Sciencemadness Discussion Board - 3-amino-1-nitroguanidine Salts

Hey buddy. Good work. I heard ANQ is actually white when recrystallized. I saw pictures and was shocked because it’s so deeply yellow.

I don't know if the work is "good", but it is work. So far, there seems to be more learning about what isn't desirable vs finding anything desirable. Hopefully something useful will shake out. But thank you for the compliment.

--Yes, the ANQ is white after recrystallizing. I have tried to use a dirty ANQ but it may end up being the case that contamination causes problems and recrystallization is necessary. not sure yet. The sodium salt seems to be energetically responsive enough to indicate successful cyclization to tetrazole from the ANQ, but its not as obvious as say a free acid high velocity detonation would be.

What do you think has the most promise for a safe and extremely powerful energetic? I think the metal complexes rule out anything other than a primary in most cases, but definitely not all.

I think ionic compounds and metal complexes are the current frontier. It seemed like it was being pushed this way by BNCP, DBX-1 etc. already, but I think this "field" has the most gold in the mine so to speak. Industry in china has moved from things like DDNP to complexes like GTG carboyhdrazide perchlorates for industrial blasting. I think in terms of primary explosive character control, complexes are the logical field that still needs expansion. The misunderstanding of perchlorates and lead by the regulatory people seems to be holding it back on focus, but the halogen compounds have probably the most to offer.

I thought as you did about metal explosive complexes being somewhat less useful other than primary explosives, but after experimenting in this area over the past couple years, I have found that there are a much larger number of insensitive explosive complexes (less mechanically sensitive than say PETN) found in this area. The primary explosive character of short DDT I've found is somewhat rare and harder to locate. golden eggs.

I do think, in terms of big picture, primary explosives are more needed than secondaries. But simply produced ones. The NAP has the most going for it, I think if it were a little better explored, it may offer a flexibility on routes and expedience/power that other primaries don't have. --Carbohydrazide and semicarbazide ligands are also of interest because they are from urea directly without need to derive guanidine first. Minimal processing and maximum expedience of reagents/preparation is desirable for any new primary explosive in my opinion. In that way, I appreciate SADS. It is the simplest primary explosive other than say mercury fulminate, or HMTD. The trouble in organic peroxide behavior is they are all technically auto-decomposing all the time. Heat, moisture, radiation or pressure accelerates the auto decomp, which rules them out IMO, unless that can be overcome. SADS on the other hand appears to have no faults other than it is slightly anemic, and it reverts to silver on radiation. I have found in my own tests that it actually lasts a long time and is very explosively responsive to heat after long storage, without direct sun. SADS is somewhat insensitive by primary standards and detonates in small single particles. The preparation route is short with minimal hazard. I think it is the fastest yielding explosive. The need of silver can be expensive, but a little goes a long way in SADS. I have been testing SADS with NC binder (10%+) and I really like what I've found. I would like to try a sun blocking material, maybe graphite or PTFE, to increase shelf life, but I think there is potential in SADS as a pellet, with another boosting explosive after it, like ETN.

For secondaries, I think there are definitely some simple ionic secondaries to be found yet which will be powerful. Nitrates/perchlorates/periodates. Glycine perchlorate at least for small production seems like it may be worthwhile.
Hexamine derivatives, although there is a lot of data on them already, seem to also have some more potential, and hexamine is very simple and universal in preparation so it is a natural area to be further explored.
Guanidine and Urea also. IMO because secondary explosives have to be produced in high quantity, materials they are derived from should be very easy to produce industrially as well as being expansive in their routes and variants etc. This is the problem of TNT as an early secondary, there is practically only TNT, TNT mixtures and HNS in that family tree, which is limiting. Versus something like guanidine which is unknown how far it extends. Guanidine can already produce many secondaries of different powers and sensitivities or primaries. Industrially or on the small scale, it's a more efficient family tree. Im not so sure about NATz though, it's getting cumbersome, if its powerful it could have some logical use. it seems like they are high temperature decomp compounds 200-400 C. I mostly just wanted to keep tack of all the tests on this thread so anyone else curious can see what I tried.

We really need a 9500m/s safe secondary

I think we should aim for 10k+ and see whats found on the way.

[Edited on 23-4-2023 by Hey Buddy]

Microtek - 24-4-2023 at 00:50

Hey Buddy:

With regards to isolating free NATz, you could try extracting with a polar solvent - maybe ethyl acetate for starters followed by distillation of most of the solvent and slow evaporation of the rest. If free NATz is fairly acidic, there's a decent probability it will also be fairly soluble in water.

I also suggest that you purify your reactants as much as you can. Impure reactants makes identification of the products exponentially harder because you can't really rule anything out. If you don't have access to advanced analytical equipment (most of us amateurs don't) that uncertainty makes it almost impossible to positively identify what you have made.

I think that metal complexes are very useful for primaries, and that organic and/or halogen ionic compounds are very promising for secondaries, but I don't think it will be easy to find a high performing metal complex secondary. The metal tends to be dead weight since it typically doesn't add to the energy release. Exceptions can possibly be found, but it would have to be a pretty exotic compound. There has been some Chinese papers on metal-organic networks that claimed extremely high performance, but they turned out to be pure fantasy (probably. They were based on assumptions and methods that were blatantly wrong).

MineMan - 24-4-2023 at 02:03

Hey Buddy. Thank you for the long reply! Any more info on what you said China is using for blasting? I know US and AUS blasting companies are very slow to change in this regard.

NiAqPerchlorate is, stunning. The copper version is actually less sensitive and more brisant. It does not ddt in microgram quantities like the nickel salt, but it is far less sensitive. Even the nickel version. I saw a picture of it in an aluminum tube that was hit with a hammer and it did not go off. In my mind, these two salts have stopped me from reading about research in primaries, because, they are basically ideal. Stability might be an issue. I saw once, with the copper salt that it was very insensitive when made. But a few months later it went off when barely touched with a hammer, just a small portion of one sample that was divided, I had never seen that before and didn’t quite believe it.

