Sciencemadness Discussion Board - Exotic Primaries - Complex Salts

Anyone had experience with Silver 5-ATz complexes such as [(2Ag)5-ATz] NO3 or ClO4? The perchlorate is mentioned in engager’s tetrazole write up and a patent but there doesn’t seem to be much discussion on it. I tried to make the nitrate the other day according to klapotke’s procedure (https://pubmed.ncbi.nlm.nih.gov/19105192/) but it didn’t seem to yield anything that great. To start, 5-ATZ doesn’t dissolve that great in conc (anything higher than azeo %) Nitric Acid, and if you add too much water, the complexation time with AgNO3 can be ruined by just dumping out the Silver salt of 5-ATz. Too high conc of acid will form the 5-ATz nitrate salt instead which has low solubility as well and hinders complexation as well.

My product crashed out of the sol immediately on addition of AgNO3 to the 5-ATz/HNO3 mix as an off-white precipitate that started to yellow to a pastel yellow on air drying on a filter.

The product is supposed to detonate on flame contact and indirectly at 298C. For me, it does crackle faintly but I can’t seem to get it to dry. I would wager it’s like AgNTz in that it is a pain to detonate when wet but really goes when dry, but I can’t get this complex to dry to see anything amazing.

This salt could be a great alternative to LA, nitrotetrazoles, and such since it’s so seemingly easy to prepare, but I can’t get make it to match klapotke’s results. -My HNO3 and AgNO3 are pure and my 5-ATz is decently pure so idk.

This week I tried the nitrate salt, with similar results. I´ve used 65 % reagent grade nitric acid (I guess close to azeotropic is what they mean with "concentrated", otherwise they state "fuming" which is close to 100 %) and had also problems to dissolve the 5-ATZ. A warm water bath helped me to dissolve it.

Then I added the AgNO3 solution dropwise. Each drop changed immediately into a cheese-like white consistency after contact with the acidic 5-ATZ solution, but redissolved after some swirling. After several drops added, the solution remains turbid and it was no longer possible to redissolve it even with prolonged swirling.

After complete addition of the silver nitrate solution the whole reaction was dense white, like yoghurt. Here is a clear difference to the cited reference (Klapötke et al), they state that after addition of water the reaction mixture becomes turbid and some precipitate was formed.

I´ve also added some water, but it was impossible for me to see if the additional water produced additional precipitate.

After standing over-night I´ve filtered the precipitate, washed three times with distilled H20, then three times with IPA and let it dry over-night.

In contrast to your result, my product remains pure white with a flour-like consistency, but the behaviour against flame seems to be the same. No ddt, just a flash (not really impressive). See attached video.

So I would like to know what was wrong if you, microtek and I were unable to repeat the deceptive easy preparation.

And BTW my yield was much lower than cited (from 2,5 gram silver nitrate more than 4,2 gram was expected, but I got only 2,6 gram - something really went wrong).

Attachment: Disilver-5-aminotetrazole nitrate.mp4 (732kB)
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dettoo456 - 20-1-2024 at 10:46

I’d attribute the yellow color I got from pure lazy experimental methods - I just had all of the starting materials lying around so I thought I’d prep the complex in <15min. I didn’t even measure yield. Besides that though, the product SHOULD detonate on flame contact, albeit weaker than AgNTz or Pb(N3)2. Mine was only able to detonate after drying fully (sitting out at room temp for a couple of days).

It had trouble combusting in contact with a fuse though, in contrast to the more standard primaries like AgNTz.

If you’re paranoid about temperature stability (or friction and shock at that), I’d recommend the complex for cap designs but besides that, standard AgNTz or DBX-1 seems to be, ironically, easier to handle.

I’ll try to report stability results in the future with samples though.

Nemo_Tenetur - 20-1-2024 at 13:44

Well, Klapötke mentioned a possible explanation:

However, it must be noticed that the crystalline state of the sample is of extreme importance when testing the sensitivity of energetic compounds, i.e., crystalline compounds tend to show higher sensitivities to impact and friction.

This could be an explanation for the weak response of my amorphous flour-like sample to flame, but not for immediate precipitation after dropwise addition of the silver nitrate to the acidic 5-ATZ solution.

The experimental parameters are well defined.

Etanol - 20-1-2024 at 22:09

This could be an explanation for the weak response of my amorphous flour-like sample to flame, but not for immediate precipitation after dropwise addition of the silver nitrate to the acidic 5-ATZ solution.

No. The crystalline state affects mechanical sensitivity, but has little effect on DDT.

Etanol - 6-3-2024 at 22:03

Quote: Originally posted by MineMan

Those sensitivities are impressive. The copper version of NAP is 2J impact but 20N friction if I remember. I regard friction as more important. There are primaries that are immune to friction. This does look like a complex snyth tho. Wish the friction was less sensitive

Excuse me, what is NAP? Nickel aminotetrazole perchlorate?

upd
O, I find, Nickel aminoguanidine diperchlorate

[Edited on 7-3-2024 by Etanol]

ManyInterests - 2-4-2024 at 08:02

I wasn't sure where else to put this, so I am asking here.

I made some more NHN yesterday. Using 130ml of 95% (closer to 96%) ethanol, 43.5g of hydrazine sulfate, and 26.6g sodium hydroxide. The only difference is I was using bought nickel nitrate and not made. I dissolved 63g of nickel nitrate in 150ml of water with 0.005% dextrin by weight of the NN. The temperature did rise over 70C a few times which caused me concern.

I put in around 50ml of the solution, or a little less. But it was an excess. Everything appeared to run smoothly. My vacuum pump had issues so it was effectively gravity filtered. As I washed out the excess nickel nitrate with copious amounts of warm water and around 350ml of 95% ethanol.

The color is mostly OK. But there is that little tinge in it that bothers me. It is drying as of now, but I am wondering if it is something I should be concerned about.

I never saw any information on recrystalizing NHN. But I did hear that ammonia (I have 27% ammonia) works as a solvent. Would it dissolve it and simply be able to crash out the impurities? If they are impurities that is.

Microtek - 2-4-2024 at 23:43

I don't know how labile the hydrazine ligands are, but I would expect at least some of them to be replaced with the rather similar ammonia ligands if you try treating the NHN as a simple salt. Ammonia is more volatile than hydrazine, so maybe you could evaporate it off to reform the hydrazine complex, but I don't think it likely.

ManyInterests - 3-4-2024 at 03:45

Well it probably wasn't something major since the NHN appears to be of good quality.

But there is one major problem: I was expecting at least 12g of yield based on all the previous attempts I made. But I only got 4! I am legit baffled as to what happened.

My estimates that is I did not freebase enough hydrazine from my hydrazine sulfate, and the heating went out of control for a bit. The other thing is that my nickel nitrate solution was too concentrated. I diluted what I had to resemble more of what people showed when they used it (it is still quite dark green).

I am going to try again with similar quantities but I will take more care with heating on my mantle to not allow it to rise above 63 or 65c. My new mantle is very powerful, but a little finicky.

Nemo_Tenetur - 5-4-2024 at 13:52

Was the filtrate almost colorless (a very weak blue) or turquoise to green? From my experience, concentrated nickel nitrate solution doesn´t hurt the yield, but I´ve always performed the synthesis with commercially hydrazine hydrate solution.

