Sciencemadness Discussion Board - Nickel aminoguanidine diperchlorate

I meticulously followed Hey Buddy's recipe:

1 g of aminoguanidine bicarbonate
0.86 g of NH4ClO4 (freshly prepared from HClO4 and NH4OH)
0.43 g of NiCO3 (freshly prepared from Ni(NO3)2·6H2O and NaHCO3)

All poured at once into 25 ml of boiling water under reflux with magnetic stirring. The solution turns bluish-gray, then it is decanted after 5 minutes and 30 seconds to remove the fraction of NiCO3 that did not react.

The beaker is placed in an ultrasonic bath (48 kHz instead of 42 kHz, but I imagine that doesn’t matter) at room temperature for 10 minutes: no precipitate forms. Another 10 minutes don’t change anything. The beaker is set aside: after a night, red needles appeared on the surface and nowhere else. They sink when the solution is stirred. Could oxygen from the air play a role in their formation?

The yield is miserable. I’ll keep the solution to see if more crystals continue to form in the coming days. But I don’t see where I went wrong.

It is odd that you didn't see any crystal formation. I saw red uNAP crystals even before I started ultrasonicating. I had ultrasonicated the stuff with some nickel carbonate present and it didn't appear to impact the formation, but there was already some NAP present in solution even before I started ultra sonicating.

For my frequency, I am not actually sure what frequency I used. But I used 30-35ml of water, which is a little more than what you used. I think that might be the thing?

EDIT: Problem! Whatever I got, it isn't NAP. I am not sure what is happening, but when I put some on foil and tried to get it to detonate, it didn't even burn, it just changed color and nothing happened.

EDIT2: I think I know why. It must be my ammonium perchlorate, I don't think it is pure enough. LL was right. I need better AP.

[Edited on 17-11-2024 by ManyInterests]

[Edited on 17-11-2024 by ManyInterests]

Laboratory of Liptakov - 17-11-2024 at 11:44

NH4ClO4 from HClO4 + NH4OH ? It should by pure salt. Is final AP white ? If AP is prepared with an excess of hydroxide, which evaporates during crystallization, it is almost impossible to make a mistake.... :cool:

pdb - 17-11-2024 at 12:14

NH4ClO4 from HClO4 + NH4OH ? It should by pure salt. Is final AP white ? If AP is prepared with an excess of hydroxide, which evaporates during crystallization, it is almost impossible to make a mistake.... :cool:

My AP is snow white. I did indeed use an excess of NH4OH. Anyway, I will try again... and succeed, provided the chemistry gods are on my side!

Hey Buddy - 17-11-2024 at 12:16

Could oxygen from the air play a role in their formation?

The yield is miserable. I’ll keep the solution to see if more crystals continue to form in the coming days. But I don’t see where I went wrong.

There has been a lot of speculation about the role of oxygen causing precipitation. Some people reported that when bubbling in pure oxygen, it causes immediate precipitation. https://www.youtube.com/shorts/KMqUBf5CH8U

Regarding yield, the patent method uses perchloric acid or nickel perchlorate hydrate. It is far higher yield. The procedure of using salts is in attempt to make the material more accessible and less hazardous in preparation. It allows a person to make a primary explosive in the field with no special equipment using inert and safe dry salts. If a person is concerned with yield, they should be using perchloric acid to maximize yield.

There was also recently a report of using NaOH to raise the pH at the end of the reaction, which then causes an immediate precipitation of NAP. This technique has been applied to perchloric acid methods but would likely function in the same way with a dry salt synthesis. uNAP as microtek stated, uses sonication which appears to force early and immediate nucleation of the complex causing it to precipitate out of solution. It should begin precipitating immediately within only a few seconds of sonication.

Etanol - 17-11-2024 at 13:10

it is decanted after 5 minutes and 30 seconds to remove the fraction of NiCO3 that did not react.

Time is not enough for the reaction

at room temperature for 10 minutes: no precipitate forms. Another 10 minutes don’t change anything.

The solubility of NAP is highly dependent on temperature. You should drop the solution until the first crystals appear, then slowly cool it to 0 degrees Celsius.

red needles appeared on the surface and nowhere else.

Red needles is NAP.

Could oxygen from the air play a role in their formation?

No. Oxygen decomposes aminoguanidine.

ManyInterests - 17-11-2024 at 16:48

it is decanted after 5 minutes and 30 seconds to remove the fraction of NiCO3 that did not react.

Time is not enough for the reaction

at room temperature for 10 minutes: no precipitate forms. Another 10 minutes don’t change anything.

The solubility of NAP is highly dependent on temperature. You should drop the solution until the first crystals appear, then slowly cool it to 0 degrees Celsius.

red needles appeared on the surface and nowhere else.

Red needles is NAP.

Could oxygen from the air play a role in their formation?