I find secondaries more interesting because, well NAQPerchlorate is basically the ideal primary, it’s quite remarkable the preparation and the raw performance.

MineMan - 24-4-2023 at 02:07

Hey Buddy:

With regards to isolating free NATz, you could try extracting with a polar solvent - maybe ethyl acetate for starters followed by distillation of most of the solvent and slow evaporation of the rest. If free NATz is fairly acidic, there's a decent probability it will also be fairly soluble in water.

I also suggest that you purify your reactants as much as you can. Impure reactants makes identification of the products exponentially harder because you can't really rule anything out. If you don't have access to advanced analytical equipment (most of us amateurs don't) that uncertainty makes it almost impossible to positively identify what you have made.

I think that metal complexes are very useful for primaries, and that organic and/or halogen ionic compounds are very promising for secondaries, but I don't think it will be easy to find a high performing metal complex secondary. The metal tends to be dead weight since it typically doesn't add to the energy release. Exceptions can possibly be found, but it would have to be a pretty exotic compound. There has been some Chinese papers on metal-organic networks that claimed extremely high performance, but they turned out to be pure fantasy (probably. They were based on assumptions and methods that were blatantly wrong).

I remember those papers, the silver complexes that they claimed 11.3kms.

Microtek, do you think the Urazine perchlorate is still the most powerful secondary? It certainly was not too excotic in preparation. If hey buddy is looking for the ultimate primary he should try metal complexing the Urazine perchlorate… it’s far denser than aminoguanidine as you know. I think we talked about this but I have been having memory issues since long covid… and can’t remember a thing.

underground - 24-4-2023 at 02:57

For powerfull secondary easy to make explosives to my mind it comes melamine dinitrate/diperchlorate. Melamine can be made by just heating up urea

dettoo456 - 24-4-2023 at 16:16

@underground Melamine is a pretty solid building block for EMs, sadly DNAM (it’s fully nitrated counterpart) isn’t stable enough to be used practically. The perchlorate like you mention supposedly has a density of 1.94g/ml which is promising but conflicting sources reference it as a hydrate or dihydrate salt, which doesn’t bode well for primaries. If you are interested, there’s a thread for this exact topic “Melamine dinitrate”. Philou has some good observations - triaminoheptazine (melem) might be an even better EM base seeing as its N to C ratio is higher. And density isn’t too different. If metathesis rxns can be done on the bases too, then melamine and heptazine nitrate and perchlorate salts could prove very interesting.

Hey Buddy - 24-4-2023 at 21:02

regards to isolating free NATz, you could try extracting with a polar solvent - maybe ethyl acetate for starters followed by distillation of most of the solvent and slow evaporation of the rest. If free NATz is fairly acidic, there's a decent probability it will also be fairly soluble in water.

I have been demoralized on the NATz project, ive been taking a leave of absence, heavy beer drinking. I did attempt evaporation which looked promising, a clear lemon colored substrate was left in beaker. No detonation. Alas, it is a dead end.

I also suggest that you purify your reactants as much as you can. Impure reactants makes identification of the products exponentially harder because you can't really rule anything out.

It is true and in the case of NATz I suspect in the route from ANQ, contamination is compounded. It may necessitate recrys at each step. I was attempting to avoid this for expedience but as roads run out it makes it necessary to repeat with recrys.

I think that metal complexes are very useful for primaries, and that organic and/or halogen ionic compounds are very promising for secondaries, but I don't think it will be easy to find a high performing metal complex secondary. The metal tends to be dead weight since it typically doesn't add to the energy release. Exceptions can possibly be found, but it would have to be a pretty exotic compound. There has been some Chinese papers on metal-organic networks that claimed extremely high performance, but they turned out to be pure fantasy (probably. They were based on assumptions and methods that were blatantly wrong).

I agree that the metal is dead weight in contribution to density, but in my understanding, the metal provides scaffolding that permits tunability of a complex with oxygen and nitrogen as the major players in power and hydrogen as a sensitization indicator which also helps in scaffold work.-- I suspect the character of metal complex explosives (which are really simply ionic explosives with bridging metal ligands) is controllable in terms of sensitivity and power, along with n-oxide addition, it seems that some very purposefully sought after characteristics could be found after the general understanding is learned about. They are still trying to decide what to call explosive complexes in the literature, whether MOFs etc.

Hey Buddy - 24-4-2023 at 21:48

Any more info on what you said China is using for blasting?

Sure, the major abrupt change they have made in blasting composition in china right now, from DDNP, which was very extensively used for general civil blasting there since the 90s, is tris(carbohydrazide) metal perchlorates. Carbohydrazide aka diaminourea, is urea with two additional aminos from hydrazine. It can be produced in a few routes other than urea also. The main two "CHZ" primary explosive complexes the chinese have used are: zinc tris(carbohydrazide) Di(perchlorate) which is known as GTX, and the cadmium analog, which is Cd(CHZ)3(ClO4)2 known as GTG. GTG I believe is the winner over time attrition in detonator compositions. The reason, is because China maintains a large supply of carbohydrazide for export as an industrial oxygen scavenger in factory equipment world-wide and so the carbohydrazide complexes sort of materialized. Then out of all the complexes, the cadmium had the most compressed late-stage DDT which meant high-impulse, and it seemed more brissant than the others.-- They also apparently used Mg, Ni and Cu which also do purportedly work as primary explosives but in the end, Zn and Cd remained.

NiAqPerchlorate is, stunning. The copper version is actually less sensitive and more brisant. It does not ddt in microgram quantities like the nickel salt, but it is far less sensitive. Even the nickel version. I saw a picture of it in an aluminum tube that was hit with a hammer and it did not go off. In my mind, these two salts have stopped me from reading about research in primaries, because, they are basically ideal.

I agree. I am very impressed by the Ni analogue and I think when it is successfully synthesized, it is my favorite primary explosive. I like everyhting about its character. There are issues with it's synthesis routes that lead to probably variable complexation which gives a range of characteristics, but even the weaker firing NAP is very powerful. When the variability is figured out, I think it will be a natural azide replacement, assuming regulatory control allows a perchlorate. Regardless, it is definitely what I would consider ideal. I will be using it a lot more, for sure.

