5-aminotetrazole is one of the most marked high-nitrogen tetrazole compounds. However, the structural modification of 5-aminotetrazole with nitro groups often leads to dramatically decreased molecular stability, while the N-bridging functionalization does not efficiently improve the density and performance. In this paper, we report on a straightforward approach for improving the density of 5-aminotetrazole by introducing 4-amino-3,5-dinitropyrazole. The following experimental and calculated properties show that nitropyrazole functionalization competes well with energetic performance and mechanic sensitivity. All compounds were thoroughly characterized using IR and NMR spectroscopy, elemental analysis, and differential scanning calorimetry (DSC). Two energetic compounds ( DMPT-1 and DMPT-2 ) were further confirmed by implementing single-crystal X-ray diffraction studies. Compound DMPT-1 featured a high crystal density of 1.806 g cm &#;3 , excellent detonation velocity (v D = m s &#;1 ), detonation pressure (P = 30.2 GPa), and impact sensitivity of 30 J.
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1. Introduction
High energy density materials (HEDMs) remain a significant class of materials chemistry because energetic material has been widely applied in the military and civilian fields [1]. However, with the development of science and technology, higher requirements are put forward for new energetic materials, including high energy levels, low sensitivities, excellent thermal stability, and facile preparation. High positive heats of formation and densities constitute two significant parameters for the energetic properties of energetic compounds, where detonation pressures and velocities are proportional to the square of the densities [2]. Thus, developing effective strategies for increasing the densities of energetic materials is highly desirable.
In recent years, nitrogen-rich heterocycles have emerged as a new class of high energy density materials (HEDMs), which have been developed to meet the needs of national defense and environmental protection. Owing to their high thermal stability, high heat of formation, and enormous ring tension of azoles with C-N and N-N bonds, they have been the main building blocks for the design and preparation of nitrogen-rich materials [3,4,5,6]. Compared with other azole units, tetrazole is a highly stable heterocyclic structure with an extremely high nitrogen content and heat of formation, which may endow tetrazole-based energetic compounds with high performance and environmentally friendly properties [7,8,9,10,11].
Furthermore, 5-aminotetrazole (AT) provides a platform for a variety of functionalized tetrazoles, which have broad applications in almost all areas of energetic materials [12]. The functionalization of AT was mainly focused on modifying the tetrazolyl backbone and the substituted group, respectively. As can be seen in , the introduction of explosophores, e.g., azido, nitro, and nitramino groups, enhances the energetic performance remarkably. Nevertheless, balancing high energy with stability is still a highly challenging task. Based on the literature, very few outstanding compounds possess superior overall performance compared to the benchmark energetic materials [13,14,15]. For most high-energy derivatives, further practical applications are impeded by relatively poor thermal stability and sensitivity.
Inspired by the attractive chemistry of high-nitrogen materials, a synthetic method for efficiently preparing 1-substituted 5-aminotetrazoles from cyanogen azide and amine was developed ( a) [16]. The excellent reaction scope enables this approach to access various monocyclic and bicyclic AT derivatives [17]. In , a new approach for various pyrazole derivatives with 2-haloethylamines, followed by a reaction with cyanogen azide, resulted in ethylene-bridged 5-aminotetrazole and nitropyrazole ( b) [18]. Most of these compounds have good thermal stability and high heat of formation, however, the density of aminotetrazole-based derivatives could meet the standard of high-density compounds. As shown in d, most AT-based compounds display a density below 1.70 g cm&#;3.
Five-membered azoles are commonly used as the framework for the construction of nitrogen-rich heterocyclic energetic materials, such as imidazole, pyrazole, triazole, and tetrazole [19,20,21,22]. Pyrazole energetic compounds have good thermal stabilities and low sensitivities, which have been considered a beneficial building block for energetic materials [23,24]. For example, 4-amino-3,5-dinitropyrazole (ADNP) has been widely used in developing energetic materials due to their good density, low friction and impact sensitivities [25,26,27]. Herein, we reported our latest progress on the energetic derivatives of AT. By incorporating ADNP, the bicyclic AT-based compounds DMPT-1 and DMPT-2 are successfully accessed. Compared to previously reported AT derivatives, these compounds exhibit higher densities and detonation properties while retaining thermal stability and sensitivity.