Commercially available nickel nitrate is almost always the hexahydate, because it is VERY hard to get the anhydrous salt. Did you respect this within your yield calculation?

And, by the way, the use of dextrin is pretty useless IMHO. I know the patent which claim a higher density, but I can´t confirm this. From my experience - dozens batches - the highest bulk density is obtained with concentrated solutions. I always use a few percent hydrazine excess to ensure complete consumption of the nickel and to avoid an incomplete complexation.

I´ve seen a paper with an NHN accident ("spontaneous explosion of a normally stable complex salt" by Herbert Ellern an Donald E. Olander ) where an incomplete complexation lead to an unstable product with self-deflagration even when moist!

Just for your information that even with such a "safe" primary shit can happen.

ManyInterests - 6-4-2024 at 18:10

Was the filtrate almost colorless (a very weak blue) or turquoise to green? From my experience, concentrated nickel nitrate solution doesn´t hurt the yield, but I´ve always performed the synthesis with commercially hydrazine hydrate solution.

Commercially available nickel nitrate is almost always the hexahydate, because it is VERY hard to get the anhydrous salt. Did you respect this within your yield calculation?

And, by the way, the use of dextrin is pretty useless IMHO. I know the patent which claim a higher density, but I can´t confirm this. From my experience - dozens batches - the highest bulk density is obtained with concentrated solutions. I always use a few percent hydrazine excess to ensure complete consumption of the nickel and to avoid an incomplete complexation.

I´ve seen a paper with an NHN accident ("spontaneous explosion of a normally stable complex salt" by Herbert Ellern an Donald E. Olander ) where an incomplete complexation lead to an unstable product with self-deflagration even when moist!

Just for your information that even with such a "safe" primary shit can happen.

I am aware that danger can happen. this is why I treat all energetics with the utmost respect.

I've bumped up another thread about this for further discussion. I am not happy with what is going on.

EF2000 - 7-4-2024 at 01:50

I always use a few percent hydrazine excess to ensure complete consumption of the nickel and to avoid an incomplete complexation.

I´ve seen a paper with an NHN accident ("spontaneous explosion of a normally stable complex salt" by Herbert Ellern an Donald E. Olander ) where an incomplete complexation lead to an unstable product with self-deflagration even when moist!

Just for your information that even with such a "safe" primary shit can happen.

Mentioned paper (doi: 10.1021/ed032p24) says that in another, more serious accident hydrazine hydrate was used in 5% excess. And that hydrazine occluded in product's crystal, higher complexation, or contamination by combustible organics are possible causes of spontaneous explosion. Meaning that both excess and deficiency of hydrazine can be dangerous.
Conclusion: Hydrazine is generally unpleasant compound.

Attachment: ellern1955.pdf (1MB)
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Laboratory of Liptakov - 7-4-2024 at 02:35

When I reading last problems about hydrazine, respectively about NHN, maybe will better focusing on SA-DS. Yes, sensitivity is higher and is it full primary, but preparation is very easy and results are constant. I know, this mention is out of thread..... :cool:

ManyInterests - 7-4-2024 at 05:30

Quote: Originally posted by Laboratory of Liptakov

When I reading last problems about hydrazine, respectively about NHN, maybe will better focusing on SA-DS. Yes, sensitivity is higher and is it full primary, but preparation is very easy and results are constant. I know, this mention is out of thread..... :cool:

I made successful NHN several times before. I think what happened wrong is that I didn't freebase it correctly. It was simply too cold to freebase (all reagents were stored in a fridge for days to cool). I was not aware that it wouldn't freebase or react if it is too cold.

All previous successful times I did it at room temperature but simply kept everything cooler in an ice bath.

Remember LL, this is the first time I ran into issues with NHN synthesis! :p

Nemo_Tenetur - 7-4-2024 at 06:13

I had only one failure with NHN. This batch was of very low bulk densitiy, difficult to dry and hard to ignite. The color was more like pale pink, precipitated in high dilution.

Then I switched back to concentrated solutions and everything was fine again. In general, I think it´s good primary. But you require several hundred milligram and some containment for reliable DDT. Such a quantity produce alot of nickel dust, this isn´t the healthiest thing.

ManyInterests - 7-4-2024 at 07:58

I had only one failure with NHN. This batch was of very low bulk densitiy, difficult to dry and hard to ignite. The color was more like pale pink, precipitated in high dilution.

Then I switched back to concentrated solutions and everything was fine again. In general, I think it´s good primary. But you require several hundred milligram and some containment for reliable DDT. Such a quantity produce alot of nickel dust, this isn´t the healthiest thing.

That is true. But with an ETN mixed in at a 1:1 ratio or with other mixtures it can be an extremely powerful initiating agent. NHN has been in use in commercial detonators for decades now. It isn't an unproven new thing.

I've made a lot of progress with using NHN detonators and I plan on continuing with them.

For LL. I wish to inform him that CHP and LL8 are on the table.

Etanol - 8-4-2024 at 04:34

Quote: Originally posted by EF2000

(doi: 10.1021/ed032p24)

Electrostatic discharge?

Etanol - 13-4-2024 at 12:29

Try to change mixing method ATz and AgNO3:
add ATz to AgNO3, not AgNO3 to ATz.
Try don't add HNO3.
Add 5mmol hot ATZ solution into 10mmol solution of AgNO3, cold it.

[Edited on 13-4-2024 by Etanol]

Etanol - 30-4-2024 at 18:46

Are exists base complexes of 5-aminotetrazole and Ni or Cu or Co and NO3 or ClO4 anions?

[Ni(ATZ)n](ClO4)2
[Ni(ATZ)n](NO3)2
[Co(ATZ)n](ClO4)2
[Co(ATZ)n](NO3)2
[Cu(ATZ)m](ClO4)2
[Cu(ATZ)m](NO3)2

m=? n=?

Complexes of Co(III)?
[Co(ATZ)n](ClO4)3
[Co(ATZ)n](NO3)3

upd
from wiki: "The N-4 is basic as indicated by its binding to metal halides, such as the coordination complex [CoCl2(aminotetrazole)4"
Then only [Cu(ATZ)4](ClO4)2 has acceptable oxygen ballance:

[Cu(CH3N5)4](ClO4)2=>CuCl2+10N2+6H2O+2CO+2C

[Edited on 1-5-2024 by Etanol]

Microtek - 1-5-2024 at 12:33

As I commented in another thread, there definitely is a Ni complex with aminoTRIazole, so I find it very likely that it forms one with 5-ATz as well. I do have some 5-ATz and some Ni(NO3)2 so I could test if something precipitates either on mixing or when adding a perchlorate (or chlorate) solution.

Etanol - 1-5-2024 at 14:37

As I commented in another thread, there definitely is a Ni complex with aminoTRIazole, so I find it very likely that it forms one with 5-ATz as well. I do have some 5-ATz and some Ni(NO3)2 so I could test if something precipitates either on mixing or when adding a perchlorate (or chlorate) solution.

