rather insensitive, probably not primaries. If I was to do this I'd try swapping iodate with bromate.

The impact and friction sensitivities of three EMOFs dried samples were determined by BAM standards. The IS and FS for [Co(atrz)(IO3)2]n is 18 J and 120 N, for [Zn(atrz)(IO3)2]n is 11 J and 80 N, for [Cu(atrz)(IO3)2]n is 18 J and 60 N, respectively.
J. Phys. Chem. C 2024, 128, 5, 2240–2246

A different prep. using sodium dichloroisocyanurate, the hypochlorite still seems the easiest.

Synthesis of 4,4'-azo-1,2,4-triazole (ATRZ): Sodium dichloroisocyanurate (20.12 g, 96 mmol) was dissolved in 200 mL of deionized water at room temperature with stirring until complete dissolution. Subsequently, 10 mL of acetic acid was added, and the mixture was vigorously stirred at room temperature for 4 hours, maintaining the reaction temperature below 10 °C
using an ice bath. Separately, 4-amino-1,2,4-triazole (10.1 g, 120 mmol) was dissolved in 10 mL of water and added to the reaction mixture. Stirring was continued for an additional 5 hours to ensure completion of the reaction. The reaction mixture was then filtered, and the solid obtained was dissolved in 300 mL of deionized water by boiling. After cooling for 3 hours, the solution was filtered again to isolate needle-shaped crystals of ATRZ. Yield: 5.12 g, 52%.

And the azide complex, interestingly has the same structure as the iodates ie. one ATRZ ligand per two counterions. Looks to be a primary although I'm not super interested in more inorganic azides.

Leveraging its distinctive structural attributes of encapsulated confinement, CA-ATRZ is substantially improved in terms of safety compared to CA, while maintaining its superior detonation performance.

Synthesis of [Cu(ATRZ)3(NO3)2]n: ATRZ (15 mmol, 2.5 g) was added to 200 mL of boiling deionized water and added into a 200 mL boiling aqueous solution of Cu(NO3)2·3H2O (4.5 mmol, 1.1 g). The resulting mixture was stirred for 1 hour, followed by filtration. Blue single crystals were obtained through slow evaporation filtrate over several days. Yield: 2.1 g, 70 %.
Synthesis of [Cu(ATRZ)(N3)2]n: Add [Cu(ATRZ)3(NO3)2]n (2 g, 3 mmol) to 120 mL of aqueous sodium azide solution (0.5 mol L-1). After 3 days, brown crystals suitable for X-ray diffraction are obtained, which are then filtered, washed, and dried to obtain final product. Yield: 0.79 g, 85 %. Td (onset) 209 °C. IR (KBr) ν = 3090(w), 2044(s), 1493(m), 1382(w), 1341(w), 1313(w), 1220(w), 1180(m), 1044(m), 880(m), 700(m), 616(s), 555(m) cm-1. Anal. calcd for C4H4CuN14 (311.72 g mol-1): C 15.41, H 1.29, N 62.91; found: C 15.38, H 1.30, N 62.93.
Inorg. Chem. Front., 2024,11, 8235-8245

Microtek - 23-5-2025 at 00:02

I have experimented with ATRZ from SDIC and 4-amino-1,2,4-triazole. In my experience the large amount of cyanuric acid that is produced (and which has quite low solubility) complicates the isolation of the product. I haven't tried it with hypochlorite.

Axt - 23-5-2025 at 06:41

I don't think I'm going to make any more 4-aminotriazole but it's probably something worth buying if you can, with the wide utility of it. I assume you've also tried the melt cast nitrates/perchlorates?

Just to remove any doubt, below is a compound det. with 800mg PETN and 300mg CATP. At least that's the weight i was aiming for but I think the scale was playing tricks on me. Regardless the black marks show where the column of each sit. PETN lightly arbor pressed, CATP hand pressed.

[Edited on 23-5-2025 by Axt]

copper aminotriazole perchlorate det 2.jpg - 638kB

MineMan - 23-5-2025 at 21:21

A insensitive Urazine metal polymer capable of DDT.

Microtek and Axt. Curious, this seems to have potential. I can’t grab the paper to see what the synth is like. It’s also unaffected by moisture and has an impressive det pressure (31GPa)

https://pubs.rsc.org/en/content/articlelanding/2022/ce/d2ce0...

[Edited on 24-5-2025 by MineMan]

MineMan - 23-5-2025 at 21:47

Quote: Originally posted by Axt

Ok, I tried it again.

CuCO₃·Cu(OH)₂ 2.63 g
70% HClO₄ 6.82 g
4-Aminotriazole 5.00 g

This is a 1:2.5 ratio, which wasn't really done on purpose rather I just overestimated how much 4-aminotriazole I had. The basic copper carbonate and perchloric acid were mixed in 100mL of water and brought up to 90C. The 4-aminotriazole was dissolved into 50mL water and poured in in one go turning the solution darker blue. The hotplate and stirrer were turned off and it was allowed to slowly return to room temperature. I was aiming for large crystals here, but it still dropped out quite fine, in quite a desirable free flowing crystalline needle powder.

It may just be the morphology, but this batch was significantly more vehemic than the prior. It thumps off in half-pinch sized quantities reminiscent of NHN. I can see how this would act as an initiatory primary.

Any sensitivity figures? Seems with the fast DDT it could be a stand alone detonator.
[Edited on 20-5-2025 by Axt]

Axt - 23-5-2025 at 23:35

Quote: Originally posted by MineMan

A insensitive Urazine metal polymer capable of DDT.

Microtek and Axt. Curious, this seems to have potential. I can’t grab the paper to see what the synth is like. It’s also unaffected by moisture and has an impressive det pressure (31GPa)

https://pubs.rsc.org/en/content/articlelanding/2022/ce/d2ce0...

[Edited on 24-5-2025 by MineMan]

You can generally open the supporting information and view the experimental details without buying the article. https://www.rsc.org/suppdata/d2/ce/d2ce00182a/d2ce00182a1.pd...

