Nickel aminoguanidine diperchlorate

Quote: Originally posted by Microtek

The mother liquor was clear and not black the way it often gets in the patent method for NAP. This black colouring is, AFAIK, characteristic of AQ decomposition under the influence of air. There are other decomposition modes of course.

Quote: Originally posted by Laboratory of Liptakov

It seems, that NAP explode soon spontaneously.....

You could do a wash to remove chloride contaminants from the finished product , then again, some “accidents “ produce unbelievable results , or changes in industry….

OK I decided to do the iNAP synthesis. I started with 75ml of 91% IPA and I boiled it, then added everything with strong stirring and kept the boil for 14 minutes. The amount of solvent I used was starting to run dry, well below 50ml, so after 14 minutes I stopped the heating and immediately poured out the stuff. I have a much larger 'yield' than last time I did it with iNAP. There was no nickel carbonate left undissolved, so the extended heating and stirring did its job in that regard, but right now the final answer will be whether or not I will finally have a useable product.

To test, I put some on a thin sheet of aluminum foil and I use a cheap torch lighter beneath it to heat the foil.

Edit: I put a photo of what my stuff looks like.

[Edited on 19-1-2025 by ManyInterests]

Quote: Originally posted by ManyInterests

Edit: Does Aminoguandine bicarbonate degrade over time? Even if stored properly?

Quote: Originally posted by pjig

For the ammonium perchlorate you can tell if you burn it with hexamine or other fuels . It puts off hcl gas (burns nose ) . You can also introduce a base like sodium hydroxide to release the gas to confirm your ammonium perchlorate. As for the aminoguanadine bicarbonate im sure one of the members will have a simple spot test you cold perform to confirm your material and its condition. [Edited on 20-1-2025 by pjig]

Quote: Originally posted by Etanol

Quote: Originally posted by ManyInterests   Edit: Does Aminoguandine bicarbonate degrade over time? Even if stored properly? This progresses very very slowly, much more than 10 years. The color of your product indicates that you have received an aminoguanidine complex, but probably with a different anion. Are you sure your NH4ClO4 is NH4ClO4? How did you prepare it? Mix 1 gram of sugar powder and 3 grams of your powdered perchlorate. How does this mixture burn?

My experience with NAP

Now I want to share my two cents concerning the different synthetic pathways and results.

The promising power and ease of synthesis draw my attention to this thread for more than one year and I´ve decided to give it a chance.

As I have no problems to get (almost) all precursors from commercial lab suppliers, I´ve bought perchloric acid, aminoguanidine bicarbonate and nickel acetate. I could also buy directly nickel perchlorate, but the price was a ripoff (several hundred Euro for a half kilogram). In such cases, I´m a cheapskate and I´ve bought commercially available nickel acetate, added the appropriate amount of 72 percent perchloric acid and evaporated it in the vacuum to dryness.

The much stronger and less volatile perchloric acid liberate the much weaker and more volatile acetic acid, conversion and yield close to 100% - for a fraction of the called ripoff-price.

The commercially available nickel carbonate isn´t pure nickel carbonate, it´s always a mixture with nickel hydroxide, in most cases not further specified. This makes stoichiometric calculations more difficult.

Anyway, I got the cheapskate nickel perchlorate and the aminoguanidine perchlorate in the same way (aminoguanidine bicarbonate and perchloric acid, no vacuum necessary).

Then I combined the appropriate amounts of concentrated solutions, boiled it for several minutes, cooled it down and the result was NOTHING.

Sad. No reaction, no orange crystals, just a dark green but clear solution.

Where was the mistake? I´ve repeated it twice, with more and less concentrated solutions, more and less heat and stored it even in the fridge for weeks.

Again, nothing. Sad.

Then I found a comment here from a fellow member that I should add aqueous 25% ammonia.

I decided to give it a last try and BINGO, almost immediately orange crystals appeared and settled down to the bottom of the erlenmeyer flask.

The quantity of ammonia seems not decisive, two drops with a pipette were enough. Therefore I think (just my speculation) that a catalytic amount is enough.

I´ve repeated the synthesis without boiling, just a warm water bath, and got a copious amount NAP.

No ultrasonication, no boiling necessary.

Then I started sensitivity testing. Some told here that it is less sensitive, but I could initiate it with a hammer hit out of my wrist. Is this less sensitive? Maybe less sensitive than lead or silver azide, but with a moderate hammer strike it goes off, no excessive force necessary.

The response to a flame seems difficult to predict. From my experience, small quantities (up to a matchhead) deflagrates in most cases. Sometimes it makes a sharp "whomp", but no bang.

The slightest confinement, however, produce a powerful and sharp bang. See the mpeg "NAP clamp", a quantity less than a matchhead partially covered between the tip of a clamp gave such a powerful explosion that the gas flame was blown off, whereas a larger quantity at the tip of a knife gave an intense "whomp!" but no bang - and the gas flame was not blown off.

After the first flame tests of unconfined samples (just deflagration, no detonation observed) I´ve decided to destroy the residual NAP soaked in the filter paper - the residual quantity was so small that I couldn´t scratch it off with a knife or spatula, thickness much less than a millimeter - and hold the filter paper in the flame.

To my surprise, I got an ear-ringing detonation! My assumption is that the very weak confinement in the porous filter paper was enough to promote ddt.

As a side note: the gaseous explosion by-products are very unpleasant and irritating to lungs and/or mucous membranes, even in tiny amounts.

To sum it up: yes, it´s an interesting and very powerful primary, easy to synthesize once you´ve found the way.

But there are some serious drawbacks. Nickel and its salts are always problematic, although maybe less problematic than lead or even mercury. The strongly irritating fumes after a minuscule explosion are a red flag for me.

Also there are still not fully evalutated stability issues (water sensitivity) and some other data/values are also not investigated (for example, compatibility with aluminum, copper and plastic, with secondaries, and - very important - it´s sensitivity against electrostatic discharge), unknown or at least not published.

Feedback and comments to my results are welcome.