Thanks. But I do not think that Ni complex will be effective. It contains very little oxygen:
[Ni(CH3N5)6](ClO4)2=>NiCl2+15N2+8H2O+H2+6C

According to the article
"SPIN TRANSITION IN HETEROANION COMPLEXES IN THE Fe2+-4-AMINO-1,2,4-TRIAZOLE–NO3−SO4−SYSTEM" (10.1134/s0022476620090048) from sci-hub

,there is a complex Fe(ATrz)3(NO3)2⋅nH2O (ATrz = 4-amino-1,2,4-triazole),
which means that the 4-amino-1,2,4-triazole is bivalent as ligand.
Then ATrz complexes are more effective, especially copper:

[Ni(C2H4N4)3](ClO4)2=>NiCl2+6N2+6H2O+2CO+4C

[Cu(C2H4N4)2](ClO4)2=>CuCl2+4N2+4H2O+4CO or 2CO2+2C at high density

Microtek - 2-5-2024 at 22:54

I tried copper, cobalt, zink, iron(III), nickel, aluminum and magnesium as the central ion in 4-amino-1,2,4-triazole complexes with perchlorate anions some weeks ago. Al and Mg does not seem to give anything. I didn't really expect them to, but it rarely hurts to try.
The copper complex seems fairly soluble, but does give an energetic precipitate that explodes on heating wrapped in Al foil, though nothing spectacular.
The cobalt complex seems to be very insoluble, and gave a high yield of very fine cream precipitate. I did a second run with slow addition of the cobalt ions to a hot, stirred solution of ATrz and NaClO4, and cooled slowly with continued stirring, and this gave a slightly more coarse powder that could more easily be filtered. I ran it through the plate dent test after discovering that I could not set it off by mechanical stimulus, either by manual hammer blows on my anvil, or by the oblique abrasive pendulum impact test at 5.5 J (the highest setting of my apparatus). In the plate dent test, it performed disappointingly - somewhere in the vicinity of TNT, possibly due to a surprisingly low density of 1.58 g/cc. The nickel complex seemed most promising as it is non-hygroscopic, insensitive and undergoes DDT in 20 mg amounts when lightly confined. I haven't tested the actual initiating ability yet, nor the power in the plate dent test.

Yorty2040 - 25-5-2024 at 09:35

Has anyone done any work on metal-ligand complexes between a metal perchlorate and melamine?

Melamine could conceivably act as a bridging ligand between two (or maybe even three) metal centers and increase the density of the product compared to aminoguanidine perchlorate complexes, while not being much more challenging to prepare.

[Edited on 26-5-2024 by Yorty2040]

dettoo456 - 25-5-2024 at 19:24

Melamine itself has solubility issues in water, so a salt would be needed, and I don’t know how prone such a salt would be to hydrolysis. I don’t have any melamine, but I do have some acetoguanamine, so I might try to mess with that and see if anything promising is yielded.

[Edited on 26-5-2024 by dettoo456]

Etanol - 4-6-2024 at 12:01

Thanks for the idea. Ligand replacement is a real breakthrough in the synthesis of metal complexes. It works!
I successfully prepared copper-bis(4-amino-1,2,4-triazole) perchlorate from [Cu(NH3)4](ClO4)2 by reaction:
[Cu(NH3)4](ClO4)2+2ATrz=>[Cu(ATrz)2](ClO4)2+4NH3
[Cu(NH3)4](ClO4)2 was dissolved in hot water, ATrz was added, then the water is depressed with a hair dryer. Dirty blue powder has formed.
I cannot call the [Cu(NH3)4](ClO4)2 a primary explosive. But despite the poor oxygen balance ATrz complex without a shell in an amount of 50-100 mg burns a very sharp bright flash. I think, placed in the shell is quite suitable.
The substance is not sensitive to friction. 10-20 mg placed in foil burns sharply when heated, but detonates when hit with a hammer on a steel plate.

upd 50mg dried subs detonated without shall!

[Edited on 4-6-2024 by Etanol]

Etanol - 6-6-2024 at 10:52

[Cu(NH3)4](ClO4)2+2ATrz=>[Cu(ATrz)2](ClO4)2+4NH3

[Ni(4-aminotriazole)3](ClO4)2 was obtained in the same way. As you said, it does not detonate without a shell, but 30-50 mg in foil detonate when heated.

How about [Cu(Diaminourea)2](ClO4)2 and [Ni(Diaminourea)3](ClO4)2? Is it stable with long storage? Is it oxidized by oxygen of air? Hydrolysis?

[Cu(aminourea)2](ClO4)2 and [Ni(aminourea)3](ClO4)2?

Is there a way to make [Cu(aminourea)2](ClO4)2 and [Ni(aminourea)3](ClO4)2 from Semicarbazide Hydrochloride?

dettoo456 - 6-6-2024 at 19:09

Carbohydrazide (1,3-diaminourea) can be prepared by amination of Semicarbazide with Hydrazine or just by amination of urea with a large excess of hydrazine. These amination reactions though, can be complex and will result in aqueous mixtures of Urea, Semicarbazide, Carbohydrazide, and Hydrazodicarbonamide. If you want a source for Carbohydrazide, pyrohobby.ru might still have some for sale, but they have a horrible payment system that isn’t secure at all.

trisCarbohydrazide Nickel diPerchlorate (NiCP) apparently works as a decent primary (and is likely stable enough in storage) to function in detonators as mentioned in some Chinese patents, but at least the trisCHLORATE (NiCC) analogue is also a strong performer; see thread: http://www.sciencemadness.org/talk/viewthread.php?tid=159732

The Cu complex may work as well, though I have no idea and don’t plan to test it. Carbohydrazide is a pain to try to make, at least for me.

[Edited on 7-6-2024 by dettoo456]

Attachment: Tris carbohydrazide nickel perchlorate (NCP).pdf (32kB)
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[Edited on 7-6-2024 by dettoo456]

[Edited on 7-6-2024 by dettoo456]

Etanol - 9-6-2024 at 00:07

trisCarbohydrazide Nickel diPerchlorate (NiCP) apparently works as a decent primary (and is likely stable enough in storage) to function in detonators as mentioned in some Chinese patents, but at least the trisCHLORATE (NiCC) analogue is also a strong performer; see thread: http://www.sciencemadness.org/talk/viewthread.php?tid=159732

Thanks. I understand correctly that carbohydrazide (diaminourea) is more stable than semicarbazide (aminourea)?

dettoo456 - 9-6-2024 at 11:29

Chemically, Semicarbazide is more stable. The hydrazine bond is less stable than the simple amide. But, Carbohydrazide will of course be better as a fuel, due to the higher energy of the 2 N-N bonds.

Etanol - 9-6-2024 at 13:11

Chemically, Semicarbazide is more stable. The hydrazine bond is less stable than the simple amide. But, Carbohydrazide will of course be better as a fuel, due to the higher energy of the 2 N-N bonds.

It seems strange to me that carbohydrazide is sold in free form, but semicarbazid is sold only in the form of hydrochloride.

dettoo456 - 9-6-2024 at 16:55

Both exist as solids at STP, but Semicarbazide is likely just too hygroscopic and basic, so it’d form hydrated solutions and/or carbonates. Same as Aminoguanidine and guanidine.

Etanol - 23-6-2024 at 06:09

What is the solubility of copper glycinate-perchlorate?
How fast is its DDT? Is it detonate unconfined or only in a strong metal shell?

I tried to prepare copper glycinate-perchlorate with electrolysis of the equimolar mixture of glycine and NH4ClO4 until hydrogen stopped released. Then I filled the solution from copper powder, flawed it and dried. Blue non-crystall powder formed, which is not detonate without confined. However, it burns better than copper tetraammine perchlorate.