I find secondaries more interesting because, well NAQPerchlorate is basically the ideal primary, it’s quite remarkable the preparation and the raw performance.

This is a good point, once the primary is settled, and it doesnt take much, then the secondary is really the greater interest. There are a lot of considerations of secondaries, IMO simplicity of secondaries in their manufacture is critical, because quantities of secondaries are so large in most applications. Any intensive process or aspect of preparing a secondary, is compounded by the quantity needed. In this regard, I suspect that ionic secondaries are the most promising. In traditional military munitions for instance, say aircraft bombs, the largest payloads are ammonium nitrate based and in small cases NQ based insensitive large bombs. This is due to the complication of large payload munitions and the preparation of material in large mass devices. Higher performance, simple materials, like ionic explosives, could entirely change this. Not that I think dropping bombs is a good thing, I only mean to use that as an example of present limitations in its scale.

Hey Buddy - 24-4-2023 at 22:00

Quote: Originally posted by underground

For powerfull secondary easy to make explosives to my mind it comes melamine dinitrate/diperchlorate. Melamine can be made by just heating up urea

I have done some experimentation with melamine as a ligand and it makes very insensitive complex secondary explosives. I havent done any performance tests like hitting steel or aluminum, but I really like the melamine molecule. More than melamine, theoretically, is melem, which is one higher step in condensation above melamine, it increases nitrogen percentage and velocity/pressure stats. The highest Ive read about would be Melem n-oxide perchlorates/nitrates which are theorized to be high velocity 10km+. I have not had the opportunity to attempt preparing melem from melamine. So i have no experience with that.

In America, I have recently found that "Oxone" is now available as a pool chemical at the hardware store under the name of "pool Shock". Oxone is used to oxideize molecules to N-oxide and is probably the best chance at melamine/melem n-oxide based iionic compounds. I also suspect oxone is capable of oxidizing TMTN to RDX which is difficult.

MineMan - 24-4-2023 at 23:42

Quote: Originally posted by underground

For powerfull secondary easy to make explosives to my mind it comes melamine dinitrate/diperchlorate. Melamine can be made by just heating up urea

It’s 7kms VOD. But it has outstanding thermal stability. I thought around 300C. But powerful, no.

MineMan - 25-4-2023 at 00:14

Any more info on what you said China is using for blasting?

I find secondaries more interesting because, well NAQPerchlorate is basically the ideal primary, it’s quite remarkable the preparation and the raw performance.

Nickel Amino Guanidine diP is easy to prepare consistently… it strikes me as more straightforward than even ETN. There is a method. The color, the deep red color is large crystals, the orange color is small crystals. I prefer the small orange micro crystals. It’s very consistent and takes 5 minutes for the whole process. It turns blue, then green, then black then red.

[Edited on 25-4-2023 by MineMan]

Hey Buddy - 25-4-2023 at 14:47

I suspect under patent conditions, it's consistent, there are complications in the correct complexation if the patent procedure is strayed from. It is yet"unknown" to researchers and munitions manufacturers, so there is no in-depth investigation of it. Im not aware of any literature on it other than the german patent, and maybe some very old german lab publishings. Im aware of the recent Cu paper. --If it were researched and understood in industry, and if they could control scalability, then the performance aspect is advantageous over other primaries. --I agree that it is a very simple procedure, and to boil something for 5 minutes is more straight forward than nitrate ester preparation. However, the preparation of AGu and Ni perchlorate requires more steps and less common precursors than erythritol and nitric acid. --That is interesting about the color of the size of the crystals, I hadnt noticed that yet. but it makes sense... There are definitely things that influence the complexation to make different performance character possible. This seems to not be encountered if the procedure is followed, but exactly what is going on is probably not understood. That's not insurmountable, but compared to lead azide, or mercury fulminate, the reaction and reagents are basically fool proof and scalable in the masses that a primary would be industrially produced (~kg qty.) I dont doubt NAP is suitable for scale, but its just so new, (relatively). It needs some professional development to really displace any legacy system. I like it a lot. I think it has many advantages. Its character is rare.

[Edited on 26-4-2023 by Hey Buddy]

Pb (5-NATz)2*4H2O, 537.3764 g/mol

Hey Buddy - 1-5-2023 at 18:52

lead 5-nitroaminotetrazolate

This material detonates aggressively.

It can detonate in single grains and seems to be quite powerful, seemingly more than most common primaries.

Pb 5-NATz is made from Na 5-NATz in the same way as lead azide from sodium azide. I used Pb(C2H3O2)2 in this attempt.
I don't currently have any tetrazole salts to side by side in comparison. --I think this stuff is pretty powerful.
It's responsive to flame while somewhat higher temp in dec point (230 C) than say Lead Azide at 190 C, (It goes without saying, it's much more powerful).
In this molecule, the Pb is divalent with NATz, similar to azide, but with hydration.
It is at least insensitive enough to handle for small scale testing. I haven't tested friction or impact yet, but will return to that at a later time after comparisons with some other primaries. Non-hygroscopic. Insoluble in H2O.
The amount used here in image is around ~5 mg.
Personally, I appreciate lead as a metal in primaries. Im less concerned with Lead products than say nickel. Lead is a universally accessible heavy metal which is lower toxicity than others, desirable attributes for general purpose heavy metal primaries.
I made this without recrystallizations throughout, just crude materials.
The preparation could likely be done wet, without drying in between ANQ->Na(NATz)->Pb(NATz)2, from ANQ forward, reducing time to stage.
I was satisfied with this material's relative preparation simplicity and high-performance.
I see 5-NATz as less tedious than a comparable tetrazole via AGu.
Looking forward to more testing on this one...

[Edited on 2-5-2023 by Hey Buddy]
UPDATE: been doing some more small detonation tests, this PbNATz is impressive. 10 mg detonations are very powerful. I dont know what velocity its detonating at, but I think it may be interacting with the Al foil in confined detonation. Making a flash that i dont see in open, unconfined detonation. It's really powerful. No doubt.