No. Oxygen decomposes aminoguanidine.

So what time would you recommend? I also decanted it/sonicated it after 5:30 minutes. Dugan Boomfax recommends 5 to 7 minutes in total. Would 7 minutes suffice?

Also what about temperature? I need to mention that when I did my addition and heating, I had completely sealed the top (I used a dollar store borosilicate glass jar with a bamboo cover, so it was 100% sealed the whole time) and I kept heating on throughout.

I tried to get it to the ultra sonicator as quickly as possible and the water temperature was at 23C at the start ultra sonication, but it didn't seem to have much of an effect. I did see red crystals from the getgo, so I thought I obtained something. In my haste, I wasn't sure if I decanted the unreacted nickel carbonate, and there was some visible in the ultrasonication phase.

But it all SEEMED OK. I am honestly wondering what exactly happened wrong. Right now I am banking on my ammonium perchlorate being bunk or contaminated.

I will need to make more perchlorate since while I have some sodium perchlorate, I am doubtful about its purity.So before I make another attempt I need to make my PbO2 cathode and make a decent quantity of sodium perchlorate, turn that into perchloric acid, and then neutralize with ammonium carbonate.

Etanol - 18-11-2024 at 03:33

Until most of the NiCO3 dissolves. I heated for about 20-30 minutes and even then not all the carbonate dissolved. I had to filter it.

Try to turn on the ultra sonicator at the same time as heating. This should speed up the dissolution of NiCO3.

It is impossible to heat the solution above 100C. Therefore 90-100C.
It is very important to maintain the volume of water in the mixture. If all the water evaporates, the hot mixture can explode.

If you have perchloric acid, you don't need to make ammonium perchlorate. You can make aminoguanidine perchlorate and nickel perchlorate, then mix it together and add ammonia or 2-3% NaOH to pH=7.5

[Edited on 18-11-2024 by Etanol]

ManyInterests - 18-11-2024 at 16:49

Quote:

I will take a note of this. Since I use water and only water and the beaker (a borosilicate glass jar actually) is 100% sealed, I don't have to worry about the water escaping, I saw the condensate on the sides of the jar as I heated. I guess just turn the hotplate at full blast and let it stay for 20 to 30 minutes? (25 minutes maybe as an aim... with max stirring of course).

Quote:

It is very important to maintain the volume of water in the mixture. If all the water evaporates, the hot mixture can explode.

Yes, I don't want a boom. Is a slight excess of water acceptable? I used 35ml in my failed synth for the 1:0.86:0.43g ratio, would something like 50 or 60ml still be acceptable?

Quote:

If you have perchloric acid, you don't need to make ammonium perchlorate. You can make aminoguanidine perchlorate and nickel perchlorate, then mix it together and add ammonia or 2-3% NaOH to pH=7.5

At first I was thinking 'how' but then I immediately realized you meant to make perchloric acid and neutralize it with nickel carbonate (for nickel perchlorate) and aminoguanidine bicarbonate for aminoguanidine perchlorate.

This still poses a problem for me, since I have yet to make perchloric acid and I have no experience in neutralizing it with bases. Using ammonium carbonate makes sense for me due to its ease and obtaining ammonium carbonate. I have kilos of ammonium carbonate, but I only have 99grams of aminoguandine bicarbonate and 99.5 grams or so of nickel carbonate. Also adding an excess of ammonium carbonate is acceptable for me since once I have neutralized all the perchloric acid, I can boil down the remaining liquid (the reaction formula is: (NH4)2CO3 + 2HClO4 → 2NH4ClO4 + CO2 + H2O ) to obtain dry, pure ammonium perchlorate. I know with this equation, but I don't have enough aminoguandine bicarbonate to really play around with it, so I would rather play sparingly with it.

Quote:

There was also recently a report of using NaOH to raise the pH at the end of the reaction, which then causes an immediate precipitation of NAP. This technique has been applied to perchloric acid methods but would likely function in the same way with a dry salt synthesis. uNAP as microtek stated, uses sonication which appears to force early and immediate nucleation of the complex causing it to precipitate out of solution. It should begin precipitating immediately within only a few seconds of sonication.

Yes, using ammonia or 2-3% NaOH as Etanol said... would 10% ammonia or even 27% work? I have both. It could have been this that caused my synthesis to fail as well?

But like I said, before I do anything, I need 100% pure ammonium perchlorate. I am sure that the other method mentioned is probably better, but it isn't something I feel able to do. Either way I will need to make a lot of pure sodium perchlorate to turn into perchloric acid.

[Edited on 19-11-2024 by ManyInterests]

Attempt with HClO4

pdb - 20-11-2024 at 06:09

This time, I tried the synthesis with HClO4. Nickel perchlorate hexahydrate is synthesized in situ, which requires adding 0.779 g of HClO4 (1.11 g of 70% acid) to the proportions in the patent.