Null - 8-8-2024 at 21:10

Quote: Originally posted by snooby

Okay guys,

ICM 103 is something nobody of us would like to try out. The pyrazole stuff seems inpossible to get hands on. However, I can buy IT and ship it around the world. Price is around 1000 dollars for 500 grams (WTF). And if I lower the price would increase (50 grams are 380 dollars). So, are there 3 or 2 other guys/girls who would like to share the costs? Price would be around 200 dollars for 100 grams. That's a LIFE supply. I AM willing to receiver the order and ship IT around our globe. Sent me an PM if you would like to join. Only first 3 guys can get involved.

Hope this is still relavent to the thread, but it appears there is a decent place to get a precursor for this at chem impex for less than $100 for 100g.

dettoo456 - 9-8-2024 at 06:36

I hate to rain on your parade but there are far cheaper, easier to mfg, less toxic, and better performing EMs out there compared to this esoteric primary; AgNTz, BNCP, DBX-1, or even micronized PETN/C. Most of the ‘next-gen’ EMs are just thought up and pushed by military contractors to win outrageously expensive contracts for the way too expensive compounds they plan to make.

I.E., LLM-105 is nothing special in terms of performance, sensitivity or environmental safety, and yet is somehow being made in bulk because a company convinced a general somewhere that it’s God’s gift to man - even though they’ll require $1000s in taxpayer dollars to produce something like 90g for a hand grenade. Same issue with Cl-20.

If this precursor was some obscure phenethylamine or indole that’d produce a highly active serotonin moderator

, then maybe that ‘investment’ would be worth it.

Also, Chemimpex along with companies like Chemdirect only ship to commercial addresses - and that’s almost universal for all chem suppliers nowadays.

Null - 9-8-2024 at 21:00

Yep, you're right. I only focused on the pricing and not the delivery requirement. I have had a few companies allow me to use "Individual" for the company, but you're probably right in this not being one of them.

I will try with something innocuous, but yeah, I was too money focused on that.

dettoo456 - 9-8-2024 at 21:33

I was able to get some personal chemical orders shipped to my work’s building from chemimpex, chemdirect, and thermo, and you might have luck with that too depending on your job, but you’d need to sort it all out beforehand of course (billing and end-use auth).

Good luck with whatever EM research or precursor procurement you’re looking into though

Etanol - 5-9-2024 at 12:15

The cobalt complex seems to be very insoluble, and gave a high yield of very fine cream precipitate. I did a second run with slow addition of the cobalt ions to a hot, stirred solution of ATrz and NaClO4, and cooled slowly with continued stirring, and this gave a slightly more coarse powder that could more easily be filtered. I ran it through the plate dent test after discovering that I could not set it off by mechanical stimulus, either by manual hammer blows on my anvil, or by the oblique abrasive pendulum impact test at 5.5 J (the highest setting of my apparatus). In the plate dent test, it performed disappointingly - somewhere in the vicinity of TNT, possibly due to a surprisingly low density of 1.58 g/cc.

Hmm, Co(II) or Co(III) ?
Co(II)- 4-ATRz-ClO4 complex may be very powerful.
CoCO3+2HClO4=>Co(ClO4)2+CO2
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

Etanol - 15-9-2024 at 02:39

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.

MineMan - 30-9-2024 at 14:03

Compared to what? If it is safe and powerful enough to initiate why are you disappointed?

dettoo456 - 4-11-2024 at 07:20

Probably because it seems to just have too low of a DDT. The most promising primaries deflagrate on open flame contact or directly detonate. This stuff seems too poorly characterized (as of now) and the fact that it melts before fully decomposing is unfavorable in general.

It could have promise though, as you suspect. Cation or anion swapping for EM complexes is always a possible pathway to find good candidates for use. Perhaps the Ag, Ni, Fe salts of BrO3, IO4, NO3, etc.

Long life, short list

pdb - 17-11-2024 at 08:05

Energetic materials have been a hobby of mine for several decades. Especially primary explosives, due to their diversity and their ability to achieve DDT, which I find fascinating. As far as I know, the phenomenon that produces a shock wave in a few milligrams of primary explosive from a flame is not yet fully understood.

What I find ironic is that this passion doesn’t involve thousands of products but only a small number, even though, in chemistry, the substances capable of exploding number in the tens of thousands. Personally, I believe I have prepared fewer than twenty primary explosives in total, which I list here:

Pb(N3)2
Hg(N3)2
AgN3
Cd(N3)2
Hg(CNO)2
AgCNO
Ag nitrotetrazole
Ag azotetrazone
Ag2C2
Ag2C2·AgNO3
TATP
HMTD
DBX-1
DDNP
Tetracene
C3H12 cyanuric triazide
3-nitrobenzenediazonium perchlorate (CAS 22751-24-2)
2,4-Dinitro-benzenediazonium perchlorate (CAS 197637-25-5)

It’s not a lot, but it has been enough to keep me captivated for thousands of hours in my life. What should one make of this? Is it absurd and sad, or just original, like other more popular passions, such as music, painting, sports, etc.?

greenlight - 17-11-2024 at 09:52

There's a lot of hobbies out there that are much stranger than synthesising and testing energetics. It is quite unique due to the danger involved and illegality in most countries which is enough to deter the majority of people. Embrace it I say, as long as your doing it safely, it's definitely something different, I have been interested for nearly two decades and on and off experimenting when I can.

You've got quite an extensive list of primaries there. I have only made a few of them as I have always used them mainly for initiation of secondaries.

We do have some theories on the DDT transition.

When dealing with primaries like TATP or HMTD you may have noticed that the same unconfined pile that poofed underwent DDT when confined in even an open ended paper tube. In small amounts in the open, the gases are able to expand freely whereas in any spatial confinement they reflect and form turbulences which increase flame velocity. This exponential rise in flame temperature and resulting gas pressure is thought to be responsible for the transfer to detonation. Most likely when a certain temperature is reached or a certain speed of flame front (speed of sound).
When you have a large enough unconfined pile, just the weight of the explosive would be enough to cause this effect as well.

As for the primarys like azides which detonate in absolutely tiny quantities the cause is theorised to be the N3 ion. Two of the nitrogen can form stable N2 gas but the third nitrogen atom is expelled along with a considerable quantity of energy. This lone nitrogen can react with another N3 ion in the vicinity. If you can imagine this all happening in one small spot with millions of N3 ions decomposing simultaneously and all forming nitrogen gas plus a lone reactive nitrogen the rapid ly violent DDT transition for say lead azide makes sense. There's more to it as its broken down into two seperate reactions, this is just what I can recall at the moment.

Etanol - 17-11-2024 at 13:06

DBX-1

2,4-Dinitro-benzenediazonium perchlorate (CAS 197637-25-5)

Wow! Can you say anything about the properties of this? Hygroscopicity, solubility, stability, DDT?

Dinitro-benzenediazonium perchlorate

pdb - 17-11-2024 at 14:39

I hesitated to include it in my list of primaries because I’ve never managed to achieve DDT in open air. The substance deflagrates, leaving a combustion residue, but doesn’t detonate.

I even tried initiating it with another primary. The photo shows a trail of 2,4-Dinitro-benzenediazonium perchlorate ("DNBDP") interrupted in the middle by 50 mg of nitrobenzenediazonium perchlorate, which constitutes a pretty powerful initiation. The fire was set at one end, and you can see that the detonation at the center failed to propagate to the rest of the DNBDP.

