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Author: Subject: New Energetic Materials - Current Research
Microtek
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[*] posted on 20-12-2022 at 00:15


Another interesting paper on nitrating amino-substituted azoles to nitramines using a simple KNO3-H2SO4 system at 0C. Apparently, this system gives better yields than HNO3-Ac2O-TFAA or other exotic mixtures. In the paper they work on assorted difficult-to-nitrate pyrazoles and triazoles, but I don't see a reason it wouldn't work on more accessible aminotetrazole or guanazole.

Attachment: KNO3-H2SO4 nitration of amino groups on azoles.pdf (830kB)
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dettoo456
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[*] posted on 16-3-2023 at 15:35


By any chance has anyone attempted nitration of 4-substituted imidazoles or 3-substituted triazoles before? I was thinking about 4-methyl-2,5-dinitroimidazole as a simple, cheap melt cast EM (it’s relative 2-methyl-4,5-DNI has melt cast potential). The easiest route being Acetone —SeO2–> Methylglyoxal —Hexamine+NH4OAc+AcOH—> 4-Methylimidazole —HNO3+H2SO4/SO3–> 4-M-2,5-DNI.
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Microtek
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[*] posted on 17-3-2023 at 14:20


According to this abstract:

https://www.researchgate.net/publication/261528645_2-Methyl-...

2-methyl-4,5-DNI has a melting point of more than 200 C. That's a little high for a melt cast I think.
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[*] posted on 17-3-2023 at 21:37


@Microtek My bad, I must have been thinking of something else. Apparently the N-methyl-2,4,5-TNI has a melting point of 105C though - although its amateur accessibility level is quite lower. Alkylated amines in heterocycles do seem to trend towards lower MPs but it’s weird that a trinitro product would have a lower MP than it’s dinitro analogue. Cited from DOI: 10.1002/prep.201100047

Microtek, is your UZP any farther along by the way? I don’t know what to do with my hydrazine and I was think of either going the TAGN or the carbohydrazide -> urazine route. Maybe nitrourazine (4-nitramino-1,2,4-triazole-3,5-dione) could be interesting although I haven’t seen anybody attempt nitration of urazine - it seems like it’d take really harsh conditions to do so.
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[*] posted on 18-3-2023 at 14:30


Yes, I also feel like the arrangement with three nitrogens in a row, with one of them being in a nitro group is probably too unstable. Still, on a sufficiently small scale it could be interesting (but not excessively interesting) to try. I'm thinking of trying an N-nitration of guanazole (3,5-diamino-1,2,4-triazole) when I have time. Guanazole is not too difficult to make.
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[*] posted on 18-4-2023 at 15:24


Bronopol (2-Bromo-2-Nitropropane-1,3-diol) is used fairly commonly in cleaning and preservatives of industrial products (see wiki https://en.m.wikipedia.org/wiki/Bronopol ). Could this be used practically if found cheap enough? I was thinking a simple nitration followed by Azide metathesis to furnish the gem-azidonitro (although I don’t know much about gem-halonitro reactions) or just nitration to the 2-bromo-2-nitropropane-1,3-diol dinitrate. Both would probably be sufficiently powerful (estimated VOD around mid 7km/s) and available. I’m sure Chinese vendors can offer it less than or equal to $25/kg, although I’d need to check.
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Σldritch
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[*] posted on 12-12-2023 at 01:31


Found this very nitrogen-rich cation [N(NNH3)4]+1 that looks suprisingly robust. Especially if stabilized as an adduct with two (thio)urea molecules. Paired with an appropriate anion it should make a very powerful explosive. No idea how to synthesize it though but there is a lot of symmetry to exploit so it has that going for it.
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Microtek
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[*] posted on 13-12-2023 at 00:29


Is there reason to think that this is anything other than a purely theoretical molecular structure? It looks... unstable to me.
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[*] posted on 13-12-2023 at 07:28


Hello!

This is my first post in this forum, I´m not a native english speaker, so forgive me misunderstandings and typo please.

Last week I found this very interesting article about a new primary called DPPE-1 with a so-called double
perovskite framework, published last month in nature communications (14, article number 7765 (2023), published 27th november 2023) :

https://www.nature.com/articles/s41467-023-43320-0


This is also the reason why I´ve decided to create an account here: I´ve read a lot here within the last months, got a pile of useful information and now I´d like to give a little back to the community.

The synthesis is very easy (pour together aqueous solutions of sodium periodate, ammonium chloride and DABCO-dihydrochloride at room temperature, filter off the crystalline precipitate, dry it, ready) with a good yield.

This primary is claimed to have superior initiation capabilities (five milligram enough to initiate RDX - wow), the impact sensitivity is acceptable, the friction sensitivity high (but not as high as silver oder lead azide) and the thermal stability seems sufficient for many applications.