[Edited on 2-5-2023 by Hey Buddy]

Hey Buddy - 2-5-2023 at 10:57

It's now the next day, I've been testing this stuff this morning and afternoon. I have to say, this is seemingly the most powerful explosive per volume that I've yet seen. I suspect it's more powerful than the NTz molecules but I don't really know that without direct comparisons of explosive work. At 10 mg+ tests, this stuff is getting slightly intimidating, approaching small rifle fire, in terms of the perceived impulse. The gas output itself is relatively low at such small scale but oh boy is it loud and powerful. I believe it is reacting with the aluminum foil in lightly confined tests. There's no foil left other than where it is clamped in place. I may try a wax witness plate on detonation to see what kind of size the Al foil, if any, is turned into on detonation. It is possibly vaporizing to Al2O3 or some other mixed product. Wax seems like it could possibly capture foil particles from small tests to analyze destructive brisance.

I did rudimentary friction and impact tests. I would consider this material insensitive. I generally use PETN as a comparative benchmark and this material is less sensitive to impact than PETN. In fact, I was unable to detonate samples on an anvil, striking with a 32 oz hammer. I was unable to set a sample off by 32 oz hammer pressed and dragged across the material on top of anvil steel.

I dont want to talk it up too much, but really can't stress enough how impressive this material detonates. It is so loud and violent and fast. It definitely creates luminous sparks from the Al foil on detonation when lightly confined.

It appears to be somewhat less flame responsive than I originally had thought. I have attempted some fuze ignitions in foil with simple visco and they failed to detonate. Probably due to poor heat contact. Those tests were very crude foil/fuze tests, with small masses of the Pb NATz. Not the best source-study of flame sensitivity but I think it needs a nice hot direct transmission for detonation. If you give it proper heat activation it really fires. Wow.

MineMan - 2-5-2023 at 15:52

It's now the next day, I've been testing this stuff this morning and afternoon. I have to say, this is seemingly the most powerful explosive per volume that I've yet seen. I suspect it's more powerful than the NTz molecules but I don't really know that without direct comparisons of explosive work. At 10 mg+ tests, this stuff is getting slightly intimidating, approaching small rifle fire, in terms of the perceived impulse. The gas output itself is relatively low at such small scale but oh boy is it loud and powerful. I believe it is reacting with the aluminum foil in lightly confined tests. There's no foil left other than where it is clamped in place. I may try a wax witness plate on detonation to see what kind of size the Al foil, if any, is turned into on detonation. It is possibly vaporizing to Al2O3 or some other mixed product. Wax seems like it could possibly capture foil particles from small tests to analyze destructive brisance.

I did rudimentary friction and impact tests. I would consider this material insensitive. I generally use PETN as a comparative benchmark and this material is less sensitive to impact than PETN. In fact, I was unable to detonate samples on an anvil, striking with a 32 oz hammer. I was unable to set a sample off by 32 oz hammer pressed and dragged across the material on top of anvil steel.

I dont want to talk it up too much, but really can't stress enough how impressive this material detonates. It is so loud and violent and fast. It definitely creates luminous sparks from the Al foil on detonation when lightly confined.

It appears to be somewhat less flame responsive than I originally had thought. I have attempted some fuze ignitions in foil with simple visco and they failed to detonate. Probably due to poor heat contact. Those tests were very crude foil/fuze tests, with small masses of the Pb NATz. Not the best source-study of flame sensitivity but I think it needs a nice hot direct transmission for detonation. If you give it proper heat activation it really fires. Wow.

Are there any papers referencing this material or is it an invention of your own? Is this similar to the molecule with 10kms. Excuse me for my poor memory

dettoo456 - 2-5-2023 at 16:11

@Hey Buddy Have you tried isolating the Ni salt of NATz? You mentioned Pb as being more preferable to work with but Ni salts are generally more common throughout energetics simply due to availability and sensitivity safety. NH2OH or N2H4 might be interesting too - the hydroxylamine salts always seem to carry the highest performance as non-metallic bases. AgNTz seems like the best bet imo for most applications but you might be on to something with nitraminotetrazoles. The ANGN route to 5-NATz could be better than 5-ATz & 5-NTz (I haven’t looked at the $/g for either route yet though).

Hey Buddy - 2-5-2023 at 16:29

[/rquote]
Are there any papers referencing this material or is it an invention of your own? Is this similar to the molecule with 10kms. Excuse me for my poor memory

No problem. --The NATz salts are described by the usual klapotke and shreeve and Lieber did earlier work with it. The metal salts are less explored. --Semenov is the only reference Ive found on heavy metal salts. His literature doesnt describe any detail on explosive profile. Some of the NATz salts just burn violently while others explode. They are basically unknown in explosive behavior, but are known about in literature. Definitely not my invention, just a tetrazole with a nitrimino group. The whole family isnt well explored. The molecule with ~10km velocity is the free acid molecule. I have attempted that molecule but no success. It is supposedly pretty sensitive to stimuli.

Hey Buddy - 2-5-2023 at 17:13

Have you tried isolating the Ni salt of NATz? You mentioned Pb as being more preferable to work with but Ni salts are generally more common throughout energetics simply due to availability and sensitivity safety.

Excellent idea. After success with Pb Acetate, the acetate route seems useful enough. I have prepared acetates of Co, Zn, Ni and Cu. They are still evaporating but hopefully done tomorrow.

Plan is to run the same procedure on these other metals and see what's found.

NH2OH or N2H4 might be interesting too - the hydroxylamine salts always seem to carry the highest performance as non-metallic bases.

NH2OH would be awesome to try. Ive never even seen it. What seems to be the preferable route? NM? I have about a gallon of NM sitting around gathering dust. Any tips?

AgNTz seems like the best bet imo for most applications but you might be on to something with nitraminotetrazoles. The ANGN route to 5-NATz could be better than 5-ATz & 5-NTz (I haven’t looked at the $/g for either route yet though).