Microtek, who also prepared it, said that DBBDP could achieve DDT, but neither Axt nor I have been able to make it detonate.

pdb - 17-11-2024 at 14:53

Quote: Originally posted by greenlight

We do have some theories on the DDT transition.

Yes, of course, when the configuration of the charge creates confinement—either because it is contained in an enclosure or under its own weight—the accumulation of combustion gases and the heat released can lead to the formation of a shock wave. Even a low explosive can be made to detonate under certain conditions.

But the question is different when a few milligrams deposited without any compression on a metal plate manage to dent or puncture it. What you say about the N3 radical, where the ejection of one nitrogen atom impacts another N3, merely describes a chain reaction. However, the majority of chain chemical reactions occur without detonation, so IMO this explanation is not sufficient to account for the behavior of primaries.

Etanol - 18-11-2024 at 03:30

I hesitated to include it in my list of primaries because I’ve never managed to achieve DDT in open air. The substance deflagrates, leaving a combustion residue, but doesn’t detonate.

I even tried initiating it with another primary. The photo shows a trail of 2,4-Dinitro-benzenediazonium perchlorate ("DNBDP") interrupted in the middle by 50 mg of nitrobenzenediazonium perchlorate, which constitutes a pretty powerful initiation. The fire was set at one end, and you can see that the detonation at the center failed to propagate to the rest of the DNBDP.

This is strange. Such properties can only occur if the product does not correspond to the formula of 2,4-Dinitro-benzenediazonium perchlorate.

But the question is different when a few milligrams deposited without any compression on a metal plate manage to dent or puncture

It appears that rapid DDT requires the presence of chemical bonds with positive enthalpy and low activation energy that can be converted into detonation products in 1-3 molecular collisions.
This contributes to a small critical detonation diameter and low detonation excitation pressure.

Axt - 18-11-2024 at 04:41

Good god pdb, it's been just shy of 20 years it's good to see you made it to 75 posts haha. This is off topic though, it's not a complex salt and the original thread is here http://www.sciencemadness.org/talk/viewthread.php?tid=3681 . Yes, I made the dinitrobenzenediazonium perchlorate and yes its ability to DDT is lower than that of the less nitrated homologues. Its counter intuitive for numerous reasons but is clearly shown in practice. It's likely due to balance between the electron deficient diazonium group and the electron withdrawing nitro groups creating a stronger bond overall. Most sensitive to least is benzene>nitrobenzene>dinitrobenzene, a clear pattern with the worst of all being the benzenebis(diazonium) diperchlorate derived from phenylenediamine which likes to detonate in solution. On the other side, one would expect electron donating groups such as methyl (aminotoluene) to create a more sensitive diazonium salt than even that of benzene.

I'm not sure what your photo is showing btw, it looks like an orange blob taped to the middle of some angle iron. I've never confined dinitrobenzenediazonium perchlorate but assumed it would DDT given any excuse with confinement.

[Edited on 18-11-2024 by Axt]

greenlight - 18-11-2024 at 09:46

Quote: Originally posted by greenlight

We do have some theories on the DDT transition.

I was under the assumption that this chain reaction with a lone reactive nitrogen for each molecule that decomposes multiplied by the billions of individual molecules present even in a small amount would trigger a chain reaction in rapid time.
But, I must agree that it wouldn't explain it fully, especially when dealing with salts that are not azides.

Maybe the ability of a primary explosive to DDT in extremely small unconfined quantities is due to not one but a combination of factors that exist in varying degrees in different types.
Theoretically it could be:

1. Enthalpy values and energy release.

2. Temperature of combustion/deflagration reaching a certain threshold.

3. Accelerating combustion/deflagration rate until velocity of speed of sound is reached.

4. Catalytic action of metal ion bonded in complex salts.

5. Knock on effect of a reactive species/ion such as with azides.

6. Adiabatic heating from instantaneous production of hot gases.

Those are just ideas at this point, I did not realise it is such an unsolved part of energetics. Very interesting.

pdb - 18-11-2024 at 12:50

Good god pdb, it's been just shy of 20 years it's good to see you made it to 75 posts haha.

It's nice to see you're still alive and still tuned in to our favorite topic !

I'm not sure what your photo is showing btw, it looks like an orange blob taped to the middle of some angle iron. I've never confined dinitrobenzenediazonium perchlorate but assumed it would DDT given any excuse with confinement.

I'll try to be more explicit. It's a pyrotechnic train consisting of a segment of 2,4-dinitrobenzenediazonium perchlorate, followed by a segment of 3-nitrobenzenediazonium, and then another segment of 2,4-dinitrobenzenediazonium perchlorate. The result shows that the detonation of the 3-nitrobenzenediazonium (which bent and pierced the angle iron) did not cause the 2,4-dinitrobenzenediazonium perchlorate to achieve DDT. I had conducted other tests at the time and failed to achieve DDT.

Etanol - 20-11-2024 at 11:46

How about Copper(II) Perchlorate Complex with Aminoguanidine?
According to the "Synthesis, Structural and Energetic properties of Copper(II) Perchlorate Complex with Aminoguanidine", its thermal behavior is not much lower than that of NAP: 215°C vs 230°C.
However, I am afraid that the combination of copper and hydrazin bond will make the product unstable and dangerous.
Also, I found a youtube video with this substance. However, the author prepared not a pure substance that does not work.
I want to make a pure product without impurities of sulfate or acetate.

pdb - 20-11-2024 at 13:17

Isn't example 2.4 of patent EP2450330A2 ?

Axt - 20-11-2024 at 13:46

Yes, although no reference gives its extraction, whether it readily precipitates or not.

Generally if the complex is very water soluble you can use the metal sulphate and sodium salt oxidiser then run an ethanol extraction. Dissolve everything in a small amount of water, add ethanol as sodium sulphate is poorly soluble in ethanol/water it precipitates, heat to 40 degrees or so and filter while hot, cool solution down to -5 in freezer and filter the complex.

Etanol - 20-11-2024 at 14:32

Thank you. But apparently this is Fake. Copper aminoguanidine perchlorate cannot exist.
When trying to synthesize, aminoguanin perchlorate slowly oxidizes copper perchlorate in a Cu2O in an hot acidic environment and instantly does this in a slightly alkaline environment.

Laboratory of Liptakov - 22-11-2024 at 07:03

Copper perchloride ? Such errors do not writte anyone from this forum. Text looks a like bullshit from AI..... :cool:

Axt - 22-11-2024 at 10:25

Thank you. But apparently this is Fake. Copper aminoguanidine perchlorate cannot exist.

You literally just linked to another prep of it, are you saying they are both lying and are both "fake".

The other is a google image translate of the patent.

Screenshot 2024-11-23 051022.png - 261kB

Laboratory of Liptakov - 23-11-2024 at 09:02

The time has come when you can't believe everything you see with your own eyes. Another error....hemesulfate ....Yes, aminoguanidine hemisulfate exist: https://pubchem.ncbi.nlm.nih.gov/compound/Aminoguanidine-hem... :cool:

Axt - 14-12-2024 at 02:15

Anyone had experience with Silver 5-ATz complexes such as [(2Ag)5-ATz] NO3 or ClO4?
My product crashed out of the sol immediately on addition of AgNO3 to the 5-ATz/HNO3 mix as an off-white precipitate that started to yellow to a pastel yellow on air drying on a filter.