Attachment: NAP clamp.mp4 (615kB)
This file has been downloaded 149 times

Attachment: NAP hammer.mp4 (1.2MB)
This file has been downloaded 154 times

Attachment: NAP knifetip.mp4 (759kB)
This file has been downloaded 137 times

Attachment: NAP spatula.mp4 (3.1MB)
This file has been downloaded 147 times

[Edited on 23-1-2025 by Nemo_Tenetur]

[Edited on 23-1-2025 by Nemo_Tenetur]

I'm also looking for copper ion alternatives to basically anything that bangs. Similar to Microtec. I observe nickel compounds including NAP thread through the user interface. For sure.....

Quote: Originally posted by Microtek

searching for alternatives based on iron,

The whole breathing is based on the oxidation of iron. So a little extra dust won't hurt anyone. If we could create a primary substance with iron ions, it would be revolutionary. After all, Fe2O3 is a reliable fire accelerator.....

Quote: Originally posted by Microtek

Thus it seems that nickel is ten times as toxic as copper but only two times as bad as cobalt. Iron is expectedly non-toxic (but ideally nothing other than air should be inhaled).

Quote: Originally posted by Microtek

I think the route through [Ni(NH3)6](ClO4)2 is your best bet. It is also a beautiful reaction in itself. There are a number of ways in the patent, have you tried following those without attempting to alter it in some way? Why would you boil it for 20-25 minutes? I think you would risk decomposing the aminoguanidine which is not very stable in the presence of air. By the way, I synthesized the copper complex, simply following the directions in the patent. It works as described and produces striking violet crystals. It is not as good as NAP and it remains to be seen how storage stable it is, but I can affirm that it is definitely not fake.

I decided to buy more aminoguanadine bicarbonate and... I noticed something. There is a significant difference in texture and color between my old purchase (which as far as I know has not changed since I got it some 2 and a half years ago) and the new one.

I pictured my stuff below and marked them. The fine white powder is the new purchase, while the one to its right is the old, it is chunky and not necessarily entirely white.

I won't be able to make another synth for another week or so, but if I make another synth and it all works out fine then I will be one very unhappy mad scientist... I almost bought from my original supplier, but I am glad I didn't. If it works I will buy another from the same guy I got this batch from and it should be happy, if a little poorer.

I hope the original ammonium perchlorate supply I have is good. Or maybe I will just use some of my lithium perchlorate (I don't think I'll be making Lithex, LL. sorry...) to make more confirmed ultra pure stuff.

ManyInterests......Lithex is too simple to make. There's nothing to mess with. You'll have much more trouble and fun making NAP......

NAP laser initiation

According to the German patent, NAP is laser sensitive. I´ve done some testing and would like to share my first results with you.

The laser pointers were bought from chinese suppliers. The three small are rated with 200 milliwatt , whereas the big (strong) blue is rated with 2000 milliwatt output. Beam diameter between 3 and 5 millimeter, beam not focussed.

Only the strong blue was able to initiate my NAP samples. I want to emphazise that this is just a preliminary result with two NAP samples irradiated out of my wrist. Surely more and better testing is necessary to get reliable results.



Attachment: Laser red.mp4 (2.9MB)
This file has been downloaded 156 times

Attachment: Laser green.mp4 (2.4MB)
This file has been downloaded 165 times

Attachment: Laser blue weak.mp4 (2.8MB)
This file has been downloaded 153 times

Attachment: Laser blue strong.mp4 (1.3MB)
This file has been downloaded 202 times

IT WORKS!

I was probably swindled on my original aminoguandine bicarb! The iNAP pops like a motherfucker! YES! IT WORKS!

Edit: I made a 2nd synth. The first picture (lighter colored stuff) is the first synth and it works. I got around 1.22g of yield. The 2nd synth is the second one and it is currently drying. It reacted a little differently... it took 20 minutes to do it instead of 17.5 minutes. I think it is because I kept the doors and windows opened that lowered the temp, but I almost ran out of solvent and I did see some of the rose colored stuff starting to form. I hope it works just as well.

[Edited on 16-2-2025 by ManyInterests]

Decided to do it a third time (because why not?) The 2nd time after it dried up was not as effective as the first, but it still popped. I am glad I am starting to get some results. I used 100ml of 91% IPA, but I think I used too much. The run time was a little over 20 minutes since something was up with the heating. I noticed that the reaction doesn't really start to kick in until the solvent is starting to run lower, so perhaps using too much of an excess is what caused it to get a little weaker.

This one was almost (and I mean almost) 20 minutes, but I had to let it out since it was almost fully dry. the color only started to get to the reddish/salmon rose towards the absolute end, which is concerning to me. but at any rate, I will wait for it to dry before trying some more. I will wait until tomorrow because I don't want to wake up any neighbors.

Quote: Originally posted by qwerty

Anybody else observe the same behaviour.

Quote: Originally posted by Hey Buddy

Quote: Originally posted by qwerty   Anybody else observe the same behaviour. I monitored a sample of iNAP and NAP from 2023 for degradation in storage in closed bottles, temp range -5 F to 115 F. I think it was around a year and half total time, two winters two summers. The samples were made from salts. There was a sample of NAP that turned dark reddish brown very early on, after only a few months, IIRC it was an early sample that was heated for a really long period of time in preparation. It was visually obvious that it changed in color pretty quickly. I still have this sample. It still detonates but is really sluggish and the performance is degraded. I had other samples of standard NAP and iNAP prepared from salts in the usual way. They didn't change over approximately a year and a half. I used them in detonators after I realized they were monitored beyond a year (which was my personal interest in the test).

Write up of my first attempt at (u)NAP

I tried following Dug's method as seen in his videos on the matter.
Aminoguanidine bicarbonate - 1g - purchased from china. It has a slight/medium ammonia smell. Could anyone tell me if that's normal?
Ammonium perchlorate - 0.86g - Made by reacting perchloric acid with aq. ammonia 25% solution and recrystalized twice.
Nickel carbonate - 0.43g - chemical supply store grade

-reagents were mixed together in a vessel
-30ml water was boiled in tall form beaker with magnetic stirring, covered with watchglass for reflux
-reagents were dumped together into refluxing water
-Mixture was allowed to react and reflux for over 10 minutes. Initially the color was green and then very slightly muddy. I expected to only need to react it for abour 5-7 minutes but I ended up leaving it for perhaps close to 15.
-mixture was decanted into a new beaker and placed in a ultrasonic bath at ~20C for 10 minutes.
No crystals were precipitated. No change was observed. Slightly red/purple colored liquid.
Mixture was allowed to cool to room temp and left covered for an hour. No crystals were formed.
After 2-3+ hours very small needle like crystals were observed at the walls of the beaker.
The mixture was left to crystalize for further 6ish hours and then the crystals were broken loose from the walls of the beaker by hitting them with the ultrasonic bath. Crystals were filtered and dried.
Final yield was 162mg - way less than I originally expected.
Tests on a aluminum foil detonated with a pop but no foil perforation was noticed.