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Subject: 5-ATZ(5-Aminotetrazole), the nitrotetrazolate ion and friends
For sure, especially if you have seen alibaba prices
But those 7.5g, turned into a nitrotetrazolate primary would last...if you have a secondary in mind, not so much.
Can someone plz check my calculation I mentioned 3 posts above, since I dont want to waste a lot of holy grale chems!!
Engager stated 0. mol NaNTZ. The molar weight of NaCN5O2*2H2O is 173.06 g/mol. 0. mol*173.06 g/mol = 1.192
g.
The molar ratio of the copper complex to sodium nitrotetrazolate is 2:1, which I don't really see the point of. But I think you should follow
Engager's instructions.
Well I calculated the same tnx: 3.5 grams of carbonato triammine copper(II) nitrate for every 1.91 grams of NANTZ.
With BNCP it is the opposite: 1.4 grams of cobalt stuff for every 2.6 grams of NANTZ.
Since NANTZ is harder to make, maybe the copperstuff is better variant to make! You need a lot less of NANTZ!
I made BNCP and NaCUNTZ. I was able to set off BNCP with a relatively simple primer such as mealpowder. However, NaCUNTZ seems to need a hotter
primer. I think I can get 5/10 in my blastingcaps with NaCUNTZ. So, I am looking for a decent priming composition. I have tried 80 leadtetroxide/20
silicon and this one burns veryy fast (flashpowder like). Mayb you guys have some suggestions for a very hot primining composition.
I synthesised a small amount of C2H4N14 bis-diazotetrazolylhydrazine, or as I prefer to call it,
ditetrazolylhexaazadiene.
When I dripped almost colourless diazotetrazole solution into hydrazinium chloride solution, it turned pink and then a fluffy yellow precipitate
formed. It hydrolyzed again before I could vacuum filter it. After a few days tiny dense grains of a yellow compound had precipitated. A single of
those grains, approx 50 micrograms detonates violently enough to rip a hole though aluminium foil when heated slowly. Still, it's not the unequivocal
primary I though it would be. A few milligrams only puff and spread out the pile when ignited. Strongly pressed it is extremely brisant.
Density was calculated to approx 1.75 g/cc by group addition method, similar to 5-azidotetrazole (1.72 g/cc), 1-diazidocarbamoyl-5-azidotetrazole
(1.72 g/cc) and 1,1'-azobis(tetrazole) (1.77 g/cc). Enthalpy of formation is most likely between + and + kJ/mol based on its structure and
similar compounds. This gives it a detonation velocity of around
m/s.
Here's my video about it: https://www.youtube.com/watch?v=qVZT5aR3ih0
DBX-1
One of the inventors passed this along to me. Sharing is caring.
I get a real chuckle knowing that some of the leading high technology contributors of this world are associated with this ..er ..uh .."amateur"
science forum.
Attachment: USA1 METHOD FOR PREPARATION OF A LEAD-FREE PRIMARY EXPLOSIVE.pdf (46kB)
This file has been downloaded times
Quote: Originally posted by Rosco Bodine One of the inventors passed this along to me. Sharing is caring.
I get a real chuckle knowing that some of the leading high technology contributors of this world are associated with this ..er ..uh .."amateur"
science forum.
You can bet on it...
Quote: Originally posted by Ragnar I would have expected the DBX-1 you synthesized to be a little more redish.