It presents an inconvenient route to urazine. The AgNO3 complex seems to readily drop out of aqueous solution. It'd be an interesting one to try, the negatives being the easiest route takes you through carbohydrazide and the expense of silver nitrate. It would be interesting to see another nitrate complex capable of initiation though.

Axt - 24-5-2025 at 00:59

There was a ResearchGate link into full pdf.

Attachment: Silver Urazine Nitrate.pdf (2.9MB)
This file has been downloaded 64 times

MineMan - 24-5-2025 at 10:28

Quote: Originally posted by Axt

Quote: Originally posted by MineMan

Thank you! That is a great tip about the supporting materials! Great to know in the future!

Why is the route inconvenient? If I recall to make Urazine requires extremely high temperatures for a few hours done the standard way from diaminourea?

Yes silver nitrate is expensive but, SADS was a common primary used on this forum for a while. If the compound is insensitive and can DDT confined in small amounts it seems to offset the cost. Other metal nitrates would be interesting, the benefit of silver being low toxicity… although I don’t know if the final product is toxic.

dettoo456 - 24-5-2025 at 12:31

The starting compound, the hydrazodicarboxylate diester, is just a little harder to procure compared to carbohydrazide.

And the interest in metal-free, or at the least, transition and heavy metal-free, stems from the metals' reactivity with cap materials and other energetics it may come in contact with, environmental safety, and especially in the case of silver compounds; air and light instability.

MineMan - 24-5-2025 at 13:49

Quote: Originally posted by dettoo456

The starting compound, the hydrazodicarboxylate diester, is just a little harder to procure compared to carbohydrazide.

And the interest in metal-free, or at the least, transition and heavy metal-free, stems from the metals' reactivity with cap materials and other energetics it may come in contact with, environmental safety, and especially in the case of silver compounds; air and light instability.

The paper states no incompatibility with metal shells or any light or air sensitivity.

dettoo456 - 24-5-2025 at 19:27

That may be the case as is reported by them, but I personally would not trust this compound(s), simply due to my own paranoia, unless I or someone else without grant funding examined its properties. Chinese & Indian publications are hit & miss, so excuse my cynisim.

[Edited on 25-5-2025 by dettoo456]

Microtek - 24-5-2025 at 21:14

I will certainly test the properties of this compound. It seems very easy if you have access to urazine, which I do through the carbohydrazide route. I am very doubtful of the merits of the coumpound as a primary though; as I read the paper it seems to deflagrate in the hot needle test which I find not so promising.
Regardless, the experiments will reveal the truth.

MineMan - 25-5-2025 at 14:27

Quote: Originally posted by Microtek

I will certainly test the properties of this compound. It seems very easy if you have access to urazine, which I do through the carbohydrazide route. I am very doubtful of the merits of the coumpound as a primary though; as I read the paper it seems to deflagrate in the hot needle test which I find not so promising.
Regardless, the experiments will reveal the truth.

I look forward to it Microtek! CuAGdiperchlorate also deflagrates out in the open up to and beyond one gram according to reports. But posters have noted here that properly confined it detonates in as little as 20mg with more initiating power than its nickel counterpart; would still like you to re-investigate that one! There was a post on it that was apparently deleted where a proper sand crusher and sensitivity test was preformed comparing it to the nickel compound and it performed better. I can’t find that post using the search engine.

A few things with this paper. They use the KJ equation to predict detonation velocity which does not work with metal ligands. They also mention a cadmium compound with a det velocity of over 10kms, but it has a lower density than the silver compound but less oxygen balance. But if I recall the paper indicates the molecule has less partially oxidized molecules.

The silver compound does have a density of 2.6g/cc and good OB, which makes me think it’s actual performance is much higher?

Microtek - 26-5-2025 at 00:43

I did examine the copper analogue to NAP (I usually refer to it as CAP) and found it to be fine, though it requires more confinement to DDT compared to NAP. IIRC, Etanol had some misgivings regarding the long term stability. For this reason I prepared a small batch some months (I think it was in october or november) ago to see if it deteriorates on storing. So far it hasn't changed noticably in appearance or performance.

I just did the synthesis of the Ag(H2Ur)NO3 complex as described in the paper. An extremely dense white powder is produced. It settles to the bottom of the beaker in seconds once stirring is stopped, and filters very well. On drying, I did the usual flame tests on foil, and found it to be completely non-energetic. On looking through the paper a second time, I found that most of the results were on substance 5, the powder form slowly recrystallized from nitric acid.

I added 1.00 g of the white powder to 8.5 ml distilled water at 85 C. It was difficult to get it suspended due to the aforementioned density. Then about 2 ml HNO3, 62% was added. This caused most of the powder to dissolve, leaving a slightly turbid solution which was filtered hot. The filtrate is evaporating at ambient conditions at time of writing. I find it likely that the initially precipitated white powder does not in fact contain the nitrate ion, but we will see what is left when the solution has evaporated, and which properties it has.

MineMan - 26-5-2025 at 12:40

Quote: Originally posted by Microtek

I did examine the copper analogue to NAP (I usually refer to it as CAP) and found it to be fine, though it requires more confinement to DDT compared to NAP. IIRC, Etanol had some misgivings regarding the long term stability. For this reason I prepared a small batch some months (I think it was in october or november) ago to see if it deteriorates on storing. So far it hasn't changed noticably in appearance or performance.

I just did the synthesis of the Ag(H2Ur)NO3 complex as described in the paper. An extremely dense white powder is produced. It settles to the bottom of the beaker in seconds once stirring is stopped, and filters very well. On drying, I did the usual flame tests on foil, and found it to be completely non-energetic. On looking through the paper a second time, I found that most of the results were on substance 5, the powder form slowly recrystallized from nitric acid.