Any ideas on what went wrong?
Does the synthesis of ammonium perchlorate seem sound?
What would be a good way to purify the aminoguanidine bicarb if the ammonia smell is not supposed to be there? I see that the solubility in water isn't great.

[Edited on 15-4-2025 by ExcerptSix]

Quote: Originally posted by ExcerptSix

-Mixture was allowed to react and reflux for over 10 minutes.

Quote: Originally posted by ExcerptSix

Mixture was allowed to cool

Quote: Originally posted by ExcerptSix

-mixture was decanted into a new beaker and placed in a ultrasonic bath at ~20C for 10 minutes.

Quote: Originally posted by ExcerptSix

I don't understand how I would be running an ultrasonic bath while heating to a boil and stirring the solution as your first quote suggested.

Quote: Originally posted by ExcerptSix

Could you confirm that a slight ammonia smell is normal from the Aminoguanidine bicarb?

Nitrobenzenediazonium perchlorate vs NAP

Large Crystal NAP Synthesis

I am a new member on this board. However, I've been reading postings on this board for about a year. I finally decided to attempt synthesis of NAP a few days ago and thought I'd share that experience and the results.

I found the synthesis, using the approach outlined by "Hey Buddy", to be very straight forward. I successfully prepared large crystal NAP, small crystal NAP (stirred), and iNAP (IPA) using Nickel Carbonate, Aminoguanidine Bicarb, and Ammonium Perchlorate in stoichiometric quantities.

I prepared large crystal NAP by placing all three reactants into 30 ml of boiling dH2O. The initial foaming was significant almost to the point of overflowing the beaker. The mixture immediately turned light green, then to a dark green, and near the end of the 7 minute boil, to a dark nearly transparent liquid with some non-reacted material swirling around the bottom. I gravity filtered the mixture hot. I noted there was a significant amount of non-reacted material on the filter paper. The non-reacted material appeared to be nickel carbonate with a few pills of amino guanidine bicarb. I allowed the dark reddish filtrate to stand w/o stirring or agitation with one deviation from Hey Buddy's approach. I forced the NAP to crystallize quickly by placing the filtrate in a refrigerator at 3-4 degrees Celsius. Understanding long exposure of NAP to liquid water would likely reduce yield and introduce non-reactive degradation products, I chose to speed up the crystallization of NAP out of solution. Quick crystallization may also produce smaller crystals than would slow crystallization. Seen with my naked eyes (admittedly old), the resulting NAP crystals are small pointed rods with the largest being on the order of 1mm in length. The first photo below shows the large crystal NAP on filter paper. I did not weigh the resultant NAP to determine a yield.

I did test the large crystal NAP after drying by placing a small amount on a piece of aluminum roof flashing. The flashing is 0.010" in thickness, substantially thicker than aluminum foil. Hence, the quantity of NAP tested was roughly the size of the head of the Q-Tip shown in the second photo for reference. Heated from underneath the flashing, the NAP detonated with a loud crack and made a substantial sized hole in the flashing as shown in the third photo. Note the third photo is turned 180 degrees from the second. Yes, I was wearing PPE (welding gloves, face shield, and muffs).

I could find no residue around the hole in the flashing or on the curled fingers on the underside of the flashing. Very clean detonation.

I'll add the small crystal NAP synthesis and the iNAP synthesis results in separate posts to prevent this from getting too long.

Small Crystal NAP Synthesis

In the first synthesis (Large Crystal NAP), I noted significant non-reacted reagents remaining on the filter paper with some of it in small pills/clumps. For this synthesis, I first ground/crushed and fully mixed the three reactants together dry hoping to more fully react the reagents in the process. In addition, I started the synthesis with the dH2O at 85 degrees Celsius (not boiling) with intent to get a more complete reaction. When I added the reagents, there was fizzing but no appreciable foaming. With vigorous magnetic stirring, the solution initially turned light green as before but turned to a darker green very slowly. After 7 mins at 85 degrees, I reset the temperature to 100 degrees and boiled the solution for another 5 minutes and the mixture turned to a dark semi-transparent liquid with some non-reacted components swirling around.

As before, I gravity filtered the mixture hot. The filtrate was a dark reddish almost black transparent liquid. Non-reacted solids on the filter paper appeared to be almost entirely green Nickel Carbonate with only very small traces of white pills of what I assume was Aminoquanidine Bicarb.

I forced the crystallization again with the beaker in an ice water bath this time with vigorous stirring using the magnetic stirrer. I don't know the rpm as my hotplate/stirrer has a simple rheostat for stirrer speed. Fine red crystals formed shortly after placing the beaker in the ice water bath. After about 10 minutes of vigorous stirring I placed the beaker in the refrigerator for about 10 minutes. I removed the beaker from the refrigerator and found the NAP crystals had all accumulated on the bottom with a nearly colorless aqueous solution on top. I decanted most of the water then filtered the NAP and remaining water. I used a small amount of IPA to rinse the remaining NAP from the beaker and wash the filtered NAP.

The first photo below shows the resultant small crystal NAP on the filter paper. The crystals appear to have a very fine sand like texture. Almost a powder consistency but under a strong light, there is some reflecting of light that indicates at least some of the material is crystalline.

I did weigh the NAP produced in this synthesis and got a net of 0.78 g. Not a great yield as I know others have gotten 1 g or more.

I also tested this small crystal NAP again using aluminum roof flashing (0.010"). The second and third photos below show the pre test and post test. This small crystal NAP detonated with the same sharp crack as the large crystal NAP test and left a hole in the flashing. The hole and the aluminum flower petals on the reverse had no visible residue from the detonation.

Acetic Acid

Quote: Originally posted by MineMan

If you add vinegar to replace some of your water my guess is you will see the yields increase.