- 25 ml of water in a beaker under magnetic stirring
- + 2.83 g HClO4 70% (2*0.6/0.7 + 0.779/0.7)
- + 0.46 g NiCO3
Once the effervescence stops:
- + 1.6 g monoaminoguanidine hydrogen carbonate
When the effervescence ceases again:
- Fast heating is applied, and the mixture is kept boiling for 6 minutes, then removed from the hot plate.
- The beaker is placed in an ultrasonic bath at 21°C for 5 minutes: no reaction.

NaOH is gradually added: each drop produces a rust-colored cloud that dissolves in a few seconds (see pic). A lot of NaOH is needed to raise the pH to 7–8!

A new attempt in the ultrasonic bath: still no reaction, nada! I will wisely wait for the 4 hours mentionned in the patent...

pdb - 20-11-2024 at 06:49

After 2 hours, red needles appeared on the surface. I will retry the ultrasonic bath.

Meanwhile, it turns out that the nickel carbonate prepared from the nitrate weighs twice the expected stoichiometric weight (Ni(NO3)2.6H2O + 2 NaHCO3 -> NiCO3 + CO2 + 2 NaNO3 + 7 H2O). Therefore, it’s not pure NiCO3 but rather a hexahydrate or another variation like Ni4CO3(OH)6(H2O)4 or some other complex.

This means that in my synthesis, I have about half the amount of nickel I expected and a significant excess of HClO4, which explains why I had to add so much NaOH to adjust the pH to 7–8.

Does anyone know how to properly prepare NiCO3 from Ni nitrate? Otherwise, I just need to double the amount of my suspect nickel carbonate in the synthesis.

[Edited on 20-11-24 by pdb]

Axt - 20-11-2024 at 08:48

Have you tried to just run it with nitrate in solution?

How soluble is Nickel aminoguanidine nitrate? if it's very soluble I'd just use as is. What about the chloride? If I was to do it, this would be the first thing I'd try:

Solution 1

Displacing AG bicarbonate with hydrochloride
2CH7N4.HCO3 + 2HCl --> 2CH7N4.Cl + 2H2O + 2CO2

Freebasing aminoguanidine
2CH7N4.Cl + 2NaOH --> 2CH6N4 + 2NaCl + 2H2O

Solution 2

Dissolution of nickel perchlorate
NiO + 2HClO4 --> Ni(ClO4)2 + H2O

Combine 1 & 2

Complexing aminoguanidine to nickel perchlorate
Ni(ClO4)2 + 2CH6N4 --> Ni(CH6N4)2(ClO4)2

Replace the HCl with HClO4 if the chloride complex has too low of a solubility. I feel like nickel oxide is more readily available than the carbonate or nickel metal itself.

[Edited on 20-11-2024 by Axt]

Microtek - 20-11-2024 at 10:03

I would suggest using the Ni(NH3)6(ClO4)2 complex like they do in the patent. You can make it by adding ammonia water to a solution of nickel nitrate or chloride or sulfate, then adding a solution of perchlorate (acid or sodium or ammonium salts) to precipitate the complex. The solid complex quickly dissolves in the boiling AQ-salt solution and the ammine ligands are quite labile and easily replaced by aminoguanidine during the reaction.
If you ultrasonicate after 5 minutes of boiling, you will see the NAP precipitating almost instantly.

Etanol - 20-11-2024 at 12:11

Freebasing aminoguanidine
2CH7N4.Cl + 2NaOH --> 2CH6N4 + 2NaCl + 2H2O

This is interesting. But how do you separate aminoguanidine from NACl?

This time, I tried the synthesis with HClO4. Nickel perchlorate hexahydrate is synthesized in situ, which requires adding 0.779 g of HClO4 (1.11 g of 70% acid) to the proportions in the patent.

- 25 ml of water in a beaker under magnetic stirring
- + 2.83 g HClO4 70% (2*0.6/0.7 + 0.779/0.7)
- + 0.46 g NiCO3
Once the effervescence stops:
- + 1.6 g monoaminoguanidine hydrogen carbonate
When the effervescence ceases again:
- Fast heating is applied, and the mixture is kept boiling for 6 minutes, then removed from the hot plate.
- The beaker is placed in an ultrasonic bath at 21°C for 5 minutes: no reaction.

NaOH is gradually added: each drop produces a rust-colored cloud that dissolves in a few seconds (see pic). A lot of NaOH is needed to raise the pH to 7–8!

A new attempt in the ultrasonic bath: still no reaction, nada! I will wisely wait for the 4 hours mentionned in the patent...

To begin with, you may not use ultrasonic. ultrasonic modifies the shape of crystals, but it does not affect the course of this reaction. Drain the solution 2 times, then cool the solution to 0C.
Are you sure your aminoguanidine is aminoguanidine? Usually the solution turns black-red at pH 7...8

Axt - 20-11-2024 at 13:26

This is interesting. But how do you separate aminoguanidine from NACl?