I added 1.00 g of the white powder to 8.5 ml distilled water at 85 C. It was difficult to get it suspended due to the aforementioned density. Then about 2 ml HNO3, 62% was added. This caused most of the powder to dissolve, leaving a slightly turbid solution which was filtered hot. The filtrate is evaporating at ambient conditions at time of writing. I find it likely that the initially precipitated white powder does not in fact contain the nitrate ion, but we will see what is left when the solution has evaporated, and which properties it has.

Thank you for the update! I am excited for the results! How would you compare the sensitivity (mechanical and impact) of CAP to uNAP or iNAP? Do you think there is a way to get uCAP as I recall users saying the crystals are about 100um cubic?

Microtek - 27-5-2025 at 02:48

The sensitivity of CAP is a little higher than that of NAP IIRC, possibly because of the larger crystals. I did do an experiment with ultrasonication of the mix during CAP synthesis and it did reduce the crystal size. I never got around to systematically testing the sensitivity of the uCAP though.

MineMan - 28-5-2025 at 13:10

Quote: Originally posted by Microtek

The sensitivity of CAP is a little higher than that of NAP IIRC, possibly because of the larger crystals. I did do an experiment with ultrasonication of the mix during CAP synthesis and it did reduce the crystal size. I never got around to systematically testing the sensitivity of the uCAP though.

Thank you microtek! I know I have been asking you this a lot! Any update on the Urazine ligand?

Microtek - 30-5-2025 at 23:43

Well, with respect to the purported Ag(H2Ur)NO3 complex, I do have a little. After having dissolved the dense white powder in dilute nitric acid and filtered the solution, white crystals began slowly precipitating over the course of about 8 hours. I left it overnight, and then filtered these crystals off and dried them. They turned out to be just as inert as the original white powder, and I'm convinced it is the same substance.
The filtrate from this last filtration was poured into a crystallizing tray and left for 48 hours. Transparent leafy crystals formed and a few were placed on a filter paper to prepare a dry sample for initials tests. On flame contact it melts and decomposes with hissing, so there is still a slight hope that something energetic can be had from this procedure. I will try dehydrating the crystals properly to see if the "melting" is really dissolving in crystal water.

MineMan - 1-6-2025 at 13:54

Quote: Originally posted by Microtek

Well, with respect to the purported Ag(H2Ur)NO3 complex, I do have a little. After having dissolved the dense white powder in dilute nitric acid and filtered the solution, white crystals began slowly precipitating over the course of about 8 hours. I left it overnight, and then filtered these crystals off and dried them. They turned out to be just as inert as the original white powder, and I'm convinced it is the same substance.
The filtrate from this last filtration was poured into a crystallizing tray and left for 48 hours. Transparent leafy crystals formed and a few were placed on a filter paper to prepare a dry sample for initials tests. On flame contact it melts and decomposes with hissing, so there is still a slight hope that something energetic can be had from this procedure. I will try dehydrating the crystals properly to see if the "melting" is really dissolving in crystal water.

Ok a bit disappointed! Didn’t the hot needle tests show a flame? What do you think could have gone wrong here?

Axt - 13-6-2025 at 03:51

Cu (4,4′-azo-1,2,4-triazole) Bromate (BLG-1)

Cu(C4H4N8)(BrO3)2

https://pubs.rsc.org/en/content/articlelanding/2023/mh/d3mh0...

It's a 2023 paper. The claim is 3mg to initiate RDX and 1mg for CL-20 that is the most efficient I've seen. They are also claiming lower sensitivity than lead azide but we know how these Chinese claims go.

Prep for 4,4′-azo-1,2,4-triazole is linked on previous page, precursor is 4-aminotriazole, a derivative of hydrazine and formic acid followed by hypochlorite oxidation to the azo bridged compound.

[Edited on 13-6-2025 by Axt]

Microtek - 14-6-2025 at 08:23

Yet another great find Axt. I looked through the supplementary material, and I think it looks promising. The photos of the lead plate tests with 30-70 mg neat BLG-1 are quite convincing assuming they are not a complete fabrication.
I will have to prepare some bromate, but in the meantime I've tried with perchlorate as the oxidizing counterion:

1 mmol 4,4'-azo-1,2,4-triazole was dissolved in about 7 ml hot distilled water along with a little HClO4. 1 mmol Cu(ClO4)2 was prepared by dissolving 0.5 mmol Cu2CO3(OH)2 in slightly more than 2 mmol diluted HClO4.
Once all the 4,4'-azo-1,2,4-triazole was in solution, the Cu(ClO4)2 soln was added dropwise. This caused immediate precipitation of a blue solid. At time of writing, I'm allowing the mix to come to room temp with stirring.

Axt - 14-6-2025 at 19:06

It seems like perchlorate doesn't form a structural analogue to the bromate/iodate/azide, rather forming the less desirable but no doubt still energetic tris(ATRZ) ligands like the nitrate.

From attachment.

Synthesis of [Cu(atrz)3](ClO4)2 (atrz-Cu). atrz (1.5 mmol, 0.246
g) in 20 mLof boiling water was added into a boiling aqueous solution
of 20 mL Cu(ClO4)2·6H2O (0.5 mmol, 0.185 g). The mixture was
stirred for 1 h, and then filtered. Blue single-crystals suitable for X-ray
diffraction were obtained by slow evaporation in a glass vial within
several days with a yield of 79%.

Its explosive props aren't well characterized, so it will be interesting to see what it does.

Can you make comment on the aminotriazole -> azotriazole oxidation, did you try the hypochlorite route?

[Edited on 15-6-2025 by Axt]

Attachment: Copper azo-triazole perchlorate.pdf (1.9MB)
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Axt - 15-6-2025 at 06:35

Here's some further info on the nitrate [Cu(ATRZ)3(NO3)2]n. Not entirely sure what to think of this one, its properties are all over the place. The props of the perchlorate are given in table from a review article (too big to attach).

Its calculated properties are also in supporting info here: https://pubs.acs.org/doi/10.1021/acs.chemmater.5b04891?ref=P...