INAP Synthesis

I followed essentially the same process using 91% IPA instead of distilled water up to the point of the iNAP dropping out of solution. Near the end of the 7.5 min boiling period, iNAP began to form on the top of the boiling IPA. Using IPA, there is no solution to filter and no filtrate to cool for crystallization. After 7.5 min I took the beaker of the heater/stirrer and let it set to cool to room temp. The salmon colored iNAP settled in the bottom of the beaker. I decanted off most of the liquid sitting on top then put the iNAP and remaining IPA through a gravity filter. The first photo below shows the wet iNAP on the filter paper. Because of the IPA used as the solvent (reaction medium?), the iNAP dries quickly and did require crushing the mass into powder gently with a toothpick. There was some non-reacted Nickel Carbonate and a few white pills of aminoguanidine bicarb mixed in with the iNAP. The iNAP yield was much higher than the NAP prepared with water. I'd estimate double the yield I got for the water based NAP.

I tested a portion of the iNAP after drying. The second photo below is pre-detonation and the third photo post detonation. I did not weigh the iNAP amount tested but I'd estimate around 50 mg. Since this synthesis and test, I did get a better scale that reads out in milligrams. I'm planning to test the three NAP forms against equivalent amounts of lead Azide in the next couple of days

NAP vs LA

After testing the three types of NAP I synthesized (large crystal, small crystal, and iNAP), I questioned whether NAP provides the same power/brisance as Lead Azide (LA) which I've synthesized previously. The iNAP I prepared seemed noticeably low on power. I made up a few test coupons out of 0.010" aluminum roof flashing. I started by testing small quantities of LA to find the minimum quantity of LA that would penetrate the test coupons in open air. Unfortunately, I failed to find the minimum. My scale will read down to 1 mg but I'm pretty sure the accuracy for determining an absolute mass fades below 10 mg. The first 9 photos below show the test coupons using 25 mg, 12 mg, and 6 mg of LA. The 6 mg charge had no trouble perforating the aluminum flashing.

Photos 10 and 11 show the pre and post test using 6 mg of large crystal NAP. The detonation left a sizeable dent in the test coupon but did not break through.

Photos 12 and 13 show the pre and post test using 10 mg of small crystal NAP. Again a sizeable dent, slightly deeper than photo 11, but did not break through the coupon.

Photos 14 and 15 show the pre and post test using 20 mg of iNAP. The iNAP detonation left a larger diameter dent in the test coupon of roughly the same depth as the other two NAP tests.

Making any concrete conclusions based on these simple tests is tough. But I'll go out on a limb and present what I believe I can take away from this.

1. On an equivalent weight basis, it appears the Lead Azide delivers more power and brisance than does NAP in any form.

2. The iNAP I prepared is significantly lower in brisance/power compared to Lead Azide as a 20 mg charge of iNAP would not penetrate the test coupon while 6 mg of LA did so easily.

I'd like to know if anyone else has made back to back comparisons of NAP performance vs other common initiators or primary explosives. If so, please share.

Although there is a correlation between micro scale power and initiation performance, testing on thin aluminium plate are irelevant.
For example mixtures with oxidizers on base NaH2PO2 or base lead phosphite as reduction agent show incredible hole in thin aluminium plate. But in thick steel cavity at 300 mg is impossible initiation ETN with them. Therefore are important words from Microtec. Reliability in the assembly (cavity) is crucial as the NAP will be used to initiate secondary materials. The same applies to CHP and many other primary-secondary mixtures. On air almost nothing, but in cavity initiation properties are observed....

Quote: Originally posted by Clay Buster

Quote: Originally posted by MineMan   If you add vinegar to replace some of your water my guess is you will see the yields increase. Nickel Acetate from Nickel Carbonate. Have you tried this yet? [Edited on 20-5-2025 by Clay Buster] [Edited on 20-5-2025 by Clay Buster]

I tested out several detonators using various grades of iNAP that I made, and all worked quite well to fully detonate various charges in the blasting caps. I used ETN:RDX, ETNETN, plain ETN, and an ETNETN:RDX charge(65:17.5:17.5 ratio) in the tube, they all worked very well, blasting apart the fence brackets I used for witness plates. I deleted the pictures, but I am very satisfied with the result.

the mention that lead azide would be superior might be true. But I never found any NAP complex, whether it is the native form or uNAP or iNAP to simply not detonate. iNAP is not as powerful or brisant as uNAP, but iNAP is MUCH safer to handle than uNAP and also a world of safety from handling an extremely sensitive material such as lead azide.

I used 0.075g of what I considered the 'better' grade of iNAP for my detonators, and 0.10g of poorer grade, but both worked perfectly to fully detonate the secondaries in the cap, and that is what is important. I was able to tightly pack (by hand, I tried to use a makeshift press, but I am not sure if it worked all that well) 1.5g of secondary, which should be enough for any charge.

So while LA is probably the superior overall, in terms of ease of manufacture and safe handling I would put uNAP or iNAP above it, and it isn't weak by any stretch of the imagination.

Amount of vinegar?

Perhaps crystal control agents could be used to alter the crystal morphology

By using a solution containing PVA and acetic acid to recrystallize NAP, or by adding PVA to the solution during preparation, sand-like and short-rod-like crystals can be obtained. Compared with ordinary NAP, iNAP or ethanol solution NAP, it has better fluidity and is easier to charge non-standard-sized micro-detonators. The sensitivity is also reduced. The amount of PVA added is 0.1%-0.01% of the solution mass. The specific process needs to be further explored. In principle, other crystal controllers for needle-shaped crystals are likely to be effective.

Quote: Originally posted by KFeNAT

By using a solution containing PVA and acetic acid to recrystallize NAP, or by adding PVA to the solution during preparation, sand-like and short-rod-like crystals can be obtained. Compared with ordinary NAP, iNAP or ethanol solution NAP, it has better fluidity and is easier to charge non-standard-sized micro-detonators. The sensitivity is also reduced. The amount of PVA added is 0.1%-0.01% of the solution mass. The specific process needs to be further explored. In principle, other crystal controllers for needle-shaped crystals are likely to be effective.