Unfortunately, the ESD value is not reported by the researcher group. This is a severe gap in this publication, as accidental ignition by electrostatic discharge is a major issue and has caused so much trouble in the past.

I also miss some solubility data, behaviour against acids and bases and compatibility tests (i.e. copper, brass and aluminum casings, sulfur from time fuse, fuel oil from ANFO mixtures etc.).

Further research in this area with appropriate precautions seems necessary. A "fine-tuning" with other building blocks could reveal yet unknown primaries with even better performance. This is "terra incognita" for the scientific community.

Kind regards,

Nemo_Tenetur

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[*] posted on 13-12-2023 at 09:30


The perovskites and MOFs seem to be all the rage for new energetics - this one could be promising though. The only issues seem to be thermal stability and mechanical but those could maybe be tuned by substituting a bulkier amine like hexamine or some other polycyclic amine. Perbromate, although difficult to obtain, could maybe be used in place of the periodate and maybe cesium swapped for sodium.

Energeticheretic did some work with piperazine perchlorate perovskites and they seemed very promising but I don’t think he is active anywhere… he might be in jail sadly.
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[*] posted on 13-12-2023 at 13:05


Quote: Originally posted by Microtek  
Is there reason to think that this is anything other than a purely theoretical molecular structure? It looks... unstable to me.


Well the model I linked is sure not very accurate but this tautomer does feature strong-ish nitrogen-nitrogen bonds. The other tautomers not so much but again this model is crude. Of course anything with this much nitrogen looks unstable but do you have a specific fragment in mind?

I think the main decomposition pathway besides tautomeriazation would be formation of [N(NNH3)3]+2 dication isoelectronic with the triaminoguanidinium cation and a [NNH3]-1 hydrazide anion. Not very favorable. Then, looking at the tautomer, who knows? My intuition says it is moderately stable. That does not mean it forms easily. Does that make it purely theoretical? You be the judge. Personally I think the energetics design field is not very serious in its research just looking for minor improvements mostly so something like this is where it is at.
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[*] posted on 17-12-2023 at 03:15


What I meant was, is there any data that suggest it may have been synthesized at some point? All I see in the link is things I would expect from a theoretical study on a hypothetical molecule. How did you find out about it?
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Σldritch
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[*] posted on 18-12-2023 at 01:29


Quote: Originally posted by Microtek  
What I meant was, is there any data that suggest it may have been synthesized at some point? All I see in the link is things I would expect from a theoretical study on a hypothetical molecule. How did you find out about it?


I thought I made it clear: I came up with it. No studies. No data. Just intuition and playing around in Molcalc, but, if you have a guess what someone might call this molecule, then, perhaps data can be found. I would expect any studies on this molecule to be military secrets, though, if it has potential at all. I guess that also explains why I get the impression that the energetics research community just does minor optimization: the paradigm-shifting research is secret, and so we don't see it.
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[*] posted on 18-12-2023 at 02:04


Well, Klapötke et al (among others) have done quite a lot of work on high nitrogen compounds. This kind of thing with long chains or networks of single-ish bonded nitrogen is usually either unstable or horrendously sensitive or both.
You can obviously play around with molecule building kits, digital or otherwise, all you like, but there is a huge step up from building a model and synthesizing the molecule in reality.

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Σldritch
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[*] posted on 18-12-2023 at 03:33


I am just saying that don't judge what works and what does not too much on published research. There are design rules of course which you can learn from, and I have, but if and when the perfect chemical explosive is found all these people are out of a job, and, that is if it is published at all. I would know because I have not published my best ideas, here, either! Then there is the issue of chemists using a very simplified model of physics and of thermodynamics especially which limits creativity, as well, not to mention the funding issue.

Regarding synthesis there may be ways of synthesizing amazingly complex molecules very simply but to my knowledge no research has been carried out in that direction, for better or worse, so there is that (I've been doing a deep dive into obscure physics lately). So there very much is an argument to be made that what the (published) energetics research community at large is doing is little better than the playing around with molecule building kits I am doing.

[Edited on 18-12-2023 by Σldritch]
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Microtek
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[*] posted on 19-12-2023 at 01:58


I completely disagree. Both on the implied existence of a conspiracy in the energetics community, and on your "observations" on simplistic chemical/physical models. Tons of research have been done on synthesizing complex molecules in a simple manner - you might say that is what all synthetic chemical research is about.

