| Pages:
1
..
29
30
31
32 |
MineMan
International Hazard
Posts: 1046
Registered: 29-3-2015
Member Is Offline
Mood: No Mood
|
|
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
National Hazard
Posts: 961
Registered: 23-9-2002
Member Is Offline
Mood: No Mood
|
|
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
International Hazard
Posts: 1046
Registered: 29-3-2015
Member Is Offline
Mood: No Mood
|
|
| 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
National Hazard
Posts: 913
Registered: 28-1-2003
Member Is Offline
Mood: No Mood
|
|
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
National Hazard
Posts: 961
Registered: 23-9-2002
Member Is Offline
Mood: No Mood
|
|
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
National Hazard
Posts: 913
Registered: 28-1-2003
Member Is Offline
Mood: No Mood
|
|
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)
This file has been downloaded 47 times
|
|
|
Axt
National Hazard
Posts: 913
Registered: 28-1-2003
Member Is Offline
Mood: No Mood
|
|
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
Hazard to Others
Posts: 231
Registered: 27-2-2012
Member Is Offline
Mood: No Mood
|
|
[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
National Hazard
Posts: 961
Registered: 23-9-2002
Member Is Offline
Mood: No Mood
|
|
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
National Hazard
Posts: 913
Registered: 28-1-2003
Member Is Offline
Mood: No Mood
|
|
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.
|
|
|
Etanol
Hazard to Others
Posts: 231
Registered: 27-2-2012
Member Is Offline
Mood: No Mood
|
|
| 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
National Hazard
Posts: 961
Registered: 23-9-2002
Member Is Offline
Mood: No Mood
|
|
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
National Hazard
Posts: 913
Registered: 28-1-2003
Member Is Offline
Mood: No Mood
|
|
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
National Hazard
Posts: 961
Registered: 23-9-2002
Member Is Offline
Mood: No Mood
|
|
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
National Hazard
Posts: 913
Registered: 28-1-2003
Member Is Offline
Mood: No Mood
|
|
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
National Hazard
Posts: 961
Registered: 23-9-2002
Member Is Offline
Mood: No Mood
|
|
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
National Hazard
Posts: 913
Registered: 28-1-2003
Member Is Offline
Mood: No Mood
|
|
| 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
National Hazard
Posts: 961
Registered: 23-9-2002
Member Is Offline
Mood: No Mood
|
|
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
National Hazard
Posts: 961
Registered: 23-9-2002
Member Is Offline
Mood: No Mood
|
|
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
National Hazard
Posts: 913
Registered: 28-1-2003
Member Is Offline
Mood: No Mood
|
|
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
National Hazard
Posts: 961
Registered: 23-9-2002
Member Is Offline
Mood: No Mood
|
|
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
International Hazard
Posts: 1144
Registered: 11-11-2010
Location: Wrongplanet
Member Is Offline
Mood: Doing science while it is still legal since 2010
|
|
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
National Hazard
Posts: 913
Registered: 28-1-2003
Member Is Offline
Mood: No Mood
|
|
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)
This file has been downloaded 30 times
|
|
|
Microtek
National Hazard
Posts: 961
Registered: 23-9-2002
Member Is Offline
Mood: No Mood
|
|
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
National Hazard
Posts: 913
Registered: 28-1-2003
Member Is Offline
Mood: No Mood
|
|
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]
|
|
|
| Pages:
1
..
29
30
31
32 |
![[*]](images/xpblue/default_icon.gif){kind=icon}