I agree AgNTz seems to be the king, it's way too early to say, but this lead salt seems to be more intensive in raw power than Na or Cu NTz. Maybe Im biased from excitment of learning about new materials--I also do have some silver nitrate around so I could do an Ag salt as well, Im less interested in silver analogues due to price of silver. But it would be worth a test.

Hopefully some other interesting materials can be found. The Pb is no slouch. I mean, it's ridiculous. -- IMO, ANQ route to NATz is easier than NTz. You just have to account for losses from NQ->ANQ->NATz. Not sure on cost of production, IMO zinc reduction to AGu is bit of an annoyance and the calcium hydroxide / urea route is better, but laborious. NATz is easier and quicker.

B(a)P - 2-5-2023 at 17:21

The Pb is no slouch. I mean, it's ridiculous. -- IMO, ANQ route to NATz is easier than NTz.

Maybe it is time to get some in a cavity and punch holes in steel?
Watching your work with great interest, thanks very much!

MineMan - 3-5-2023 at 02:30

Quote: Originally posted by B(a)P

The Pb is no slouch. I mean, it's ridiculous. -- IMO, ANQ route to NATz is easier than NTz.

Maybe it is time to get some in a cavity and punch holes in steel?
Watching your work with great interest, thanks very much!

Seconded! Silver amino tetrazole is too sensitive. What makes this promising is it’s more powerful and less sensitive than the red nickel salt talked about earlier. Would be really curious to see what 50mg does to a soda can, as that’s the street cred for primaries

Microtek - 3-5-2023 at 03:27

Remember that the purpose of a primary is not to do work, but rather to initiate secondaries. A better test would be to see how much material is needed to initiate something moderately sensitive, eg. TNT or plasticized RDX.

Hydroxylamine*HCl is an easy synthesis from nitromethane and hydrochloric acid. Just heat a mix of NM with an excess of aqueous HCl for about 12 hours. You can do it under reflux, or under slight pressure. I suggest beginning at a relatively low temp (maybe 50-70 C) and then raising when the mix is homogenous (just to decrease the pucker factor).
Then distill of the majority of the water and HCl off and crystallize the product. There are threads about it here on SM.

[Edited on 3-5-2023 by Microtek]

[Edited on 3-5-2023 by Microtek]

50 mg fuze failure

Hey Buddy - 3-5-2023 at 08:50

I attempted a can test with 50 mg of material, primed with TiH2/KClO4 & NC it was confined in Al foil taped to side of can. It appeared to deflagrate and didn't detonate. This seems to be a more leaning towards high power secondary explosive with a higher flame sensitivity. Flame responsiveness is greater than ETN, but much less flame responsive than styphnate, SADS, NAP.

I would consider this a secondary explosive or second stage detonator material. 50 mg was massive compared to the other tests I was doing. It would have destroyed and separated the can, it was a lot of material. In terms of heating it from underneath in foil confined and unconfined, it reliably detonates every time. So it detonates over flame more reliably than ETN.

MineMan - 3-5-2023 at 10:18

I attempted a can test with 50 mg of material, primed with TiH2/KClO4 & NC it was confined in Al foil taped to side of can. It appeared to deflagrate and didn't detonate. This seems to be a more leaning towards high power secondary explosive with a higher flame sensitivity. Flame responsiveness is greater than ETN, but much less flame responsive than styphnate, SADS, NAP.

I would consider this a secondary explosive or second stage detonator material. 50 mg was massive compared to the other tests I was doing. It would have destroyed and separated the can, it was a lot of material. In terms of heating it from underneath in foil confined and unconfined, it reliably detonates every time. So it detonates over flame more reliably than ETN.

Thank you Buddy!

I have an easy solution. Mix 10-20mg of Ni amino guanidine P with 50mg of this molecule and test again. To me this is promising, as excessive flame sensitivity indicates all other sensitivities.

Will you please try it using this method and compare the 50mg can to 50mg can of the nickel red?

50 mg Pb NATz, low density. 10 mg NAP low density prime. Two layers standard Al foil confinement

Hey Buddy - 3-5-2023 at 11:47

Didnt quite separate the can like I predicted, but it did fold it in which is neato.

Hey Buddy - 3-5-2023 at 11:51

Mix 10-20mg of Ni amino guanidine P with 50mg of this molecule and test again.

I didnt read your request carefully, that last test was just sprinkled in Al foil and then NAP sprinkled at the top where fuze contacts, not mixed, just fyi. --I just reread. I will now go do a 50 mg NAP can test...standby

[Edited on 3-5-2023 by Hey Buddy]

60 mg NAP hand pressed, no prime, visco, 2 layers standard Al foil confinement

Hey Buddy - 3-5-2023 at 12:29

[Edited on 3-5-2023 by Hey Buddy]

MineMan - 3-5-2023 at 14:02

Thank you! Really impressive all it needs is 10mg of NAP. This seems to be the perfect primary. My guess, is confined in a 1mm aluminum tube it will DDT every time. This could be quite the discovery! Congrats Buddy!

Transition metals 5-NATz

Hey Buddy - 3-5-2023 at 21:33

I have attempted displacement and isolation by Cu, Ni, Zn and Co AcO. All of them successfully displace easily. Cu, Zn, and Co become opaque by the end of complexing. The Ni is curious, in that it becomes a translucent purple like grape kool aide and on sitting it appears to precipitate a fine white powder to the bottom of the beaker but it is easily redissolved in the H2O and was entirely lost on filtering. I made a fresh batch of Na NATZ tonight and will attempt the Nickel again with cooling and decanting?

These salts are drying and will be processed for data probably not tomorrow but day after. I will also attempt a calcium and barium salt. I do have weird metals that could be attempted. I have vanadium, antimony and bismuth. Not really sure if any of those would be worth trying? I have a suspicion on the Ca salt that forms hydrates, I believe it can double complex with a Cu or Ni to be a CuCa/NiCa salt which may alter the hygroscopic properties. I wish I understood complexation more precisely to understand what is really going on.