I dare you to share some of those amazing insights you have developed (beyond just hypothetical molecules; anyone can do that). If you won't, well then you are the conspiracy (or maybe just a troll).
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[*] posted on 19-12-2023 at 12:48


@Microtek I personally agree with Σldritch in the sentiment that the current EM research community isn’t exactly full of innovators as it relates to new molecule prep. I mean, look at most papers that come out of PEP nowadays; they’re mostly about modifications to old energetics like RDX, Cl-20 (not old but technically 20th century), and more physics or physical chemistry related topics. Klapotke and some of the less-trustworthy Chinese contributors are the only ones really pushing new molecules, and even then, it’s mainly just “addition of azide group here or nitro here or azo bridge there, etc”. Klapotke’s Si-PETN info was actually interesting, just as some of his N-B heterocyclic stuff but that never seemed to go anywhere.

Though, especially since some of the key motivators in EM chemistry are cost-benefit analysis and scale-up engineering, radical changes to explosives and propellants aren’t likely to even see the light of day (or less likely to make it to large scale applications).

TKX-50 is great but it’s way too expensive to make and not enough has been done to improve synth routes. Even ADN likely won’t go very far into commercial or military use.

Theoretical molecules won’t help matters though - and molbase is practically useless.
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[*] posted on 19-12-2023 at 12:56


@ Σldritch, idk what your personal insights are, but I’d say most people here are just invested in making EM’s safer, more attainable, and cleaner (the green shit is actually a worthwhile pursuit imo). As much as a fancy 3D cube or C2N14-like material is cool to look at, it simply isn’t realistic.

[Edited on 19-12-2023 by dettoo456]
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Σldritch
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[*] posted on 19-12-2023 at 13:53


Quote: Originally posted by Microtek  
I completely disagree. Both on the implied existence of a conspiracy in the energetics community, and on your "observations" on simplistic chemical/physical models...


I implied no such thing. I just expect military contractors to keep military secrets.

As for models chemical explosives are now treated as closed systems. There are no closed systems in the universe or we would be unable to study them experimentally. Hence energy can be collected from the environment and be used to boost chemical explosives. One could argue that is what a (thermo)nuclear weapon is. Where this energy comes from is not always clear, though, so saying it is 'free' energy is convenient. If you do not believe in such a concept I would recommend a long and reflective look at the Sun, with emphasis on reflective, lest you burn out your retinas with all that limitless free energy.

What comes to mind first and foremost, though, as a way to amplify chemical explosives is this link.

But as discussed a chemical explosive is only as good as the industrial process producing it, though, there may be ways around that but it is pretty far out. You'd never believe it possible if I told you, and, while I know it is possible in principle myself I am not sure it can be practical without opening pandoras box...

Of course I share the goals of many other explosives enthusiasts here but I also kind of felt this was among the more speculative threads fitting for my idea which did not really deserve its own thread.
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[*] posted on 19-12-2023 at 16:01


Sounds like ideas better suited to a think-tank rather than an amateur forum then.

Defense companies may have an incentive to push for compounds like Cl-20 or LLM-105, or BTTN, etc, but I believe they’d do that to simply make more profit, not to keep jobs. For example, BAE can use their lobbyists to talk to generals about fancy 3D ultra-powerful explosives and the generals will sign whatever check BAE gives them because the generals (government) literally control one of the largest wealth collectives in all time; the US defense budget. The government doesn’t care how much an explosive will cost or how great it’ll be in reality, they care about what the defense companies or lobbyists tell them (or secret backroom deals they make). So even if a new EM came out that was fantastic, if BAE or Northrop Grumman didn’t have any interest in it for whatever reason, it wouldn’t leave the research lab. And that happens constantly. That doesn’t mean people would be discouraged from doing PEP research though, it just means that you need to be a great negotiator with defense companies.
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[*] posted on 20-12-2023 at 00:54



Quote:

There are no closed systems in the universe or we would be unable to study them experimentally. Hence energy can be collected from the environment and be used to boost chemical explosives. One could argue that is what a (thermo)nuclear weapon is. Where this energy comes from is not always clear, though, so saying it is 'free' energy is convenient. If you do not believe in such a concept I would recommend a long and reflective look at the Sun, with emphasis on reflective, lest you burn out your retinas with all that limitless free energy.


This is so chock-full of logical fallacy, pseudo science, and plain old misconceptions, that I hardly know where to begin. The link you provided is to a pseudo science conspiracy nut who practices alchemy. I think it is now firmly established that you are just trolling here. I will stop responding to your posts now.
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[*] posted on 20-12-2023 at 03:10


There's obviously a conspiracy between the military and scientists.
I once had a chance to look into one certain hangar on a certain base (obviously I can't say where). What have I seen...
Giant robots for combat in space, giant bio-robots with souls of pilots' mothers inside, tanks huge as fortresses, fighter jets with thermonuclear engines, alien life progenitor impaled with super weapon, and more. I had to fight for my life with nanomachines-infused US senator, so I couldn't look into other hangars, maybe there were those secret explosive formulas
As I'm typing this, their agents may be already on my doorstep, I'm not as trained in gorilla warfare, so farewell my friends




Wroom wroom
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Σldritch
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[*] posted on 29-12-2023 at 02:13


Here is something more creative: the synthesis of ground-state diatomic carbon at room-temperature (link).