Quote: Originally posted by snooby The DBX-1 turned almost black in the end. When dry it became little chunks of DBX-1 who where impossible to be powdered. They were quite sensitive for
impact but did not work when ignited by fuse unfortunately. The synth I used was whithout the use of NaNTZ. Maybe this synth was not so good after
all. I now have an amount of cupric(II)cloride and I will try the synth again in a while. I indeed decided to put away the stuff. Have you tried DBX-1
yourself btw?
I tried recently it. With the method Rosco Bodine posted here http://www.sciencemadness.org/talk/viewthread.php?tid=&a...
The synthesis worked just fine even when I haven't reach the temp. of 100°C at the end (had about 80°C)
My DBX-1 was first reddish but finally after it was fully dry it also gets its almost black apperance. These chunks were
difficult to powder but possible. I broke them up carefully. Finally I got the rusty colour stated in the literature. Also much more flame sensitiv
and gives a greenish flame when ignited.
____
Only fictive!
[Edited on 26-9- by Mr.Greeenix]
You will get efficient and thoughtful service from Boraychem.
I synthetised 5-Aminotetrazole two times now.
The first time small scale with the method posted by Engager. The yield was ok and the product was very pure.
But now I scaled it up a little bit.
Approximately 10g Aminoguanidin bicarbonat ; 200ml 15% sulfuric acid ; 10g Nano2
and much sodium carbonate for the PH.
The problem is that I had a massiv yield of about 100g. I suppose that this is too good to be true
After cooling there were only crystals left in the beaker no more fluid, so I guess that all impurities also crystallized.
The Ph of my "5-Aminotetrazole" is neutral.
Is someone able to explain this yield?
Does someone know how to remove the sodium carbonat or sodium sulfat (Cause I neutralized with sulfuric acid) in my 5-Aminotetrazole. Suitable
Recrystallization?
(Video to this method: https://www.youtube.com/watch?v=oTjgHo-EdXY) he also had a massiv yield but I halved the amount of chemicals used.
Thank you
@Mr.Greenix it sounds like you have much sodium sulphate hydrate in there! 5-aminotetrazole crystallises as the monohydrate so you should get about
7.5g at 100% yield but you usually only get about 75% with the Thiele method.
Try treating the product with dilute HCl to ensure that it is the free tetrazole derivative, then leach with water until you have got rid of most of
the sodium salts and then recrystallise from water. 5-aminotetrazole is very soluble in hot water but sparingly soluble in cold water and salt
solutions so the recovery during recrystallisation is usually good.
By the way, always allow the filtrate to stand for several days or a week in contact with a few grains of the initial product and also stir
occasionally making sure you rub the vessel walls occasionally. 5-aminotetrazole has a terrible tendency to supersaturate.
PS just because somebody makes a youtube video it doesn't mean they know what they are doing!
Here is a doctoral dissertation of interest
694 pages - 35.1 MB
Advanced Energetic Materials Based on 5-Aminotetrazole - Synthesis, Characterization, Testing and Scale-up - Stierstorfer_Joerg.pdf
https://edoc.ub.uni-muenchen.de//1/Stierstorfer_Joerg.p...
http://www.hedm.cup.uni-muenchen.de/personen/staff/stierstor...
http://www.hedm.cup.uni-muenchen.de/index.html
Also another interesting and more recent doctoral dissertation for which a link was posted earlier, and then disabled temporarily due to a
confidentiality about a pending patent application, is again available for download since the patent has issued for the DBX-1 process described
therein.
http://www.sciencemadness.org/talk/viewthread.php?tid=&a...
The dissertation is
Advanced Energetic Materials - Piercey_Davin.pdf
linked here again
https://edoc.ub.uni-muenchen.de//1/Piercey_Davin.pdf
[Edited on 3/26/ by Rosco Bodine]
Anyone for 1,6-ditetrazolylhexaaza-1,5-diene? Dornier335A has it on Youtube. VoD ms. Sensitivity is, of course, just about unparalleled. Formula
C2H4N14 - it contains 87.5% nitrogen by weight.