Does anyone know what the likely complex would be for Zn, Ni, Co? If they would complex as 1,2, or 3 NATz? Cu is listed in semenov as complexing as one NATz per Cu and dec at 240 C

[Edited on 4-5-2023 by Hey Buddy]

UPDATE:
I have been a bit distracted, but I did test these materials today for burn and hammer. They are all explosive and fairly mechanically insensitive.
The Zn and Cu seemed a bit slow and low powered. The Co reminded me a of some tetrazoles with micro popping on flame.

It appears at first glance that Pb NATz is superior. Ag makes sense to attempt I suppose. It also makes sense to test Ca, Ba, and Sr, as those may possess some power. And of course try to isolate the Ni. --If the Ca salt is hygroscopic but detonates well, a co-metal salt might alter that hygroscopicity.

I made small batches enough to test basic properties to probe the materials. I will do a side by side between the materials to measure performance at small mass.

I have found a better medium than an aluminum can for small det tests...believe it or not, a grocery store standard food can works pretty well. @ 25 mg to 75 mg detonations, it causes formations without blowing apart the can and it leaves very clear and measurable indentations on the inner radius that can be calipered or just eye balled. It seems fairly sensitive to the force work of small detonations. In testing this, the charge weight was changed by 5 mg in a series of 4 on a can, the resulting dents are relatively scaled and resolved enough to tell the difference between ~5mg changes. I also tested the Glycine perchlorate (made by displacement with NH4ClO4) on this preliminary can test and can confirm that NAP @ 10 mg can detonate Glycine Perchlorate in 50 mg mass in a hand pressed column @ ~5/6mm diameter. I thought that was interesting. makes glycine perchlorate even more interesting, as it is a simply made melt cast, low critical diameter explosive. Purported to be 8km+ Vd. Even if 8 km were inaccurate and its Vd were a lot lower in the 7km range, it is still greater pressure, velocity and prepared much, much more simply than legacy TNT. All very exciting stuff. Having lots of fun with this stuff.

[Edited on 5-5-2023 by Hey Buddy]

[Edited on 5-5-2023 by Hey Buddy]

Hey Buddy - 3-5-2023 at 22:09

Hydroxylamine*HCl is an easy synthesis from nitromethane and hydrochloric acid. Just heat a mix of NM with an excess of aqueous HCl for about 12 hours. You can do it under reflux, or under slight pressure. I suggest beginning at a relatively low temp (maybe 50-70 C) and then raising when the mix is homogenous (just to decrease the pucker factor).
Then distill of the majority of the water and HCl off and crystallize the product. There are threads about it here on SM.

This is what I was interested to know. I'm doing it in my mind right now. Thank you Microtek

Pb vs Co vs Cu vs Zn

Hey Buddy - 5-5-2023 at 10:35

50 mg loads of CoNATz, CuNATz, ZnNATz and PbNATz were fired at ~90 degrees from each other along the mid circumference of a food can.
All were lightly hand tamped in Al foil in a standard diameter of ~5mm.
All were primed with 10 mg NAP.

The order from smallest impression to the largest is Zn<Cu<Co/Pb

Co did make a greater impression in the can than Pb on this sample. In my judgement, this is probably an anomaly. PbNATz seems noticeably more powerful than Co, although Co is also powerful.

Zn and Cu were noticeably less powerful in all testing. Co and Zn both seem to have a tendency of micro detonations.
The Zn test didn't have a full detonation as micro pops could be heard after the main load was fired. I believe despite this, it still seems like Zn is the least powerful, with Cu also somewhat anemic compared to Pb.

Pb and Co are down selected for next stage testing against Ag, Ba, Sr, Ca. Hg is purportedly an effective primary explosive according to semenov. This is the only material he describes as a primary explosive.
I don't plan to test Hg analogue.
Hg is probably one of the least desirable cations for explosives in general, due to the hazard of Hg and it's lower availability.

[Edited on 5-5-2023 by Hey Buddy]

MineMan - 5-5-2023 at 13:14

This is exciting

Camera broke

Hey Buddy - 5-5-2023 at 23:01

Ca, Sr, Ba, Ag salts are made.
Ca(OH)2, Sr(NO3)2, Ba(NO3)2, Ag(NO3).
Sr reaction is translucent similar to Ni attempt.
All other metals opacified in 5 minutes or so on reaction @ 70 C.
Going to be using cell phone pics for follow up.

[Edited on 6-5-2023 by Hey Buddy]

Hey Buddy - 5-5-2023 at 23:21

Remember that the purpose of a primary is not to do work, but rather to initiate secondaries. A better test would be to see how much material is needed to initiate something moderately sensitive, eg. TNT or plasticized RDX.

This is true. The ONLY purpose of primaries is initiation.
Other tangential interests of primries include:

-Simplicity of preparation
-Sympathetic detonation
-Critical mass/diameter

I will continue can impression down selection.
From those results of seemingly most-brisant NATz compounds, I will further test initiation ability.

Do you think RDX is better test than PETN? I have PETN already, but no RDX prepared. I could prepare plasticized RDX but which one? C4 analogue?

Microtek - 6-5-2023 at 08:05

You can use PETN as well. The point is simply that if the secondary is very easy to initiate, even a poor primary will work (eg. nitroglycerine can be initiated with blackpowder), so it will be difficult to get reliable data. So you need to make it challenging for the primary. Fortunately this can be accomplished by using more inerts in your PETN. You could start with maybe 20 % inerts, made up of either the binder/plasticizer system plus CaCO3 or other suitable material, or possibly the binder/plasticizer could account for all of the inerts.

Metal Nitrimino Tetrazoles continued...