Diatomic carbon is interesting from an energetics POV, not primarly because it would make a good explosive, I think, but because it would make a good propellant enhancer. The ground state of diatomic carbon contains about as much energy as the combustion of the same amount of carbon to the dioxide releases. Better yet, it may not even be explosive! This is because, if pure, it should not contain enough energy to boil itself, greatly increasing safety during handling. Not only that, it may be pourable cryogenic liquid, easing handling even further, in comparison to, say; metal(hydrides), which it also has the advantage over of not producing any ash, besides not containing any rare or toxic elements. But there is more! Producing diatomic carbon in the ground-state seems to pull energy out of nowhere.

Here is Henry Rezpa clowning himself by implying diatomic carbon could not have been produced in the paper above because it would break 'the laws of thermodynamics' when there is in fact no such law of thermodynamics (link). It seems he is wisely realizing the limitations of his model here, though, as he claims the source of this energy is unknown, but it is not! For a long time it has been known energy can be pulled out of the vacuum/time domain. Tesla new it! There is no mystery here.

In conclusion, because the ideal energetic is as much a chemical process as it is the final product of that same chemical process producing it, that chemical process should extract energy from the environment. It seems entropy driven irreversible reactions is the way to do it, which should not suprise anyone, because irreversible obviously means non-equilibrium conditions where of course the infamous second law of thermodynamics does not necessarily apply.

[Edited on 29-12-2023 by Σldritch]
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[*] posted on 30-12-2023 at 17:58


Quote: Originally posted by Σldritch  
Here is something more creative: the synthesis of ground-state diatomic carbon at room-temperature (link).

Diatomic carbon is interesting from an energetics POV, not primarly because it would make a good explosive, I think, but because it would make a good propellant enhancer. The ground state of diatomic carbon contains about as much energy as the combustion of the same amount of carbon to the dioxide releases. Better yet, it may not even be explosive! This is because, if pure, it should not contain enough energy to boil itself, greatly increasing safety during handling. Not only that, it may be pourable cryogenic liquid, easing handling even further, in comparison to, say; metal(hydrides), which it also has the advantage over of not producing any ash, besides not containing any rare or toxic elements. But there is more! Producing diatomic carbon in the ground-state seems to pull energy out of nowhere.

Here is Henry Rezpa clowning himself by implying diatomic carbon could not have been produced in the paper above because it would break 'the laws of thermodynamics' when there is in fact no such law of thermodynamics (link). It seems he is wisely realizing the limitations of his model here, though, as he claims the source of this energy is unknown, but it is not! For a long time it has been known energy can be pulled out of the vacuum/time domain. Tesla new it! There is no mystery here.

In conclusion, because the ideal energetic is as much a chemical process as it is the final product of that same chemical process producing it, that chemical process should extract energy from the environment. It seems entropy driven irreversible reactions is the way to do it, which should not suprise anyone, because irreversible obviously means non-equilibrium conditions where of course the infamous second law of thermodynamics does not necessarily apply.

[Edited on 29-12-2023 by Σldritch]




What is the synth like?
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Σldritch
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[*] posted on 31-12-2023 at 02:25


Quote: Originally posted by MineMan  
What is the synth like?


I presume your point is that I should not post about something I have not tried myself nor that which is not do-able in an amateur setting as I already provided the link to the synthesis but while this is beyond my ability currently (unless some kind soul would like to make a sizeable donation for my lab) it may not be beyond the resourceful amateur at all.

Acetylides are explosive for a reason after all... Heating Cu2C2•H2O under vacuum is supposedly non-explosve and deposits carbyne on the vessel wall. Why does it do that? Perhaps diatomic carbon is produced and traces of volatilized copper catalyzes the production of carbyne. Then, suppose we replace the copper with, say, mercury (HgnC2) which perhaps does not catalyze that transformation and also ensures a lower temperature of decomposition as the mercury absorbs heat as it boils perhaps you would be able to trap some diatomic carbon if you are clever.

Maybe the hardest thing with its isolation would be its sensitivity to air/light and that it ought to have a boiling-point lower than that of nitrogen (considering its mass). It does not seem impossible to work around though.

Edit: having written this perhaps you were asking how the idea I concluded with would be inplemented in practice. Well, besides this idea of using diatomic carbon as an energetic I have one other idea employing these same principles of using an irreversible strongly entropy driven reaction to efficiently synthesize a very energetic compound. It is my secret, though, as I need to eat too, and, as I have grown older I am not too keen to introduce another weapon into the world. Especially as we stand on the brink of WWIII.

[Edited on 31-12-2023 by Σldritch]
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