Quote: Originally posted by MineMan

Quote: Originally posted by KFeNAT   By using a solution containing PVA and acetic acid to recrystallize NAP, or by adding PVA to the solution during preparation, sand-like and short-rod-like crystals can be obtained. Compared with ordinary NAP, iNAP or ethanol solution NAP, it has better fluidity and is easier to charge non-standard-sized micro-detonators. The sensitivity is also reduced. The amount of PVA added is 0.1%-0.01% of the solution mass. The specific process needs to be further explored. In principle, other crystal controllers for needle-shaped crystals are likely to be effective. This is really interesting! Can you share more on your findings?! For industry bulk density and flow ability are the two bigs for primary explosives! Perhaps if 1 percent was used it would coat the crystals even more and make them far less sensitive! Can you try it with 1 percent and also try rapidly cooling the solution with stirring and an ice bath? [Edited on 30-5-2025 by MineMan]

Quote: Originally posted by Etanol

to KFeNAT, Hmm, Its correctly that you were able to get NAP in a slightly acidic environment of acetic acid and then recrystallize it from acetic acid without decomposing of NAP? This is strange for me, because I tried to get NAP in the aqueous solution with ways: Ni(ClO4)2+2AGu&CH3COOH=[Ni(AGu)2](ClO4)2+2CH3COOH and Ni(ClO4)2+2AGu&CH3COOH+2NH3=[Ni(AGu)2](ClO4)2+2CH3COOH4N But both reactions do not go. Instead of NAP I received a green solution of NI(CLO4)2 in a slightly acidic environment and a blue solution of a nickel complex with acetic acid in a neutral environment. [Edited on 31-5-2025 by Etanol]

Quote: Originally posted by KFeNAT

and then add alkali to make aminoguanidine recombined with Ni2+ to generate NAP. However, it is important not to use ammonia to neutralize acetic acid, because the alkalinity of NH3 is not significantly greater than that of aminoguanidine. ... Therefore, NaOH must be used to obtain a purer product, and the amount of NaOH required should be slightly less than the amount of acetic acid in the solution..

Quote: Originally posted by Axt

I have formed the acetate, but for the reason of producing a "universal solution" that can be used to precipitate whatever counterion one wishes just by adding its neutral salt, whether it be NaClO4, NaNO3, NaBrO3 etc. The acetate does seem to be significantly more soluble than the rest. I aimed to try chlorate and periodate, but I only tested bromate successfully. Ni4CO3(OH)6⋅4H2O + 8CH6N4⋅H2CO3 + 16CH3COOH + 8NaOH → 4Ni(CH6N4)2(CH3COO)2 + 8CH3COONa + 9CO2 + 23H2O 4Ni(CH6N4)2(CH3COO)2 + 8NaBrO3 → 4Ni(CH6N4)2(BrO3)2 + 8NaOOCCH3 Assumed Solubility BrO3 < NO3 < Cl < ClO4 < OOCCH3 But I'd have to test perchlorate. I cannot say I've noticed ammonium complexes interfering with the actual quality of the product, but rather definitely slows the precipitation, and any excess does hold it in solution preventing precipitation completely; thus, implying it's significantly more soluble that the AGu complex. They are some nice and neat crystals KFeNAT. If you had to do it would this be best from recrystalisation or integrated into the reaction liquor? I think I have PEG 4000 somewhere.

Quote: Originally posted by KFeNAT

To what pH did you add the NaOH?[/rquote] It is usually controlled between 8-9, which is related to the amount of acetic acid used and the concentration of the solution. The pH of the solution when the "excess" acetic acid in the solution is completely converted into sodium acetate is the pH that needs to be achieved in theory, and it is also the upper limit of the pH value. For example, in a solution of 0.6g acetic acid added to 30ml water, the pH value of the solution is about 8.5 when the acetic acid is completely neutralized.

tried to use dextrin with lower solution viscosity as a crystal control agent, and tried adding amounts of 0.2% and 1%. But the effect was not good, no obvious crystal morphology could be seen, and the product was not ideal.May be a mixture of products with various morphologies.

Regarding the sensitivity of sandy PVA-NAP

I used a homemade drop hammer for the test, relying on the impact of a steel ball fixed to the end of the shaft to sample, and the drop height was determined by calipers, and the mass of the entire drop weight was exactly 600g. Unfortunately, there was no significant reduction in the sensitivity of PVA-NAP in this test method.

Quote: Originally posted by KFeNAT

I used a homemade drop hammer for the test, relying on the impact of a steel ball fixed to the end of the shaft to sample, and the drop height was determined by calipers, and the mass of the entire drop weight was exactly 600g. Unfortunately, there was no significant reduction in the sensitivity of PVA-NAP in this test method.

Quote: Originally posted by MineMan

Quote: Originally posted by KFeNAT   I used a homemade drop hammer for the test, relying on the impact of a steel ball fixed to the end of the shaft to sample, and the drop height was determined by calipers, and the mass of the entire drop weight was exactly 600g. Unfortunately, there was no significant reduction in the sensitivity of PVA-NAP in this test method. I don’t understand how it is the same sensitivity as HMTD and LA is even less so? Reading papers CAP has a sensitivity of impact 20 less than LA which is reported at .1joules.

As far as I know, there is only one case where LA is so sensitive, that is, the solution is prepared with little stirring, so that a LA with significant needle-like crystals is obtained, which is not only extremely sensitive but also has a risk of self-explosion. But in fact, the sensitivity of LA is not high when the process is correct, the LA I used in the control test above is just a product that always maintains high-speed stirring during preparation, without adding any crystal control agent, and I have also tested the product with dextrin, and its sensitivity is lower than that of pure LA

Quote: Originally posted by Etanol

Clay Buster, these tests do not show the NAP power/brisance relative to the LA, but the deflagration to detonation transition. Apparently, the NAP did not detonate in all your tests. It is classic deflagration.

Quote: Originally posted by MineMan

Quote: Originally posted by Clay Buster   Quote: Originally posted by MineMan   If you add vinegar to replace some of your water my guess is you will see the yields increase. Nickel Acetate from Nickel Carbonate. Have you tried this yet? [Edited on 20-5-2025 by Clay Buster] [Edited on 20-5-2025 by Clay Buster] I do not understand the use of Ni carbonate. It seems users here always report non reacted solids. I think the acetate form is superior from listening to others. I assume if you start out with acetate there will be acetic acid… but maybe not enough for optimal yields. For carbonate I would expect the addiction of acetic acid to help substantially.

