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Axt
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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.
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Microtek
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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.
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Microtek
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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.
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Axt
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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
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Compared to attachment.
Attachment: maybecarbohydrazide.mp4 (4.2MB)
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Axt
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And this for the zinc complex, very feeble under flame, quite sensitive under impact.
Attachment: ZnCP.mp4 (6MB)
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Microtek
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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).
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Axt
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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]
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Microtek
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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.
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Etanol
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Quote: Originally posted by Microtek  | | 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
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Microtek
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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]
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Microtek
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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.
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Microtek
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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
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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.
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Axt
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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
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| Quote: Originally posted by Axt | | 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.
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MineMan
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| Quote: Originally posted by Microtek | 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?
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Microtek
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@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.
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Axt
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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]
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Etanol
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| Quote: Originally posted by Microtek |
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.
|
| Quote: Originally posted by Axt | 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].
|
| Quote: Originally posted by Etanol |
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. |
Wow. Indeed, when 0.01 mol Cu(ClO4)2 water solution is added to 0.05 mole 4-aminotrizole water solution, the blue crystals insoluble in cold water are
formed. The mass of crystals after drying was 6.11 g, which is very close to the theoretical 5.99g that correspond to the [Cu(4-ATRz)4](ClO4)2.
However, it is weaker than the [Cu(4-ATRz)2](ClO4)2.
4 - is the maximum stable number of triazole in this complex.
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Laboratory of Liptakov
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If you add anything to Cu(ClO4)2, it will almost always be energetic or highly energetic. Even filter paper soaked in this perchlorate behaves like
paper soaked in nitroglycerin. They are indistinguishable in the well-known hammer test. The paper turns into micrometeorites that remain under the
skin.
Development of primarily - secondary substances: CHP (2015) neutral CHP and Lithex (2022) Brightelite (2023) Nitrocelite and KC primer (2024) Diper
60 (2025)
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Microtek
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Axt, I would think that dissolving iron powder in perchloric acid would form the Fe(II) ion rather than Fe(III). You could probably oxidize it, maybe
with H2O2. I did an experiment today where I dissolved FeCl3 in ethanol and added a solution of NaClO4 in ethanol. This precipitated white,
crystalline powder which I assume to be NaCl. The idea would then be to either evaporate the ethanol (without heating), or use it directly for
preparation of the FAT3 ([Fe(4-ATRI)n](ClO4)3) complex.
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Axt
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I'm basing Fe(III) on the orange colour of the residue, I'm guessing that because I used the "mix and run" technique it ran hot and heavy enough to:
2Fe + 6HClO4 → 2Fe(ClO4)3 + 3H2
Actually, it's not that bad as there is an incubation period before it erupts, just don't do it in your kitchen.
In a more controlled setting Fe + 2HClO4 → Fe(ClO4)2 + H2 would likely be preferred particularly with excess iron, but this is supposedly light
green in colour.
Frames of Hexakis(dimethylsulphoxide)iron(III) perchlorate's blackpowderish deflag are attached below. I might have to play with solubilities to try
and get a bromate anion, it should be more "vehemic" even though the oxygen balance is already rubbish. Your ethanol extraction of Fe(BrO3)3 from
FeCl3 looks like a possibility, Iron bromate is not a well documented compound, assuming it exists.
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