To summarise the nitrate, low sensitivity, extremely high heat of detonation, relatively low density (1.64-1.68) and wildly calculated VOD's 9160 & 6780.

Attachment: copper azo-triazole nitrate.pdf (1.2MB)
This file has been downloaded 41 times

Etanol - 15-6-2025 at 11:21

Quote: Originally posted by Axt

Here's some further info on the nitrate [Cu(ATRZ)3(NO3)2]n..

[Cu(atrz)3(NO3)2]
[Ag(atrz)1.5(NO3 )
If the formula of these complexes is correct, then I see no reason to do this.
They are very weak. The energy of -N=N- recombination is insufficient to create a high-explosive for this molecular mass. And it contains very little oxygen.

[Cu(atrz)3(NO3)2=[Cu(C4H4N8)3(NO3)2=>Cu+6H2O+12C+13N2

"Among them, the heat of detonation of complex 1 is 3.62 kcal/g (6.08 kcal/cm3 ), which is even higher than those of CL-20 (about 1.5 kcal/g)and octanitrocubane (ONC;
about 1.8 kcal/g ), the most powerful organic explosives known."

Taking into account the formula and the equations of detonation, this is a clear fake. How can you believe in it?

If the atrz formed the complex
[Cu(atrz)1.5](NO3)2
or
[Cu(atrz)](NO3)2
or
[Cu(atrz)1.5](ClO4)2
it would make sense.

[Edited on 15-6-2025 by Etanol]

[Edited on 15-6-2025 by Etanol]

Microtek - 15-6-2025 at 13:07

I have experimented a little with the Cu(atrz)n(ClO4)2 complex. I only got 136 mg from the experiment described above, and the filtrate still had a slight blue tint. The dry product is a pale blue powder, and on heating about 1 mg on a piece of Al foil (from below) it detonated with a very sharp, hard bang, reminiscent of azides. On flame contact from above it pops, but the reaction does not propagate through all of the mass.
Confined in a model cap (brass, 7.5 mm ID) it ignited and detonated from an e-match, but not from the flash of gun cotton.

I also prepared som KBrO3, so I'm almost ready to see if the bromate complex is as impressive as the paper claims. Regardless, I think that the performance of Cu(atrz)n(ClO4)2 calls for making some more 4,4'-atrz. I will try the hypochlorite method to see if it is more convenient than the one using SDIC.

Axt - 15-6-2025 at 20:55

Quote: Originally posted by Etanol

this is a clear fake. How can you believe in it?

I don't. It's a compilation of the available information to shed light on this particular family of complex salts. The supporting info linked above argues against it by providing a heat of combustion figure lower than the heat of detonation figure in that attachment, you would expect a high heat of combustion for something so oxygen poor so it's of no surprise that it far exceeds RDX. There is still a general trend for these "MOF's" to have very high heats of formation though.

I don't know where the "9160m/s" in the review article is coming from. The only figure in the references provided is that attached here, which seems plausible.

copper azotriazole nitrate props.png - 234kB

Etanol - 16-6-2025 at 22:19

Quote: Originally posted by Axt

It's a compilation of the available information to shed light on this particular family of complex salts.

Yes, 6780-6860 m/s 18.56-19.15 GPa and Qdet=4388-4562 KJ/kg at 1.63 g/cc looks more realistic.
Can 4-aminotriazole be oxidized with KMnO4 to 4,4'-atrz as aminotetazole?

Microtek - 16-6-2025 at 23:53

Yes, undoubtedly. The usual oxidizers are SDIC (sodium dichloroisocyanurate) or hypochlorite.

On a related note, I followed the NaOCl procedure detailed on p. 30 of this thread, except that I used an equivalent amount of household bleach (ca. 2.5 %). To compensate for the low concentration, I added the aminotriazole as a solid instead of in solution. At first it seemed to not be very exothermic, but on adding a little more, the temperature shot up to about 20 C and a lot of foam was formed. I added ice directly to the reaction and got the temp back down to about 10-15 C, which was still above what it should have been. As the foam died down, I observed a lot of white precipitate. I maintained stirring and cooling for 4 hours, and left the reaction sitting at room temp overnight. The white solid is still there, and I'm wondering if it is ATRZ or maybe some chlorinated derivative.

Axt - 17-6-2025 at 06:22

This article is on point.

"We also attempted to treat 4-amino 1,2,4-triazole with other oxidative reagents such as KMnO4 in HCl [8,18,19] or NaOH [20], MnO2 [21] and H2O2[22]. Unfortunately, these methods failed to afford the desired product. "

It also mentions that a chlorinated derivative does form when an excess of sodium dichloroisocyanurate is used. Their melting points are considerably different, non-chloro decomposes at 300C, tetrachloro melts at 217-220C.

[Edited on 17-6-2025 by Axt]

Attachment: chlorinated azotriazole.pdf (92kB)
This file has been downloaded 36 times

Microtek - 17-6-2025 at 13:29

It's surprising that permangante doesn't work. Thanks for the paper by the way, I was looking for that one specifically. In most of the papers I've found on 4,4'-azobis(triazole) from SDIC, they sort of skip over the part where they deal with the large mass of precipitated cyanuric acid. I do think 4,4'-AZTR is more soluble than cyanuric acid, but it's not as if it is very soluble itself, and the amount is considerably less. Perhaps a hot water extraction and then recrystallization is in order. Fortunately, Ive just made a melting point apparatus that can deal with quite high temps.

Axt - 17-6-2025 at 19:05

Cyanuric acid seems to be significantly soluble in hot water (from chemister.ru)
water: 0.27 (25.5°C) [Ref.]
water: 0.7 (50°C) [Ref.]
water: 2.6 (90°C) [Ref.]
Вирпша З., Бжезиньский Я. Аминопласты. - М.: Химия, 1973 pp. 28 [Russian]

I can't see why a hot basic solution (bicarb?) couldn't be used. I cannot find data for sodium cyanurate, only that it's "soluble". This assumes ATRZ hasn't an amphoteric nature, it's "weakly basic" although not basic enough to form isolatable acid salts. This is the reason its iodate "salts" in the table above are cocrystals not true salts.