Hey Buddy - 7-5-2023 at 17:21

Ba, Sr, Ag all displaced successfully, Ca is inert, which seems like it has some error in preparation, as CaNATz should be explosive.
The other three salts were dried gently and probed for flame responsive detonation. Ba and Sr gave micro popping on burning.
Ba pops were the strongest but there was no observed detonation.
Ag deflagrates.
These salts as tested, should all be in their hydrated forms with whatever crystal water they have. Presumably if heated, they would become anhydrous which would make them more sensitive and easier to achieve detonation. The Barium and Calcium salt are both known to have different performances and sensitivities in hydrated form versus anhydrous.
Barium is reported in literature to be dehydrated at 200 C.
Of all these salts, so far, the Pb clearly stands apart. It has an interesting profile:

Pb 5-NATz
1) It detonates on flame over foil
2) it does not DDT, but deflagrates on a visco fuze
3) it is insensitive to friction and impact
4) it is obviously very powerful as a primary explosive
5) Tiny critical mass threshold of detonation

There is an obvious question of if the Pb NATz (being natively a tetra-hydrate) can lose water of crystallization, how far would it change its profile? It is worth looking into but I suspect with the insensitivity combined with high power and easy detonation, the hydrate could be more desirable. Anhydrous could potentially be even more powerful though...

I have not yet re attempted nickel. To be honest, I'm now thinking about formic acid condensation to triazole... I assume some sort of nitro amino triazole.
If a primary explosive could be found in that family, it would simplify precursors eliminating the need of nitrite and requiring only formic acid.
I plan a reattempt of the Ni, and probing if it's possible to dehydrate the Pb, but I'm looking forward to potential Triazole condensation salts with similar metal cations. Pb NATz will get further testing to probe initiating ability. I intend to use RDX and PETN as the standards. Hopefully an interesting triazole can be found.

underground - 8-5-2023 at 12:57

I am not a chemist but i got a bunch of diaminourea and was thinking if DAU will react with Nano2 the same way as ANG to form tetrazoles. Maybe an urea tetrazole based ?

[Edited on 8-5-2023 by underground]

Hey Buddy - 8-5-2023 at 19:32

It should respond by cyclization and also respond to other things like formic acid too. Personally, I don't know what form the urea semicarbazide/carbohydrazide cyclizes into with NaNO2. It could be a triazole or a tet. Im sure someone will know. I think NTO is from semicarbazide cyclization, If I'm not mistaken.

Formic Acid Cyclization is simple

Hey Buddy - 8-5-2023 at 19:52

I have now prepared the cyclization product of ANQ + HCOOH several times.
It's straight forward and provides good yield.
It is sort of a boring less-chromatic color change so I will spare the photos.

ANQ is dissolved in water and heated to 70 C on stirring.
My ANQ was crude, thus imparting an orange tint to the solution.
At 70 C formic acid at 2x molar excess was added drop wise.
I'm not certain if a 2x excess is appropriate, it may create a formate, which may not be desirable. This is simply an account of what was done. First, equal molar formic acid was added, then as the reaction seemed slow, more was added.
The solution loses some color turning more-white.
The solution undergoes a mass change and becomes slightly more volumous.
In my case, the mass change started to cause the material to rise out of the solution, so more water was added to keep everything in solution.
I was undecided about the time needed for the reaction, so I left the solution to stir at 70 C for 20 minutes.
The azole condensed product was filtered and washed with cold water.
The material is white after filtering and loses all orange tint from crude ANQ.

I'm uncertain of this material's exact identity. I believe it may be a Nitro Amino Triazole. I believe this material will complex not only with metals but possibly oxidizers too. I dont know the weight of this molecule and so I will be attempting complexing in excess with the metal cations.

I am going to repeat this formic acid +ANQ cyclization with strictly stoichiometric formic acid to identify if any difference presents itself between the two products.

[Edited on 9-5-2023 by Hey Buddy]

Microtek - 9-5-2023 at 01:34

Take a look at the attached paper. It seems that ANQ does indeed form 5-nitramino-1,2,4-triazole with formic acid.
Another interesting possibility would be oxalic acid which might form a bicyclic bis(5-nitraminotriazole).

They are said to be fairly strong acids, so you might want to make some ammonium-, hydrazinium- or hydroxylammonium salts...

Attachment: kurzer1963.pdf (1.6MB)
This file has been downloaded 220 times

Hey Buddy - 9-5-2023 at 06:38

They are said to be fairly strong acids, so you might want to make some ammonium-, hydrazinium- or hydroxylammonium salts...

It seems like there may be two products depending on the molarity of formic acid. I assume a formate results under 2x formic acid conditions. If the cyclization product is acidic, does a formate even seem possible or realistic? There are definitely two different materials formed from the respective formic ratios.

The difference between 1x formic and 2x is the following:
1x: Material remains off white. Material separates from water/acid to bottom of beaker.
2x: Material becomes white. Material expands in volume becoming almost fibrous in appearance.

If a formate is produced, then perhaps a nitrate/perchlorate could be coordinated by a metal cation?

Hey Buddy - 9-5-2023 at 06:42

Another interesting possibility would be oxalic acid which might form a bicyclic bis(5-nitraminotriazole).

I think I have some oxalic sitting around. I also have some sodium oxalate...

MineMan - 11-5-2023 at 11:58

Any update, or do you think NAP is so good there isn’t a point to the lead complex?

MineMan - 11-5-2023 at 12:09

Any update, or do you think NAP is so good there isn’t a point to the lead complex?

Hey Buddy - 11-5-2023 at 14:07

Any update, or do you think NAP is so good there isn’t a point to the lead complex?

Well, I think in terms of what's known and available, NAP is the most practical and useful of primaries. I think NAP is an equal jump from lead azide, as lead azide was from mercury fulminate, IMO.