Quote: Originally posted by octonitrocubane Anyone for 1,6-ditetrazolylhexaaza-1,5-diene? Dornier335A has it on Youtube. VoD ms. Sensitivity is, of course, just about unparalleled. Formula
C2H4N14 - it contains 87.5% nitrogen by weight.
Here's the video
https://www.youtube.com/watch?v=WowrwV-0ca8
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https://www.youtube.com/watch?v=qVZT5aR3ih0
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[Edited on 3/27/ by Rosco Bodine]
The first link in Rosco's post shows its properties very well, but I'll provide some more information here.
Ditetetrazolylhexaazadiene is described in Engager's
Energetic Derivatives of Tetrazole with the name bisdiazotetrazolylhydrazine and
briefly in Fedoroff. It's synthesised by mixing diazotetrazole solution with a solution of hydrazinium chloride and sodium acetate. My product
immediately dissolved/decomposed after forming though, probably due to too basic conditions. Replacing the hydrazinium chloride with hydrazine sulfate
worked well, and sodium acetate buffer doesn't seem necessary, although the product is whiter without.
The product seems stable after drying but rapidly dissolves in basic solutions to give a strongly yellow solution. It hydrolyses slowly in water to
give gas bubbles (nitrogen?) and 5-azidotetrazole. My product is stable in acidic solutions though.
Now comes the fun part: it's more explosive than anyone has probably ever dreamt of. My calculated performance at the measured density 1.8
g/cm3 is
m/s and
420 kbar.
In addition, it's critical diameter is microscopic. I played around with tiny grains under a microscope, trying to make as small flakes as possible. I
got an 18 micron thick flake, approximately 0.4 micrograms, to detonate (it put a dent in the aluminium foil).
This performance is not without downsides of course; it is exceptionally sensitive. Filter papers covered with ditetetrazolylhexaazadiene explode if
ripped (something I discovered without protection...) Light tapping with a hammer sets it off, as does pressing. More videos will come in the future!
[Edited on 27-3- by Dornier 335A]
Regarding the aminoguandine bicarbonate precursor for aminotetrazole
A point of interest is a second independent confirmation regarding the pyrolitic decomposition of calcium cyanurate to pure calcium cyanamide. I
think Davin first reported this does in fact work even as a "campfire" cyanamide produced in the hot coals of a wood fire kind of adapted process so
long as there is venting of the byproduct gases from the heated to orange heat container allowed, but not allowing air ingress into the reaction
mixture.
It looks like maybe a hacksaw cut was made to defeat the sealing of the threads and allow controlled venting for the "bomb" used for the pyrolysis
which is good technique. A small press fit "freeze plug" type of safety overpressure blowout plug is a good idea also in the top end cap for a
reactor like this in case venting is ever obstructed to prevent pressure buildup in the reactor. Probably a good easy safety vent providing a "gravity
seal" would be to use a 3/8" clevis pin dropped into a 3/8" hole drilled into the end cap, with the loose seal at the shoulder being sufficient. The
shaft of the clevis pin could be scored with a diagonal groove cut using a hacksaw, and if pressure from venting raised the clevis pin to the cut
groove it should regulate there by gravity like a pressure cooker regulator, and function as a loosely fitted check valve and regulator.
https://www.youtube.com/watch?v=AF11Xuh0SaQ
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allowfullscreen="true"></embed></object>
[Edited on 3/27/ by Rosco Bodine]
Having just synthesised five grams, its safe to say that I will never touch it again. One flake on the floor nearky gave me a heart attack. 4 grams
contained with aluminium foil within a plastic bag lit at the bottom of the water bottle absolutely shred it. Despite being able to isolate ~10 micron
flakes, it has yet to not detonate...
early thread missing images archived
Some of the early pages of this thread have dead linked missing images so attached is an old backup pdf which has viewable most of the missing files
Attachment: Tetrazole thread archival images.pdf (2.4MB)
This file has been downloaded times
NeonPulse
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Hazard to OthersPosts: 417Registered: 29-6-Location: The other end of the internet.Member Is OfflineIsolated from Reality! For Real this time....
posted on 24-4- at 01:54
Ok so it has been quite a journey from pool chemicals, urea, sodium bicarbonate and hydroxide , ammonia, hydrochloric, sulfuric, nitric acids copper
sulfate sodium nitrite and anything else I had forgotten but finally I got to make some of the copper nitrotetroazolate primary I had aimed for.