Edit: Looking up the pKa, it looks like you'd only get a monosodium cyanurate with bicarb. You might be able to get a disodium cyanurate with carbonate and trisodium with hydroxide. The solubility of the mono is still low at "0.8%" https://www.msdsdigital.com/system/files/MONOSODIUM_CYANURAT... . No data on disodium, trisodium is high at 1000g/L https://www.echemi.com/sds/cyanuricacidtrisodiumsalt-pid_Sev... .

[Edited on 18-6-2025 by Axt]

Microtek - 17-6-2025 at 23:43

Yes, the problem is that 4,4'-aztr follows about the same solubility curve; very low solubility at lower temps, and then increasing significantly as you get above ~60 C. I'm planning on charting the solubility of 4,4'-aztr in order to find a workable strategy, but I only have about 0.1 g left. I will see if it reacts with NaOH.

Edit:
I did a quick melting point measurement on the mystery substance and it melts with decomposition at about 200 C, so it seems to probably be a chlorinated derivative of 4,4'-aztr. When exposed to flame, it puffs off semi-energetically. The question is if it is possible to do anything interesting with it, like maybe replacing some of the chlorine atoms with azide groups.

I also followed the "chlorinated azotriazole" paper's method for 4,4'-aztr using SDIC. When I added the aminotriazole soln in one portion (to avoid having a molar excess of SDIC) the temp shot up to 50 C with a little effervescence. It is stirring and slowly cooling now, and we will then see about the isolation of the product.

[Edited on 18-6-2025 by Microtek]

Axt - 21-6-2025 at 15:08

Quote: Originally posted by Microtek

The question is if it is possible to do anything interesting with it, like maybe replacing some of the chlorine atoms with azide groups.

The answer is, yes. The tetraazide (and lower members) is in the attachment, from reacting the chloro compounds with sodium azide. It's spaz'd out on nitrogen C4N20.

Here's the props, don't shoot the messenger but they say these values are under-calculated in the text.

d = 1.795 g/cm3
VOD = 9370 m/s
DetP. = 38.43 GPa
HOF = 2274 kJ/mol
Decomp. = 136C
IS = <3 J

EDIT:
It won't attach for some reason:
Qi, C., Li, S.-H., Li, Y.-C., Wang, Y., Zhao, X.-X., & Pang, S.-P. (2012). Synthesis and Promising Properties of a New Family of High-Nitrogen Compounds: Polyazido- and Polyamino-SubstitutedN,N′-Azo-1,2,4-triazoles. Chemistry - A European Journal, 18(51), 16562–16570. doi:10.1002/chem.201202428

https://sci-hub.se/10.1002/chem.201202428

This is the detailed prep of the tetrachloro compound. They are running 5:1 ratio SDCI:ATZ and higher temps. From S. H. Li, H. G. Shi, C. H. Sun, X. T. Li, S. P. Pang, Y. Z. Yu, X. Q. Zhao, Chin. J. Energ. Mater. 2009, 17, 7–10.

Sodium dichloroisocyanurate (SDCI) (79.20 g, 360 mmol) was dissolved in 400 mL of water, and 80 mL of AcOH was added. After 1 hour, 4-amino-1,2,4-triazole (6 g, 72 mmol) was added. The reaction mixture was stirred for 3 hours at 50°C. After cooling to room temperature, the solution was neutralized with NaHCO₃ to pH 7 and extracted with AcOEt. The extract was washed with water and dried over MgSO₄. The solvent was evaporated to dryness in vacuo. The residue was purified by column chromatography (silica gel, 1:3 EtOAc/CHCl₃), and the title compound was obtained in a yield of 3.2 g (30%) as a colorless crystal. A single crystal of the title compound was obtained by slow evaporation from acetone at room temperature. Melting point: 197–199°C.

And for the tetraazide:

3,3’,5,5’-Tetra(azido)-4,4’-azo-1,2,4-triazole (15): NaN3 (0.29 g, 4.5 mmol) was added to a solution of compound 11 (0.30 g, 1.0 mmol) in DMF (15 mL) at RT and the reaction mixture was stirred for 2 h. The mixture was poured into water, stirred for a further 1 h, and then filtered. The residue was dissolved in CH2Cl2 and purified by recrystallization from CH2Cl2/petroleum ether. Yield: 0.13 g, 40%; Tdecomp : 136.8C (DSC, 108Cmin)

[Edited on 22-6-2025 by Axt]

Microtek - 24-6-2025 at 07:42

The idea of neutralizing the cyanuric acid seems to work well. I did a SDIC based coupling reaction, filtered to isolate the solid products and then added three molar equivalents of ca. 1M NaOH assuming full recovery of cyanuric acid. After stirring about 10 seconds, the mix was vacuum filtered and washed with a small amount of water. The filter cake was recrystallized from the minimum amount of boiling water, with slow cooling resulting in well defined pale yellow needle shaped crystals in decent yield. I still need to make sure that the crystals are in fact 4,4'-AZTR, but I am fairly sure that they are, based on the way they behave on flame contact as well as solubility.

Edit:
I did a "melting" point test with a small amount of the predried (110 C, 30 min) crystals. No change was observed up to 300 C, but shortly thereafter the sample exploded with a sharp report that left my ears ringing. Curiously, the capillary tube I was doing the test in didn't shatter.