This Pb(NATz)2 is a different material with different character entirely. It is more powerful, and insensitive, somewhat high temp, so if that is needed then it can fill that role. The azoles I have no idea of, so far they seem like secondary explosives. Still working on it...

underground - 16-5-2023 at 15:13

Well, i tried a reaction of 0,3mol of diaminourea with 0,3mol of Nano2 and 16ml of 30% HCL for the DAU neutralization and acidification. I used a magnetic stirrer and an ice bath. Then the addition of Nano2 started. The clear liquid become opaque meaning a reaction was taking place. After adding a few drops of Nano2 solution i did not noticed any increase in temperature and i felt quite confident to do the reaction out of the ice bath, since the temperature of the liquids was already too low and the best temp for ATz is about 15-20c. After removing the small beaker from the ice bath i let it mix without adding any further Nano2 solution. Luckily i was away from the vessel because a very small but bristant detonation occured. The detonation wasnt very loud because obviously it happend inside the solution but the beaker broke into pieces.
I dunno if i have messed up so hard or if a different kind of tetrazole is produced that it is so sensitive

[Edited on 16-5-2023 by underground]

Hey Buddy - 16-5-2023 at 16:44

Exciting. --Glad you are unscathed. You can use polypropylene for HNO2, just fyi, for detonations when testing random energetics. A PP beaker is very cheap. They can even handle diluted nitric acid to a certain degree (they phase change to brittle under 0 C).
I don't know what cyclization of carbohydrazide produces. If it is detonating in solution, there is a possibility it could be a sensitive tetrazole, or it could also be an intermediate prior to tetrazole formation, and the intermediate is detonating. Maybe something like an unstable organic azide carbonyl intermediate. I'm not sure. Surely someone will know. If you are already detonating in solution under NaNO2/HCl, you may get a different route or product from NaNO2/Acetic acid or NaNO2/H2O. It couldn't get any worse or more violent... well, i suppose with all that nitrogen and acid involving unknown products, I suppose it may be possible to release HN3. But if small reactions, it is probably not a great threat. HN3 has a very alarming potent smell and you cannot mistake it. the body will involuntarily avoid it when it is smelled. It's not like HNO2 which in my opinion smells a bit like bleach.

[Edited on 17-5-2023 by Hey Buddy]

underground - 18-5-2023 at 17:10

After searching a bit on net about the reaction of DAU and nitrous acid i found this.

"With nitrous acid it forms the highly explosive carbonyl azide CO(N3)2"

So DAU does not cycle to form tetrazoles. Most likely this is the reason why AGu is used. Actually the NH-NH2 group reacts to form -N=N-N=. So because DAU got 2 NH-NH2 groups, CO(N3)2 is formed. Most like the same would happened with diaminoguanidine forming HNC(N3)2. I bet monoaminourea would form tetrazoles or aminonitrourea.

[Edited on 19-5-2023 by underground]

Microtek - 18-5-2023 at 23:03

Hey Buddy:

Regarding the cyclization of aminonitroguanidine, I found by reading the attached paper and US patent 2744116 that heating with formic acid (or other organic acids) produces a stable addition compound, not a cyclic molecule.
It is only when you heat the addition compound with alkali (eg. K2CO3) that the heterocycle is formed.

Attachment: aminonitroguanidine_reactions_Henry.pdf (414kB)
This file has been downloaded 188 times

Hey Buddy - 19-5-2023 at 14:30

Great catch. I haven't been working on the triazole because it was unclear what was going on. Maybe this explanation will get it on track. Thanks.

dettoo456 - 21-5-2023 at 18:07

@Hey Buddy Have you made TAGN before? I was thinking about ANGN and such, and it seems good but if there are stability issues (as others have mentioned about it in the past), and it’s prep requires only GN, 98% H2SO4, Hydrazine, and HNO3, then why not just try to make TAGN, and then try formylation with cheap CH2O2? Afaik, the rxn hasn’t been done before, but in any case it’d cyclize to the hydrazinotetrazine or 5-hydrazino-4-amino-1,2,4-triazole; both great EM building blocks. The TAGN synth from GN & N2H4 is easy and high yielding too (>80%). The stability of both tetrazine and triazole aren’t known but I’m guessing they be better than a disubstituted amidine like ANGN (although I know ANG is useful to work towards 5-NATz).

Anyway though, food for thought. Good luck with the 5-NATz primaries.

Hey Buddy - 21-5-2023 at 19:48

@Hey Buddy Have you made TAGN before? I was thinking about ANGN and such, and it seems good but if there are stability issues (as others have mentioned about it in the past), and it’s prep requires only GN, 98% H2SO4, Hydrazine, and HNO3, then why not just try to make TAGN, and then try formylation with cheap CH2O2? Afaik, the rxn hasn’t been done before, but in any case it’d cyclize to the hydrazinotetrazine or 5-hydrazino-4-amino-1,2,4-triazole; both great EM building blocks. The TAGN synth from GN & N2H4 is easy and high yielding too (>80%). The stability of both tetrazine and triazole aren’t known but I’m guessing they be better than a disubstituted amidine like ANGN (although I know ANG is useful to work towards 5-NATz).

Anyway though, food for thought. Good luck with the 5-NATz primaries.

I've made DAGN and TAGN from GN + 2/3N2H4 but it was in search of unknown primary explosives and I thought they didnt seem to fit that bill when testing, so I didnt revisit it. IIRC it was good yield. I used alcoholic hydrazine so that Guanidine never even went into solution really. made it easy to filter. Cyclization with that would be interesting...
NAP is so good that it has stalled my motivation to investigate primaries.

[Edited on 22-5-2023 by Hey Buddy]

[Edited on 22-5-2023 by Hey Buddy]

Microtek - 22-5-2023 at 22:28

Do you have a reference for a good synthesis of a diaminoguanidine salt (or the free base I suppose)? I'm worried that I will get a mix of mono-, di-, and triaminoguanidine if I just do the hydrazinolysis with 2 equivalents of hydrazine.
I found a paper (chinese, so it requires checking) that claimed condensing DAG with oxalic acid and cyclicizing with base yields a bi(1,2,4-triazole) with four amino groups. These can then be nitrated and the product can form di- or tetra valent salts. The dihydroxylammonium salt is close to CL-20 in VOD and Pcj, with similar thermal stability and lower sensitivity. At a glance, their methods look OK, but it remains to be seen if their results can be reproduced.

Attachment: Tetranitramino-bis(1,2,4-triazole)_and_salts.pdf (1.2MB)
This file has been downloaded 189 times

Hey Buddy - 23-5-2023 at 06:38