In referernce to http://www.sciencemadness.org/talk/files.php?pid=689047&...

Dettoo, did you change anything from the literature procedure to make this work? I gave it a go and achieved as much as you did in this post, it just dumps the silver aminotetrazolate out as soon as the silver nitrate solution is added. Nothing like as described in the article.

The article sems to be wrong, it uses equal molar quantities of silver nitrate and aminotetrazole thus impossible to achieve their stated 80% yield of Ag2(CH2N5)NO3.

I just went and checked the original 1972 patent (US3663553) for the perchlorate and they are using the same nonsensical molar ratio as well. Make it make sense.

[Edited on 14-12-2024 by Axt]

dettoo456 - 14-12-2024 at 06:34

I have not revisited this complex any time recently, as the product was pretty lackluster IMO (performs on the level of MTX-1). Klapotke has a stellar reputation regarding EM synthesis methods as well, so I don’t know why this particular preparatory method from him seems so finicky. I’m assuming the amphoteric nature of the 5-substituted tetrazoles is what is causing these inconsistencies. pH control is likely more important in this case than I guessed.

On page 3 of the article you linked, the authors notice that the complexes are “ are extremely insoluble in every common solvent, and only dissolve in concentrated acid solutions (e.g., hydrochloric, nitric, or perchloric acid) to form the corresponding 5- amino-1H-tetrazolium salt (chloride, nitrate, or perchlo- rate) in which the silver cations are no longer coordinating to the tetrazole ring”.

If I get time I can try again, though I’d currently like to mess with DPPE-1 & its Ag analogues. I’ll need to make some more HNO3 before I prep the Ag 5-ATz complex again :|

[Edited on 14-12-2024 by dettoo456]

Axt - 14-12-2024 at 10:52

As I posted that it was stirring so I just threw an extra molar equivalent of silver nitrate into it. It actually did get near 100% yield, 3.6g by using 0.02mol AgNO3 and 0.01mol 5-ATZ but it's no more energetic, just sputters with an energetic puff now and then. I can't say this was comparative to MTX-1 which will at least POP. I'll just throw this one in the bin of failures.

I really wanted a nitrate to work, I tried "DAN-2" the nitrate perovskite but I wouldn't even class it as an energetic, barely burns. DAP-2, DAP-4 and DPPE all follow their prep details well though, instantly dropping out of solution as small cubes. I cannot quantify their sensitivity but it's much more than the articles state.

I'm looking at copper aminotriazole chlorate with mild interest. Only if its soluble in ethanol enough to extract it from the sulfate as I'm not using barium chlorate.

[Edited on 14-12-2024 by Axt]

Attachment: copper aminotriazole chlorate.pdf (725kB)
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dettoo456 - 14-12-2024 at 14:01

The DPPE-1 I trust to at least perform, as another member here shared some of his experience in preparing it along with showing properties. I made what I thought to be the K-DABCO-ClO4 too, though that burned about as well as black powder (like you mention with the DAN-2). I have around 500g of DABCO though, so those perovskites are more enticing at the moment than tetrazole complexes.

I may try a CuAG-IO4 complex now that I think about it, may be an interesting alternative to NAP if it hasn’t already been tried and found to be shit.

[Edited on 14-12-2024 by dettoo456]

Axt - 16-12-2024 at 12:36

The DPPE-1 I trust to at least perform, as another member here shared some of his experience in preparing it along with showing properties. I made what I thought to be the K-DABCO-ClO4 too, though that burned about as well as black powder (like you mention with the DAN-2). I have around 500g of DABCO though, so those perovskites are more enticing at the moment than tetrazole complexes.

I may try a CuAG-IO4 complex now that I think about it, may be an interesting alternative to NAP if it hasn’t already been tried and found to be shit.

[Edited on 14-12-2024 by dettoo456]

I'd be happy to be proven wrong, but I don't think copper will form complexes with periodate. I have tried it with ethylenediamine and ammonia and only received what I took for copper periodate (I'm sure that can be easily tested, but I haven't). Light green powder that when ignited It would smoulder through the mass releasing a bit of iodine smoke.

The potassium DABCO perchlorate and its ammonia analogue burn more like some type of rocket fuel. Potassium DABCO nitrate I would have loved to be a blackpowder like propellant, but as best I can determine just turns black and splutters a bit.

MineMan - 18-12-2024 at 14:52

Thank you. But apparently this is Fake. Copper aminoguanidine perchlorate cannot exist.

You literally just linked to another prep of it, are you saying they are both lying and are both "fake".

The other is a google image translate of the patent.

There is a thread on this, where the user compares it to NAP.

MineMan - 18-12-2024 at 14:53

Thank you. But apparently this is Fake. Copper aminoguanidine perchlorate cannot exist.

You literally just linked to another prep of it, are you saying they are both lying and are both "fake".

The other is a google image translate of the patent.

There is a thread on this, where the user compares it to NAP.

Microtek - 3-1-2025 at 01:19

I have been evaluating ZnCP as a primary for indoor testing due to concerns over the potential production of nickel carbonyl gas when using nickel based primaries such as NAP, NHN or NiCP (NAP is IMO still the state of the art primary where good ventilation is possible, or outdoors).

I have prepared ZnCP in a number of different ways, but while the substance seems to be ZnCP, I'm not impressed with its power. For this reason I wanted to ask here, if anyone has prepared ZnCP and has some experience with it.

Axt - 3-1-2025 at 22:24

I've no answer Microtek but are you making the carbohydrazide yourself? The only accessible literature route I see is cyanuric acid + hydrazine hydrate (40% to 100% concentration), the prep seems quite trivial. US3258485.

The only zinc salt I can remember making was Bis(ethylenediamine)zinc(II) Bromate (possibly tris) which would flash on ignition, with notably less vehemence than the copper analogue which would go off with a bang. The zinc complex that did catch my attention was the tetrakis(DMSO)zinc(II) perchlorate complex, anhydrous and melts at about 70 degrees. No explosive properties mentioned although the silver analogue is said to be the most violent and dangerously explosive.

Microtek - 4-1-2025 at 02:39

I'm using commercial carbohydrazide, and it has worked as expected in other syntheses such as NiCP (which is almost as good as NAP) or CoCP. The reason I was going for ZnCP apart from the low toxicity is that reportedly, the chinese have begun using this material in their caps. One explanation could be that they use a large amount of primary, maybe 200-300 mg in a cap. Another could be that they use it in conjunction with something else, much like the common LA/LS mix.

Axt - 4-1-2025 at 05:20

This report seems to affirm your experience. Co and Ni Fired, Zn did not. Although it doesn't clearly state by which manner it failed, it reads as if it didn't ignite.

Attachment: Ni Co Zn carbohydrazide complexes.pdf (410kB)
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Axt - 5-1-2025 at 23:29

It might be worth converting the carbohydrazide to urazine and complexing that, if only for experimentation. Urazine is highly dense and purported to be the highest VOD, urazine perchlorate salt at 9799m/s @ 2.12g/cm3. Urazines prep is online in https://sites.lsa.umich.edu/jbuss/wp-content/uploads/sites/8... , page 29 (it's just heating carbohydrazide with HCl). It's perchlorate salt and copper complex is given here https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002... .