Acetic Acid Addition

Quote: Originally posted by Etanol

to KFeNAT, Hmm, Its correctly that you were able to get NAP in a slightly acidic environment of acetic acid and then recrystallize it from acetic acid without decomposing of NAP? This is strange for me, because I tried to get NAP in the aqueous solution with ways: Ni(ClO4)2+2AGu&CH3COOH=[Ni(AGu)2](ClO4)2+2CH3COOH and Ni(ClO4)2+2AGu&CH3COOH+2NH3=[Ni(AGu)2](ClO4)2+2CH3COOH4N But both reactions do not go. Instead of NAP I received a green solution of NI(CLO4)2 in a slightly acidic environment and a blue solution of a nickel complex with acetic acid in a neutral environment. I tried the NAP synthesis with small amounts of acetic acid and got the same green solution with no crystallization. [Edited on 31-5-2025 by Etanol]

Quote: Originally posted by Clay Buster

I tried the NAP synthesis with small amounts of acetic acid and got the same green solution with no crystallization.

Quote: Originally posted by KFeNAT

NaOH required

Following on my theory of the forced precipitation of NAP from IPA i did the following experiment.

Prepare a batch of NAP from salts:
NiCO3 0,43gr
NH4ClO4 0,86gr
AG 1gr
Use 27ml of water for the boil.

After 10min of boiling I decanted the liquor from the unreacted nickel carbonate into 380ml of IPA previously chilled to ±5°C under stirring at 600rpm. Solution turned a salmon orange colour and immediate precipitate was observed. I let it sit for an additional 10minutes in the freezer then filtered. Washed the filtrate with an addition 40ml of IPA and let it dry. Final yield was ±0,48gr.

The colour is almost identical to the INAP I previously prepared. Behaviour is identical to other NAP variants I prepared. So it may not be conclusive that the IPA complexes but I personally doubt it.

[Edited on 18-6-2025 by qwerty]

Acetic Acid Addition with pH Pushed to ~8

Quote: Originally posted by Etanol

Quote: Originally posted by Clay Buster   I tried the NAP synthesis with small amounts of acetic acid and got the same green solution with no crystallization. Add 3-5% NaOH solution to pH8. Quote: Originally posted by KFeNAT   NaOH required

Quote: Originally posted by Clay Buster

Is this what you are suggesting? Have you tried this approach? If so, what was your result?

NAP Produced with Acetic Acid

Quote: Originally posted by Etanol

Quote: Originally posted by Clay Buster   Is this what you are suggesting? Have you tried this approach? If so, what was your result? Yes, I tried this approach. However, I would like to wait for the evidence of other experimenters who would confirm or refute my opinion. My opinion is the product is contaminated with [Ni[AGu]2] diacetate. It is weaker and has a longer DDT than clear NAP.

I was partially successful in producing small crystal NAP using acetic acid to convert the insoluble Nickel Carbonate to soluble Nickel Acetate on the front end of the synthesis followed by addition of NaOH to pH= 9/10 on the back end. The wet NAP I produced shows the same appearance as the water produced NAP I've prepared previously. A more detailed of the process I followed is provided below.

I weighed out 0.43 g Nickel Carbonate and 0.86 g Ammonium Perchlorate and placed both into a tall form 200 ml beaker with 25 ml of DH2O. I placed the tall form beaker into a water bath on the hot plate and put a stir bar into the beaker. I set the temp at 99 C.

Sidebar: I use a hot water bath because, in a few of my previous NAP runs I've had the unfortunate experience of the boiling NAP solution "burp" with some of the burps violent enough to eject the solution from the beaker. This usually occurs near the end of the boil as the solution is turning very dark green. I believe there some type of reaction occurring at the interface of the beaker bottom and the boiling solution. My hot plate has a temperature thermocouple but no rheostat; just full on or full off. So, the hot plate surface and the bottom of the beaker are getting pretty hot near the end of the boil. The hot water bath provides enough thermal inertia to prevent the bottom of the beaker getting too hot.

Back to the synthesis: As the hot water bath and solution in the beaker are getting up to temperature I weighed out 1 g Aminoguanidine Bicarb (AGB) but held off adding the AGB to the reaction beaker. I dripped in a weak solution of acetic acid into the reaction beaker until I got the pH down to about 5. At this pH, the Nickel Carbonate begins to dissolve and the hot solution becomes almost transparent green. I let the Nickel Carbonate and Ammonium Perchlorate get up to a light boil and slowly add the 1 g AGB. There is a reaction that occurs as the solution foams up to about 2/3s of the beaker but quickly dies down back to a light boil. I boiled the solution for about 6 min and then added a NaOH solution dropwise to a pH of 8/9.

At 7.5 minutes, I turned off the heat and gravity filtered the hot solution collecting the filtrate in a 50 ml beaker. I placed a stir bar in the 50 ml beaker and placed the beaker into an ice bath with the stirrer running fast. I've found that aggressive stirring of the filtrate in an ice bath causes the NAP to crash out of solution quickly in the form of very small crystals.

I got a very healthy NAP yield on this run. Photo of wet NAP below. I said above I was "partially successful" because I still had some unreacted Nickel Carbonate in the filter paper from filtering the hot NAP solution. For my next attempt, I will use a bit more acetic acid and see if I can get all of the Nickel Carbonate to go into solution as Nickel Acetate along with the Ammonium Perchlorate. I should see the green solution go completely transparent at that point.

After the NAP dries, I'll test it to see if it is as forceful on aluminum flashing as the NAP I've produce previously.

NAP dried out and I tested it. I weighed out 10 mg and placed it on 0.010" aluminum flashing. Heated from underneath with a propane torch. Full detonation and blew through the aluminum like the standard NAP I've produced. Photos below. I also compared this batch of NAP to the standard NAP I have on the shelf. In all appearances, it is identical.