[Edited on 24-6-2025 by Microtek]

[Edited on 24-6-2025 by Microtek]

Microtek - 25-6-2025 at 13:38

I prepared what I believe to be BLG-1. 1 mmol aztr and 2 mmol KBrO3 was dissolved in 10 ml water at 70 C. Then a soln of 1 mmol CuSO4*5H2O was added dropwise with stirring. There was no immediate precipitate, but after 1 hour of continued stirring while the temperature slowly dropped a dense blue solid had formed. This was filtered off and washed with a small amount of water, and the product was dried 30 minutes at 110 C. Yield was 48%.
The product pops if ignited from above in very small amounts, and detonates if flame heated from below. In fact it behaves a lot like NAP, though it leaves more soot.
I did initiation tests in which 200 mg RDX was pressed into a brass tube (7.0 mm ID, 0.5 mm wall thickness) at about 25 MPa. On top of this, 10 mg BLG-1 was lightly pressed. A 3d printed flash cap with a little gun cotton was inserted, and the assembly was fired against a witness plate (steel, 2 mm thickness). Full detonation was achieved with a deep dent and spalling of the back side.
The test was repeated with 4-5 mg of BLG-1 (my scale only has a resolution of 1 mg, so these small masses begin to be a little uncertain), and again the base charge detonated. It was noted that the RDX seemed a little under initiated with a less pronounced dent and no spalling. It is quite possible that the RDX could be initiated with just 3 mg as claimed in the paper, but that really wouldn't be desirable. Already 4-5 mg is not enough to cover a 7 mm disc in a continuous layer, so I doubt I would ever want to use less than maybe 10 mg.
At any rate I now need to look into the sensitivity of the substance, and I will also revisit the perchlorate analogue with my new batch of AZTR which seems to be much more pure than the one I used earlier.

Axt - 26-6-2025 at 13:05

It's good that something seems to have held up to the hype for once. I calculated the column length of 3mg of BLG-1 in a 6mm detonator and even at 1/2 max density it was less than a sheet of paper. I'd expect its performance would be more efficient in smaller diameters to increase the ramp up distance or perhaps a smaller dia. insert. But yes, working with these miniscule amounts seldom makes much practical sense.

I did test sodium carbonate on cyanuric acid (10g CA, 20g SC, 100mL boiling water) and it wasn't promising at all, so it does seem to require the harsher hydroxide treatment.

Microtek - 28-6-2025 at 13:54

I have done some sensitivity tests on BLG-1, and unfortunately it seems a lot more sensitive than NAP in the oblique abrasive impact test. I tested samples from the highest setting and worked my way down until I got a non-reaction. I had to go all the way down to 12-13 cm, whereas NAP has 3 non-reactions out of five attempts at 95 cm. So BLG-1 is about 10 times as sensitive in this test as NAP.

I am testing AZTR with other combinations of metal center and counterion, starting with Fe(II) and perchlorate.

symboom - 28-6-2025 at 16:53

Sounds great azotriazole is an interesting compound with copper and bromate what about perbromate it's stable ion.

https://pubs.acs.org/doi/10.1021/acs.cgd.3c00133

[Edited on 29-6-2025 by symboom]

Axt - 29-6-2025 at 17:30

Shame about the sensitivity, I wonder if its inherent to these rigid 3D bonded structures like the perovskites.

What process are you using for the azotriazole prep Microtek? I had half a go using NaOCl and total fail. I'll try one more time closely following the molar quantities and dilutions but it doesn't look good.

That review article is the one I referenced on the proceeding page that was too big to attach, I've compressed it and it is here.

Attachment: 4-4-azobis(1-2-4-triazole)-review 2023-compressed.pdf (1.2MB)
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Microtek - 30-6-2025 at 00:11

Well, I have tried a number of the methods.
I adapted the method in this open source paper: https://www.sciencedirect.com/science/article/pii/S266713442...

Lacking syringe- and peristaltic pumps, I just added small portions of the reactants to a stirred beaker, beginning with the aminotriazole.
Then, 40 minutes into the additions I began removing the same volume as the combined additions, and quenching the removed mix in cold water.
After about 1.5 hours, everything was in the quench beaker, and I vacuum filtered it. I then shut down suction and added three molar equivalents of NaOH (1M) to the filter cake. After stirring about 10 seconds (during which the filter cake was markedly reduced due to solution of the formed cyanurates), I turned on suction again. I washed the remaining solids with water, applied more suction, and finally recrystallised from 90 C water (AZTR has a solubility of around 4 % at this temp and around 0.8 % at 5 C).

I also did other synthesis methods that seemed to work reasonably such as a couple where the SDIC soln is acidified with acetic acid and aged for 4-6 hours before adding the aminotriazole. However, having read about (and experienced) the tendency of AZTR to form chlorinated derivatives, I wanted to avoid an excess of hypochlorous acid which comes with adding aminotriazole to SDIC instead of the other way round.
I also hadn't refined my method of separating the AZTR from the cyanuric acid, so I can't really compare one method with another.

Axt - 30-6-2025 at 01:52

Thankyou. Can you describe the additions, as in effervescence? temp control? foaming? Just trying to fill in the blanks from the lit.

4-Aminotriazole should have had a topic in itself but this is something you may be interested in, If i had acetic anhydride I'd try it just for the novelty, an N-N-NO2 nitroimide via nitration of 4-ATZ. Russian Journal of Organic Chemistry, Vol. 38, No. 9, 2002, pp. 1343-1350.

1,2,4-Triazol-1-io-4-nitroimide (I).

4-Amino-1,2,4-triazole, 16 g (0.19 mol), was added in portions with stirring to 25 ml of acetic anhydride at such a rate that the temperature did not exceed 55-60oC. The resulting solution was cooled to 0oC, and 50 ml of concentrated nitric acid was added dropwise over a period of 3 h, maintaining the temperature at 0oC. The mixture was stirred for 0.5 h at 0oC and was gradually warmed up to room temperature. The mixture was kept for an additional 1 h and was poured into 500 ml of water containing ice. The solution was evaporated on a water bath to a volume of 50-70 ml
and diluted with methanol, and the precipitate was filtered off and recrystallized from aqueous methanol. Yield 9-10 g (37-40%), mp 179oC (decomp.) [2].