All components were OTC or made from OTC components except the 70% nitric acid( which could easily be synthesised OTC anyway) including the ammonia
which I made from NaOH and ammonium sulfate, the hydrazine, the cyanamide ( my method was shown in video above) which all together formed the basis of
the 5-ATZ and finally the CuNTZ.
Basically I had followed Engagers work here. It's his legacy here it would seem...
I must say though I'm pretty impressed by this compound although it is not the best initiator made from the 5-ATZ and really want to attempt the
silver variant and the Mercury variant especially. This particular salt gave me no troubles synthesising it and I was expecting the micro explosions I
had read about but luckily for me none happened. The only problems were the NOx fuming and thevery slow filtering of the ultra fine green mud.
It seems to have a tiny critical diameter and minute grains go off with a crack when heated on foil putting pin holes in it but with confinement in
foil and heated it gives a pretty loud report and sends silver foil confetti flying. I want to test it a little more but so far I can see why
primaries based on 5-ATZ and its salts are of interest as green energetic materials.
there is a way.
AllCheMystery!
https://www.youtube.com/channel/UCWbbidIY4v57uczsl0Fgv7w?vie...
Where there is a willthere is a way.AllCheMystery!
Voila! ..... Verdigris Patina Terribilis
seafoam green with attitude
The color reminds me of the patina on roofs and statuary
[Edited on 4/24/ by Rosco Bodine]
roof
Oh my God. On roofs I see Neon - Cu NTZ compounds! Is not necessary huge a complication of synthesis. Much easily is scratching from the roof. Without
acid and others chemical tools. I seems, that only what you needed is knife and ladder. Thanks for info......LL
NeonPulse, is that Cu(NTZ)2 or is it the acid copper nitrotetrazole salt? Because that one is supposed to be very
sensitive.
Liptakov, I climbed my local church's roof and found this:
It turned out to be copper(II) 5-azidotetrazolate though! Be careful!
NeonPulse
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Hazard to OthersPosts: 417Registered: 29-6-Location: The other end of the internet.Member Is OfflineIsolated from Reality! For Real this time....
posted on 24-4- at 22:51
It's the acid copper salt. It's colour is much paler than the picture portrayed but the camera seem to get it right. It would be much better if it
had a higher density like crystals rather than the fine fine powder. It doesn't seem overly sensitive but a lot of care is still taken while handling
the dry product. Once it had been dried for weighing I have sprayed a mist of water to dampen it and put it in a container till it's needed.
Is it right that being stored underwater will slowly decompose it? I think I read that in some PowerPoint presentation about green initiators some
time ago.
Wet storage is much preferred to missing fingers and I can easily see a small amount doing a lot of damage to a careless handler.
I know it seemed overly complicated but it's not really.Basically I wanted to see if this could be done using all OTC chemicals and it seems that with
a bit of work and effort it can. However for all that work put in over a few weekends the end result was only a few grams of the green stuff. But
that's enough since a little bit goes s long way.Most people would probably say it's hardly worth the time but hey, I think it's time well spent.
I'll Give the photo another go:
there is a way.
AllCheMystery!
https://www.youtube.com/channel/UCWbbidIY4v57uczsl0Fgv7w?vie...
Where there is a willthere is a way.AllCheMystery!
For more information, please visit 5-Aminotetrazole Monohydrate.
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