[Edited on 8-8-2025 by Clay Buster]

NAP Produced from Perchlorate Reactants

Quote: Originally posted by Etanol

It seems, aminoguanidine perchlorate is soluble in hot ethyl alcohol and acetone. Na2SO4, NaCl, Agu-sulphate and AGu-chloride is not. How about this way?: NiCO3+H2SO4(37%,water solution to pH5...4)=>NiSO4+CO2+H2O NiSO4+2NaClO4*H2O(in water solution)=>Ni(ClO4)2+Na2SO4 =>(drying)=>(hot extraction with C2H5OH or acetone)=>Ni(ClO4)2(organic solution) 2AGuH2CO3+H2SO4(37%,water solution to pH5...4)=>(AGu)2H2SO4+H2O+CO2 (AGu)2H2SO4+2NaClO4*H2O(water solution)=>2AGuHClO4+Na2SO4 =>(drying)=>(hot extraction with C2H5OH or acetone)=>Ni(ClO4)2(organic solution) Ni(ClO4)2+2AGuHClO4(10-20% excess)+2NaOH (to pH7,5...8)=>NAP+2NaClO4 Hot AGuHClO4 is dangerous! It do not form crystall, but melts. At high temp its melt explodes! [Edited on 11-8-2025 by Etanol]

Quote: Originally posted by Clay Buster

What would be the advantage of preparing the perchlorate based reactants to get to NAP?

Quote: Originally posted by Hey Buddy

You can boil NH4ClO4 and NiX for a long time to produce Ni(ClO4)2*6H2O, the reaction for NAP doesnt begin until AGu ligand is added. The whole thing is really simple. [Edited on 29-5-2025 by Hey Buddy]

I attempted to make iNAP again and, while somewhat successful, my yield was very poor. My experience with using IPA (91%) to synth NAP has been hit and miss. Today was another miss.

I read through most of the 16 pages on this topic and ran across Hey Buddy's post above. I decided to try a slightly modified approach to the aqueous NAP synth which appears to have been very successful. I made three batches using the process summarized below.

45 ml DH2O in a 150 ml tall form beaker placed on a hot plate with strong stirring. Temperature set to 97 degrees which on my hot plate gives a continuous lightly rolling boil.

Add to the beaker 0.86 g Nickel Carbonate and 1.72 g Ammonium Perchlorate and boiled without AminoGuanidine Bicarb (AGB).

First synth boiled the first two components for 3 min then added 2 g AGB.

Second synth boiled the first two components for 5 min then added 2 g AGB.

Third synth boiled the first two components for 7 min then added 2 g AGB.

Prior to adding the AGB, the Nickel Carbonate and Ammonium Perchlorate in water make a minty green solution that is constant in color.

After adding the 2 g AGB, the reaction is very quick and the solution quickly turns darker green going to almost black within 2-3.5 min. The first synth took the longest time to turn black at about 3.5 mins. The second synth took between 2.5 and 3 minutes to turn black. The third synth took only about 2 min to turn black.

After adding the AGB I continued the boil for only 3.5 to 4 minutes as the solution color did not appear to darken further. I removed the beaker from the hot plate and filtered the hot solution through a coffee filter into a 100 ml standard beaker.

The filtrate and 100 ml beaker with magnetic stirrer was placed into a cold water bath (2 - 5 C) and stirring was turn up to high speed (just below splashing).

I'm pretty sure I pulled the 100 ml beaker out of the cold bath and stopped stirring too early. I placed the beaker into the fridge to further cool and crystalize. Rather than getting the small crystal form of NAP, I got medium sized long needle crystal NAP on this first synth. But, the yield was good and the color looks good. I tested an ~15 mg pile on some aluminum roof flashing and it detonated with sharp crack and shredded the flashing.

The second synth, I left the beaker and solution in the cold water bath with very strong stirring until I saw the small NAP crystals form in the solution (about 2-3 mins). I removed the beaker and placed it into the fridge.

The third synth was stirred and cooled as in the second synth.

I've found that with strong stirring in a cold water bath, I get a very small grain crystal NAP that appears to have the same power and detonation characteristics of the large needle crystal NAP. Of course, than only works out if you leave the beaker in the bath with stirring long enough for the small crystal formation (somewhere between a temp of 20 - 25 C).

I've also found that, once I see the small crystals form in the cooled stirred solution, I get a higher NAP yield if I place the solution beaker in the fridge for 30 - 45 min. After the short stay in the fridge, I filtered the contents through another clean coffee filter to capture the NAP. I also use a light IPA wash to clean out all the NAP crystals from the beaker and help dry the filtered NAP crystals a little quicker. The second and third synths final filtrate was nearly colorless clear with only a very slight hint of color.

I still found residual Nickel Carbonate on the hot solution filter paper, Interestingly, the 3 minute pre-boil residual was still minty green but the longer pre-boil residual was a much darker green on the 5 minute boil and nearly black on the 7 minute boil. It also appeared there was less residual on the hot solution filter paper for the 7 min pre-boil.

Once the NAP dries out (tomorrow), I'll weigh the result and see what I got for a yield. If nothing else, pre-boiling the Nickel Carbonate and Ammonium Perchlorate appears to speed up the reaction with AGB and the quick distinct color change provides some certainty that the NAP reaction has completed.

NAP Yields After Pre-Boiling Nickel Carbonate and AP

Quote: Originally posted by Clay Buster

Once the NAP dries out (tomorrow), I'll weigh the result and see what I got for a yield. If nothing else, pre-boiling the Nickel Carbonate and Ammonium Perchlorate appears to speed up the reaction with AGB and the quick distinct color change provides some certainty that the NAP reaction has completed.

I weighed the dried NAP from the second and third synths and got the following.

5 min pre-boil 0.992g
7 min pre-boil 0.928 g

I was surprised by this result as the pile of NAP from the 7 min pre-boil, despite weighing less, was visibly larger by volume than the 5 min pre-boil. Upon closer inspection of the two piles of NAP, it was apparent that the 7 min pre-boil NAP was a much finer grain almost powder compared to the 5 min pre-boil NAP. Since both are crystallizations from true solutions, I attribute the grain size and density differences to the speed and maybe duration of stirring while cooling/crystallization occurred. I did have strong/fast stirring on both but I purposefully had the stirring as high as possible w/o splashing out the solution on the 7 min pre-boil batch. Takeaway here is that the crystallization and bulk density of the NAP you produce is impacted by the energy you put into the solution as it is cooling/crystallizing. I believe this will be true whether you use strong stirring or an ultra-sound bath. The photos below show the two batches side by side in identical glass bottles. The lower volume batch is the heavier of the two, 5 min pre-boil batch.