[Edited on 30-6-2025 by Axt]

Microtek - 30-6-2025 at 08:41

Interesting. I might try that at some point, though I will be away from the lab for some time.

About the synthesis of AZTR, there wasn't much foaming or effervescence when the SDIC, acetic acid and aminotriazole was added in small portions, but there was a lot of precipitation of cyanuric acid (and AZTR, presumably). This is also the case when the SDIC and acetic acid are allowed to react before the aminotriazole is added.

The reaction is fairly exothermic, but for the "three-drop" method, the optimal temp was found to be about 20 C, so temp control can be done with a simple water bath (no ice if you have cold tap water).

Also, I tried the azide substitution on the chloro-derivative of AZTR that I had accidentally produced. The reaction did not give a very high yield (about 65 mg from a 1 mmol basis, so about 20%), but the product is about as efficient an initiator as the copper bromate complex discussed above, only much more vehemic. It has a sensitivity to match, but I will have to make a little dextrinated lead azide just to see how that performs in my apparatus.

Axt - 30-6-2025 at 17:37

I've been defeated. I tried following the NaOCl route as closely as possible but apart from a small amount of white powdery precipitate in the initial stages of the reaction there was nothing more on standing. The SDIC route has also killed me, I'll describe my process here as detailed as possible

SDIC·2H₂O ---------------- 25.7 g ----- 0.100 mol
Acetic acid (glacial) ------- 9.08 g ----- 0.151 mol
4-Amino-1,2,4-triazole ----8.8 g ------- 0.105 mol
Sodium hydroxide ---------12.0 g ------ 0.300 mol
Water (total) ---------------201.3 g ----- ~11.2 mol

25.7 g of sodium dichloroisocyanurate dihydrate was dissolved into 125 mL of water with stirring and brought down to 5C by placing it in a freezer, at the same time 45.4 g of 20% acetic acid is cooled by the same means. The acetic acid is introduced to the SDIC in one portion at 5C and stirred as it is allowed to come to room temperature over the following hour in which time a fine suspension of cyanuric acid forms turning the solution milky white. In the mean time 8.8 g of 4-amino-1,2,4-triazole was dissolved into 40 mL of water.

Into a 400 mL beaker with stir bar sitting in a cold water bath is injected by way of a 3 mL pipette 1 squirt of the 4-ATZ solution followed by 4 squirts of the SDIC/AcOH solution. The additions in that order are continued at a pace to maintain the temperature at 20C. This takes approximately 30 minutes. The solution is seen to turn orange with slight effervescence and foaming which was easily dissipated by turning the stir speed from 250rpm to 400rpm. After the final addition the solution was allowed to stir for a further 30 minutes then vacuum filtered. The product was stirred into 12 g of sodium hydroxide in 300 mL of water and vacuum re-applied. Only a small amount of brown-buff coloured residue remained.

This light brown residue was energetic, flaring off on ignition leaving little residue. Presumably that the desired product but the yield is abysmal. The only thing i can see to change in a re-attempt is to well cool the reaction solution to 5C then filter then cool the hydroxide to 5C too and re-filter. Frankly I should have thought to do that this time, but do you cold filter Microtek? I just re-read your round abouts solubility figures.

[Edited on 1-7-2025 by Axt]

Microtek - 1-7-2025 at 00:42

Hmm, I don't cool it much before filtering, just to about room temp. I do cool the hydroxide soln since I have a feeling it does slowly react with the product (though that may not be an issue when the cyanuric acid is there to absorb it). I will say that my yields haven't been up to the claimed 90 % mark either, and just getting to the ~50 % level took some tinkering.

You could maybe try the method where SDIC and acetic acid is combined and stirred for 6 hours before the aminotriazole is introduced. I would still modify that procedure by adding the SDIC/HOAc to the aminotriazole rather than the other way round, which they seem to have done in the paper.

Axt - 1-7-2025 at 11:13

I tried the exact same procedure as above with cooling but had the exact same result. Does your crude product look the same? Does it match the deflagratory properties of the attached vid?

What solvent did you use for the azide substitution? Article mentions DMF, closest I'd have to that is NMP. Curious if just acetone would fill the role as it does for cyanuric triazide.

I found a fascinating route to the N-nitroimide, by the reaction of 4-ATZ with sodium ethoxide and a nitrate ester (ethyl nitrate, diethyleneglycol dinitrate and PETN are examples given). Gives a calculated density 1.82 and confirms that its zwitterionic nature can be broken and precipitated as its metal salts. Melts at 172C with explosion.

[Edited on 1-7-2025 by Axt]

Attachment: 4-Nitramino-124-triazole (4-NRTZ).pdf (260kB)
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Attachment: azotriazole.mp4 (7.6MB)
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Microtek - 2-7-2025 at 12:09

Yes, my crude does look something like that. I recommend a recrystallization from water. It makes beautiful needles that are similar to nitroguanidine, but smaller.
I haven't tried burning as large amounts as demonstrated in the video, but it does flash when ignited.
Regarding the azidation, I used DMF since I had some (though it is quite old and has a certain yellow tint). The AZTR didn't fully dissolve in the DMF, but the reaction worked anyway. This might be an indication that it is more important to use a solvent that promotes substitution, rather than one that dissolves the substrate completely. I do have a lot more of the tetrachloroazobis(triazole) so I might experiment more at some point. I'm particularly interested in seeing if less than all four of the chlorine atoms can be substituted, thus tuning the properties of the product.

The nitraminotriazole looks easy, and it would be interesting to explore both metal complexes and nitrogen rich salts. The only problem is time...