I threw some a small amount of hydrazine and cyanuric acid together, held at 110 degrees the past 36hrs and received what I believe to be a poorly soluble portion of hopefully urazine and a larger portion of hopefully carbohydrazide. Definitely buy it if you can, surely the better option to distilling hydrazine but the patent seems to work.

Microtek - 6-1-2025 at 01:01

I was experimenting with the urazine derivatives some time ago, but found that the perchlorate, while very powerful indeed (and also very sensitive), was too hygroscopic for most uses. I did do a little work on urazine complexes, but nothing systematic as that wasn't my focus at the time. I didn't find anything worthwhile to report.

On a side note, the major byproduct of the carbohydrazide to urazine reaction is hydrazine hydrochloride. I tried adding 50% sulfuric acid to the filtrate, and did receive large amounts of white precipitate that is probably hydrazine sulfate (though I haven't analysed it properly). If so, the reaction is efficient enough that it could be a valid alternative to the usual amateur pathway to HS (if you can buy carbohydrazide).

Axt - 6-1-2025 at 03:29

Yeh I should have searched the forum for urazine, you've mentioned it a couple times before. Can you comment on the isolation of the salt? there's no details in the article and presumably it's pretty soluble.

What about the solubility of the ZCP? does it precipitate from water or other?

Microtek - 6-1-2025 at 11:32

UzP is very soluble. I isolated it by reacting with a stoichiometric amount of perchloric acid and then evaporating the water at elevated temperature.

ZnCP is not very soluble in cold water, but fairly soluble in boiling water. In the method I followed, the reactants are combined (dropwise addition of CHZ soln to Zn2+ / ClO4- soln) which precipitates the product. Then temp is raised to reflux which redissolves the ZnCP. The temp is then allowed to come to 10C (or just room temp) with stirring to crystallize the product in a slightly less fine morphology.
As far as I can tell, there is no reason to go to the trouble of preparing ZnClO4, any soluble Zn(II) salt along with a soluble perchlorate will give the same product.

Axt - 7-1-2025 at 06:45

As far as I can tell, there is no reason to go to the trouble of preparing ZnClO4, any soluble Zn(II) salt along with a soluble perchlorate will give the same product.

Have you tried many other salts? Mixing my putative carbohydrazide with zinc sulphate results in immediate precipitation, I don't know if you can confirm the insolubility of the sulphate with the commercial grade or not.

Mixing it with silver nitrate also produces an immediate white precipitate, this is unstable and seems to reduce to silver when drying. Adding the wet white product to hot water immediately turns it black/brown.

Microtek - 7-1-2025 at 09:12

No, I just tested it by dissolving ZnO in sulfuric acid and adding a carbohydrazide soln. No precipitate was formed. Your carbohydrazide might contain some hydrazine (as the bicarbonate maybe), which could give slightly soluble hydrazine sulfate and would also explain the reaction with silver.

Axt - 7-1-2025 at 10:45

You are correct about bi/carbonate being present, it fizzed under a drop of HCl.

The solution turned opaque milky with no noticeable precipitate settling out, but I stopped at that because I didn't have much to waste. Zinc carbonate being practically insoluble it does explain that.

Hydrazine reduces silver nitrate on contact, immediate browning and fizzing. I assume carbohydrazide would form a carbonate too, this seems most likely based on the silver complex being at least transiently stable. I dried the precipitate and there were a couple bits less black than pitch black that decomposed energetically when ignited.

Microtek - 7-1-2025 at 13:02

IIRC, I experimented with synthesizing carbohydrazide myself before deciding that buying some was the way to go, possibly because it was annoying to isolate. I do think that your urazine is probably fine since the low solubility makes it easy to purify.

Microtek - 14-1-2025 at 01:28

Just a heads up: The paper by Talawar et al on page 27 of this thread has some erroneous numbers in the synthesis description. The ratio of nickel to carbohydrazide is given as 0.07 mol to 0.02 mol. In would make sense if these numbers were simply reversed, but the masses are also wrong (and also don't match the molar amounts either). I think it's obvious that you should go with a molar ratio of 1 Ni to 3-4 CHZ and 2 ClO4, but just wanted to point this out to anyone wanting to replicate the work.

Axt - 14-1-2025 at 14:39

Yeh the mole ratio is way off, the gram weights they provide correlate to a 1:2 ratio, best ignored.

I did try ZCP, without success.

0.41g (5mmol) zinc oxide in 20mL of water was dissolved by the addition of 1.44g (10mmol) of 70% perchloric acid. Another solution comprised of 1.35g (15mmol) of carbohydrazide in 10mL of water is then poured into the Zinc perchlorate.

There was an immediate milky precipitate like before which was filtered off, this was inert and amounted to <100mg. Leaving it sit for a bit resulted in a bit more white very fine precipitate that was mildly energetic, when held in a flame it would eat it away to nothing but wasn't self sustaining. I'm guessing what I arrived at via cyanuric acid/hydrazine was not carbohydrazide although its preparation went exactly as described. How does carbohydrazide react to being ignited, or heated on a spoon/foil?

Attaching a Polish doctoral Dissertation on some explosive complexes, I've ran it through a google document translation. It's all very interesting but I cannot identify anything of practical interest, most failing to act as initiating explosives.

I attempted to make the Copper aminotetrazole nitrate but just ended up with a thickened green solution with no noticeable precipitate, it's as if it polymerised. In attachment it is evaporated out, but I've got like 3 litres of this slime.

[Edited on 14-1-2025 by Axt]

Attachment: Explosive complexes Dissertation - english.pdf (6.4MB)
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Axt - 15-1-2025 at 05:15

. How does carbohydrazide react to being ignited, or heated on a spoon/foil?

Compared to attachment.

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Axt - 15-1-2025 at 06:21

And this for the zinc complex, very feeble under flame, quite sensitive under impact.

Attachment: ZnCP.mp4 (6MB)
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Microtek - 15-1-2025 at 11:21

My carbohydrazide melts, ignites and burns with a pale flame while emitting a hissing/roaring noise. It leaves no residue and produces no smoke. The ZnCP, when ignited in the open, flashes and burns while spitting out particles. It is not as fast as flash powder and doesn't burn as completely, often blowing itself out.
I read a little of the polish thesis, and it seems the author uses lead azide (200 mg) to ignite the complexes, so they may not be capable of DDT on their own. Also, witches eyes detonate with a velocity of 8750 m/s apparently (p. 100).

Axt - 15-1-2025 at 12:07

That description of carbohydrazide would fit mine when its heated underneath. as does the self-extinguishing albeit mine sounds less energetic. I've has a few things sputtering and self-extinguish, the silver aminotetrazole nitrate and copper triamino nitrotetrazolate does as well.
.
Both self-acceleration to detonation as well as primed with lead azide are tested in that dissertation. Self acceleration starts page 88 nickel hydrazine nitrate, cadmium hydrazine perchlorate and Copper/nickel aminotetrazole perchlorate being the only few.

"Witch eyes" I believe is a translation error for RDX. No idea what "kitchenette" is maybe PETN. 4-aminotriazole still looks interesting, it'd be a hydrazine formic acid condensation product.

[Edited on 15-1-2025 by Axt]

Microtek - 16-1-2025 at 11:38

I see now. It seems that there aren't any really intersting candidates from my perspective unfortunately. The [Cu(5-AT)2](ClO4)2 looked good, but then I read that it was extremely hygroscopic.