On to the yield calc with a caveat. I've been retired for several years now and I'm a nuclear physicist not a chemist. However, I question if the yield calcs I've seen in previous postings here are correct. One post I ran across by Hey Buddy said the following.

"Yield is ~.91 g which is low compared to other procedures, a 100% yield would be 2.96 g"

I'll summarize mine below and please show me where I'm wrong if I'm off base here.

The chemical formula for NAP is Ni(CH6N4)2(ClO4)2

Note this formula is slightly different than in the first posting of this thread. There are two aminoguanidine molecules in the formula above. However, the chemical formula above is consistent with the patent linked below.

https://patents.google.com/patent/EP2450330A2/en

and it is consistent with the chemical name in the patent.
nickel (II) di(monoaminoguanidine) diperchlorate

I calculate the molar mass at 405.81 g/mol

Using Nickel Carbonate, Ammonium Perchlorate, and Aminoguanidine Bicarb (AGB) to produce NAP should therefore look something like the following.

Ni(CO3) + 2(NH4ClO4) + 2(CH6N4H2CO3) = Ni(CH6N4)2(ClO4)2 +2(H2CO3)

In the reaction, the bicarb may remain in solution or may break down to water and carbon dioxide. Given the pH values I've measured, I suspect much of the bicarb remains in solution. I believe most of the NH4 off gases during the reaction.

Calculating the yield based on 2 g AGB should look like this.

2 mol of AGB produces 1 mol NAP at 100% yield
AGB molar mass = 136.11 g/mol

I used 2 g AGB and got 0.992 g NAP

(2 g AGB)/(136.11 g/mol) = 0.014694 mol AGB

(0.992 g NAP)/(405.81 g/mol) = 0.002444 mol NAP

Since I need two mol of AGB to produce one mol of NAP, my molar yield is

(2 x 0.002444)/0.014694 = 33.3%

Doing the math in mass (vs mols) results in 1 g of AGB = 1.491 g NAP at 100% yield.

Let me know if I didn't get this correct.

Seeing that synth reports are still a thing on the subject I'll write up my last two synths using HClO4 since I have it.
I'm looking at my reagents the following way:
-Basic Nickel Carbonate (most nickel carbonate is basic, and mine being from the chem store it's stated as such) - Ni4CO3(OH)6(H2O)2 - 432.852 g/mol
-Aminoguanidine bicarbonate AGB - C2H8N4O3 - 136.11 g/mol
-HClO4 - 70% lab grade - 100.46 g/mol

For the first try I was going for 20mmol scale
A - Ni4CO3(OH)6(H2O)2 + 8HClO4 = 4Ni(ClO4)2
so for 20mmol of Ni(ClO4)2 I used :
-5mmol(2.164g) Ni4CO3(OH)6(H2O)2
-40mmol(4.018g) HClO4 and since mine is 70% - 4.018/(0.7*1.6713) = 3.434ml

B - AGu perchlorate 40mmol
-AGB 40mmol - 5.444g
-HClO4 - due to a typo during calculations I used 2.339ml

-A and B were carried out in two beakers with 50ml RO water each. A was clear green liquid after addition of acid and for once i didn't have any undissolved nickel carbonate.
-After addition mixture is light green to dark green
-Under stirring and hotplate set at 160C pH balancing with 25% aq ammonia to 7.5-8 pH the mixture turned black.
-Boiled under stirring for 10minutes
-Crystallization under ultrasonic bath with addition of ice to keep the temp of the bath from getting too hot.
-Yield was 4.797g. Crystals look darker and seem to be larger than previous synthesis with ammonium perchlorate which yielded under 500mg per synth. I'm theorizing that my ultrasonic bath was underpowered for the mass of crystallization going on or perhaps it crystalized too fast?

Second attempt at 10mmol
-basic nickel carbonate - 1.082g
-HClO4 70% - 1.717ml
-25ml water

-AGB - was to be 2.722g but i read somewhere in the thread that a little excess would be good so I used 3g
-HClO4 70% - 1.7ml
-25ml water

-When adding acid to AGB not all seemed to dissolve. When added to the nickel beaker CO2 was released so it seemed that there wasn't enough acid in the AGB beaker and there was some unreacted AGB which reacted when combined.
-ph balanced to 7.5-8 pH mixture turned dark green then black
-boiled under stirring for 8minutes
-Ultrasonicated in water, after a minute or two with no precipitation i noticed what looked to be undissolved nickel carbonate at the bottom.
-I decanted the still hot/warm black liquid to a new beaker. I could not see the undissolved solid in either beaker. maybe i was imagining?
-Continued the ultrasonic bath and the precipitation formed.
-Yield was 2.7938g. Crystals look slightly lighter in color and a bit finer than the first try but no real way to measure.

Comparing to my previous sub 500mg ultrasonicated yields it looks as if the smaller yields had a lighter color and are perhaps finer crystals.
Colors of the photo came out a bit wonky but the sample containers are as follows from left to right - Oldest batches , 20mmol , 10mmol.

Would a higher power sonication risk breaking the beakers?
Seems like I always need to add aq ammonia to turn the mixture dark. Is it the same for the rest of HClO4 users?
Would slower or faster cooling in the sonication be better for finer crystals?
I also noticed changes of the vibration of the beaker in relation to the position in the bath so the whole thing is a little fiddly for repeatability. Perhaps I'm not always getting the excitation of the mixture in the same way.

I think the next attempt I'll try to cool under fast stirring in an ice bath and compare since I don't have a stronger ultrasonic cleaner.

Looking at salt synth, 20 mmol and 10mmol through a microscope with the same magnification:
Salt:


20mmol scale:


10mmol scale:


Taken through x40 objective and x10 eyepiece.

Salt synths yielded around 300-400mg. Clearly with a smaller scale sonication worked better although the largest crystals in all samples looked to have around the same diameter. I'm trying to think up a good empirical way to test friction sensitivity between the samples.



[Edited on 4-10-2025 by ExcerptSix]

A new publication on NAP

Quote: Originally posted by pdb

Articles on NAP are rare enough that they're worth pointing out. Here is one that came out a month ago and thus is unfortunately not available online : https://onlinelibrary.wiley.com/doi/10.1002/prep.70039