Axt - 6-7-2025 at 05:33

Hmmm. I recrystalised the azotriazole and yes, small matted felt-like needles that peel off the filter paper (attached), fast deflagration with no residue. Attempted BLG-1 but used ATRZ, copper nitrate and sodium bromate, 1:1:2 the process matched your experience blue crystals precipitating not immediately but on standing for an hour, but it is quite timid when ignited. Significantly slower than even the copper aminotriazole perchlorate although faster than nickel aminoguanidine nitrate. It makes me think the nitrate has precipitated preferentially. I don't have much left to test, but it would be good to run it again sans bromate and see if the nitrate product matches this product. It is still quite impact sensitive, but produces a weak snap not an ear splitting crack that you'd expect.

[Edited on 6-7-2025 by Axt]

Microtek - 6-7-2025 at 23:25

How did you ignite it? When flame ignited from above on a piece of Al-foil it pops, but does not penetrate the foil. When heated from below, it detonates and penetrates the foil. However, even then the detonation is not that impressive; it is not nearly as sharp as typical nitrotetrazolates or azides. Nevertheless, it is impressively efficient as an initiator.

Axt - 7-7-2025 at 01:38

I kept the filtrate, and it deposited a small amount of extra precipitate. Much more vehemic than the first major crop, and yes about the equivalent of NAP. Crystals are attached, what i presume to be the nitrate is quite jagged, whereas the bromate is quite cubic.

The first crop I would characterise as vehemic as blackpowder, when ignited with a smouldering splint even quite large quantities wouldn't do more than puff. Very small quantities of the second crop give that distinctive loud POP. Further evidence is provided by the colour of the flash on ignition, there is no blue tint like you should get from a Cu + Br reaction on the first but there is in the second.

I possible thought i had is even if the bromate is less soluble it may be less favourable to form its 3D structure, it doesn't get a chance before the nitrate precipitates. I'll probably try precipitation from the acetate with excess bromate.

Regarding the chloro derivatives, did you use the fine white precipitate from NaOCl reaction? or run it again with the SDIC literature method?

[Edited on 7-7-2025 by Axt]

Microtek - 7-7-2025 at 03:00

I used the inadverdent NaOCl product. It gave quite a large amount of amorphous powder that seemed quite uniform and clean, though I haven't done any kind of analysis of it beyond the melting point measurement. It could obviously be a mon-, di- or trichloro derivative as I can't find melting points for those.

Axt - 7-7-2025 at 06:14

You could try dissolving some of the putative tetrachloro compound in Ethyl acetate and acetone, it won't mean much if it does dissolve but if it doesn't it would be a qualitive test that it isn't the tetrachloride as they use ethyl acetate to extract it from the CA in the article and acetone evaporation to form single crystals.

All the lower chloro compounds are also soluble in acetone, The only odd one out I see is DCM was used for the tetraazide whereas acetone was used for the lower azides.

[Edited on 7-7-2025 by Axt]

Axt - 7-7-2025 at 19:58

Combining these two solutions while hot, leaving in fridge overnight seemingly gave the correct compound. Didn't measure yield but the filtrate was clear. It's a distinct cyan colour rather than the light blue.

Approx molar ratio C₄H₄N₈ : NaBrO₃ : CH₃COOH : Cu₂(OH)₂CO₃ = 3 : 28 : 8 : 1

0.3 g ATRZ
2.5 g NaBrO3
25 mL Water

0.13 g basic copper carbonate
0.32 g 90% acetic acid
25 mL Water

Microtek - 7-7-2025 at 23:29

I see you use a large excess of bromate. Did that improve yields relative to what I got? I used the stoichiometric ratio for all reactants and noted a slight blue tint to the filtrate, indicating that not all the copper ions were pricipitated.

Axt - 8-7-2025 at 00:41

I can't say anymore than the filtrate was clear.

I measured the filter paper vs a non-used paper and it come out a yield of about 180% :/ no amount of meddling with the reactive species will give this. I didn't try scaping it all off to get a proper measurement. With such a small quantity (100% would be 0.57 g) the overshoot could easily be explained by different paper weights and the excess bromate soaking into and drying in the paper (I just used kitchen absorbent paper to filter).

This did take more than the hour to precipitate, it was quite slow in this ratio and concentration.

I just hit the remainder of my azotriazole with a ball-peen hammer, it does respond quite similar to RDX ie. moderate hit creates a weak snap. I would have liked to make enough to try and fire by itself but it's such a pain in the arse to make.

[Edited on 8-7-2025 by Axt]

Axt - 8-7-2025 at 05:42

The straight 4-amino-1,2-4-triazole complex of copper bromate is more vehemic that the azotriazole. Of course there are highly vehemic compounds that have poor initiating ability, this may well be one of them being a very fuel heavy hydrate. It's highly insoluble, the fine sky-blue powder will drop out from dilute solutions of the sulphate as [Cu2(4-ATRI)6](BrO3)4·H2O. Constitution is according to https://doi.org/10.1021/acs.inorgchem.8b01045 https://sci-hub.se/10.1021/acs.inorgchem.8b01045 .

CuSO4.5H2O + 3C2H4N4 + 2NaBrO3 --> Cu(C2H4N4)3(BrO3)2

NaBrO₃ --------- 1.0 g ----- 6.63 mmol
CuSO₄·5H₂O --- 0.8 g ----- 3.20 mmol
50 mL water

C₂H₄N₄ --------- 0.84 g ----- 9.99 mmol
50 mL water

--> theoretical 1.83 g copper 4-amino-1,2-4-triazole bromate.

Axt - 8-7-2025 at 07:01

This was 600mg low density NRTZ pressed just enough to hold together and 20mg BLG-1 not pressed at all, just poured in and matchhead pushed on top. Definitely an NRTZ detonation, not as potent as the PETN at higher density and loading but that is to be expected.

EDIT: I just fired Copper 4-aminotriazole bromate under similar circumstances but with a primary loading of 35 mg (the weight of the caked lump) and the results were practically identical so I cannot draw any conclusions. Should have picked a more sensible base charge as all this might be proving is that NRTZ initiates easy, why I'm a bit dubious about pressing it.

[Edited on 8-7-2025 by Axt]

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