I have turned to a different strategy for preparing primaries with a good balance of properties. It's inspired by the old practice of adding SADS to NHN to make it DDT more reliably. I have been experimenting with copricipitating silver nitrotetrazolate with CoCP. Aiming for a 20% AgNT content, the product was very insensitive, giving zero reactions out of ten attempts at the highest setting of my oblique abrasive impact apparatus. PETN gives about 40% reactions at that setting.
I then placed a small amount of the product in an old porcelain mortar and ground it with a porcelain pestle. On vigorous grinding it did detonate, and broke the mortar.

Etanol - 16-1-2025 at 13:16

I see now. It seems that there aren't any really intersting candidates from my perspective unfortunately. The [Cu(5-AT)2](ClO4)2 looked good, but then I read that it was extremely hygroscopic.

This is a very strange formula. For the cationic complex, [Cu(5-AT)4](ClO4)2 is more likely. For double salt, Cu(5-AT)ClO4 or nCu(ClO4)2*m(5-AT)HClO4

1) Zhao, Fang-Hua; Che, Yun-Xia; Zheng, Ji-Min; Grandjean, Fernande; Long, Gary J. . (2012). Two Acentric Mononuclear Molecular Complexes with Unusual Magnetic and Ferroelectric Properties. Inorganic Chemistry, 51(8), 4862–4868. doi:10.1021/ic300394c

2) Brubaker, Carl H.. (1960). Metal Tetrazole Complexes: Bis-(5-aminotetrazolato)-copper(II). Journal of the American Chemical Society, 82(1), 82–85. doi:10.1021/ja01486a017

Microtek - 17-1-2025 at 00:10

I would tend to agree, and I don't know if the formula is correct, it is simply the way they name it in the thesis. I have read other papers (by Stierstorfer, et al) that used XRD to investigate the structure of some complexes and found quite unexpected complexation around the metal atoms.

[Edited on 17-1-2025 by Microtek]

Microtek - 23-1-2025 at 00:43

Since CoCP is a carbohydrazide complex, and since carbohydrazide quite readily reduces Ag+ ions, I looked for other ligands that might work at least as well, but not give blackening of the product. I first looked at 4-amino-1,2,4-triazole (4-ATRI) since I have a fair amount of that. It turns out that both copper, iron(II), manganese, zink and cobalt(II) perchlorates give energetic precipitates with 4-ATRI. The copper variant is an amazing blue colour so deep it seems almost ultraviolet. Unfortunately, it is not quite energetic enough for my tastes. The iron and cobalt variants seemed to be powerful enough when confined, but was not quite "vehemic" enough. In order to improve that aspect I experimented with coprecipitation of AgNT. After a number of failures I discovered that AgNT seemingly undergoes some sort of reaction with 4-ATRI (maybe complexation) that renders the AgNT unimpressive.
Mechanically mixing the AgNT and other complex salt ( [Co(4-ATRI)n](ClO4)2 or CoCP or other ) works fine and the product is very impressive and not very sensitive, but for safety reasons I would like to avoid handling dry AgNT. One option would be to wet the materials with something like alcohol or gasoline during mixing, possibly with added wax to reduce sensitivity further.

Microtek - 25-1-2025 at 14:23

For some reason, I can't edit my posts, so I'm just going to append:

I found some interesting papers on copper(4-ATRI)n(ClO4)2

https://arc.aiaa.org/doi/10.2514/1.7931 and attached.

From this it seems that depending on whether three or four 4-ATRI ligands are inserted into the complex you will get either a primary explosive on par with lead azide, or a burn rate modifier that is insensitive to friction and only moderately sensitive to impact.

Looking at the aerosol toxicities of transition metal salts, it seems that only iron compounds can really be thought of as harmless, so that is where I have focused my attention.

Attachment: Cudzilo-2.pdf (633kB)
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Etanol - 26-1-2025 at 00:19

From this it seems that depending on whether three or four 4-ATRI ligands are inserted into the complex

This is very strange. I think it is worth checking these syntheses. I made a complex of copper perchlorate with 4-aminotriazole and it was not poorly soluble and not light blue. It is impossible to recrystallize from the water. It was very well-soluble in water dark blue crystals with the properties of primary explosive after complete drying.

Axt - 26-1-2025 at 01:54

I was going to say the tris 4-aminotriazole complex forming a polymeric structure could explain its lower solubility but that does not correlate with the above either. 200mg was the minimum to initiate PETN, usable but not particularly potent [attached].

How are you making iron perchlorate? I'm assuming HClO4 doesn't attack Fe2O3 too well, but have never tried.

[Edited on 26-1-2025 by Axt]

Attachment: Copper aminotriazole perchlorate.pdf (502kB)
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Etanol - 26-1-2025 at 02:26

I was going to say the tris 4-aminotriazole complex forming a polymeric structure could explain its lower solubility but that does not correlate with the above either. 200mg was the minimum to initiate PETN, usable but not particularly potent

I took 4-aminotriazole assuming [Cu(4-ATRI)2](ClO4)2 and the product strong detonated without a shell in the mass of about 30-50 mg. It was stronger than the nickel complex.

MineMan - 26-1-2025 at 19:01

I see now. It seems that there aren't any really intersting candidates from my perspective unfortunately. The [Cu(5-AT)2](ClO4)2 looked good, but then I read that it was extremely hygroscopic.

I have turned to a different strategy for preparing primaries with a good balance of properties. It's inspired by the old practice of adding SADS to NHN to make it DDT more reliably. I have been experimenting with copricipitating silver nitrotetrazolate with CoCP. Aiming for a 20% AgNT content, the product was very insensitive, giving zero reactions out of ten attempts at the highest setting of my oblique abrasive impact apparatus. PETN gives about 40% reactions at that setting.
I then placed a small amount of the product in an old porcelain mortar and ground it with a porcelain pestle. On vigorous grinding it did detonate, and broke the mortar.

Isn’t that about the same as small crystal NAP from reports? Have you tried any of the friction and impact insensitive primaries that only respond to flame… I believe it was a Chinese paper here posted 2 years back, I recall you saying the preparation was not too bad?

Microtek - 27-1-2025 at 00:08

@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.

Axt - 27-1-2025 at 02:39

Yes, good point, although it reads as 200mg minimum its evidence for such a claim is lacking or not published.

I had a look around and found some iron powder, I've so much forgotten stuff covered in spider webs, I feel like I can find anything if I just look hard enough.

Iron powder reacts very vigorously with perchloric acid, it's a sit it outside mix and retreat type reaction where I let it boil itself dry, this may be hazardous on larger scale. I then extracted the remains with acetone. Into the acetone extract I dribbled a bit of DMSO which immediately precipitated a putative Fe(DMSO)6(ClO4)3 complex as a fine yellow/buff powder. This is energetic, flaring off somewhat like blackpowder and is quite impact sensitive leaving a pungent smell. It is unlikely to be vehemic to the point of practical value.

[Edited on 27-1-2025 by Axt]

Etanol - 27-1-2025 at 09:00

I found some interesting papers on copper(4-ATRI)n(ClO4)2

https://arc.aiaa.org/doi/10.2514/1.7931 and attached.

From this it seems that depending on whether three or four 4-ATRI ligands are inserted into the complex you will get either a primary explosive on par with lead azide, or a burn rate modifier that is insensitive to friction and only moderately sensitive to impact.