No need to, it stays in solution. It assumes Ni(AGu)2(ClO4)2 is a whole lot less soluble than Ni(AGu)2(Cl)2. But then you can just use excess HClO4 assuming you are only after a couple grams and keep the NaClO4 in solution, HCl is only to save on HClO4.

Hey Buddy - 20-11-2024 at 14:19

Does anyone know how to properly prepare NiCO3 from Ni nitrate? Otherwise, I just need to double the amount of my suspect nickel carbonate in the synthesis.

[Edited on 20-11-24 by pdb]

I know a guy who prepares it through NiCl2 metathesis which worked well, and changes color between the two Ni salts for visual confirmation.

Just for reference, NiCO3 is available widely as a glaze component from any ceramic supply shop across the world. In the US, it is around $18-25/lb.

[Edited on 20-11-2024 by Hey Buddy]

[Edited on 20-11-2024 by Hey Buddy]

Axt - 20-11-2024 at 16:12

I you are desperate enough, you could extract the nickel hydroxide from dead NiMh batteries.

pdb - 21-11-2024 at 05:51

This time, I followed example 2.3 from the patent and Microtek's advice:

Synthesis of Hexaammine Nickel(II) Perchlorate Ni(NH3)6(ClO4)2

Ni(NO3)2·6H2O + 6 NH3 (aq) → Ni(NH3)6(NO3)2 + 6 H2O
Ni(NH3)6(NO3)2 + 2 HClO4 → Ni(NH3)6(ClO4)2 + 2 HNO3

- 2 g of Ni(NO3)2·6H2O in 5 ml of H2O
- add 1.86 g of NH3 (aq)
- add 1.57 g of 70% HClO4

Instead of attempting to isolate Ni(NH3)6(ClO4)2, the synthesis continues according to the patent:

- add 55 ml of H2O
- add 4.08 g of 70% HClO4
- add 3.81 g of aminoguanidine hydrogen carbonate
- after effervescence, fast heating until boiling, kept for 5 mn: the solution turns gray.
- ultrasonicating 4x5 mn: no precipitation occurs until the temperature drops to around 30°C.

The filtrate continues to deposit some NAP over the following hours.
However, the yield is only 32%, far from the 89% claimed in the patent

Laboratory of Liptakov - 21-11-2024 at 11:18

water solution: Ni(NO3)2 - anhydride 10g + NaHCO3 9,2g = 6,5g NiCO3 (insoluble) + 9,3g NaNO3 (hi soluble) + 2,4g CO2 + 0,1 H2O

water solution: NiCl2 (anhydride brown) 10g + 13g NaHCO3 = 14g Ni(HCO3)2 (insoluble in water) + NaCl

water solution: NiSO4 (anhydride) 10g + 10.9 NaHCO3 = 7.7g NiCO3 (insoluble) + Na2SO4 9.2g + CO2 2.8g + H2O 1.1g

Procedure from Ni(NO3)2: 2g Ni(NO3)2 hexahydrate insert as crystalls into glass + 2g NaHCO3 as dry powder added. Add 40g dH2O and temperaure increase on 80 C on waterbath. Partially open cap was used. After 60 min. at 80 C is solution decantated, added 100g normal water, washing and decantated or separated on Buchner device. After drying you have fine and pure powder of NiCO3... :cool:

[Edited on 22-11-2024 by Laboratory of Liptakov]

Etanol - 22-11-2024 at 07:46

Instead of attempting to isolate Ni(NH3)6(ClO4)2, the synthesis continues according to the patent:

- add 55 ml of H2O
- add 4.08 g of 70% HClO4
- add 3.81 g of aminoguanidine hydrogen carbonate

Bad idea. Ni(AGu)2(ClO4)2 and Ni(AGu)2(NO3)2 mix formed.

Microtek - 24-11-2024 at 02:56

Yes, the advantage of isolating the Ni(NH3)6(ClO4)2 is the absence of any ions that might interfere with the reaction, ensuring that whatever you get really must be NAP. Also, I would suggest heating the AQ*HClO4 solution close to boiling before adding the Ni(NH3)6(ClO4)2.

pdb - 24-11-2024 at 11:44

Procedure from Ni(NO3)2: 2g Ni(NO3)2 hexahydrate insert as crystalls into glass + 2g NaHCO3 as dry powder added. Add 40g dH2O and temperaure increase on 80 C on waterbath. Partially open cap was used. After 60 min. at 80 C is solution decantated, added 100g normal water, washing and decantated or separated on Buchner device. After drying you have fine and pure powder of NiCO3

Thank you LL. There is a typo I guess... you mean 4 g (or more precisely 3.46 g) of Ni(NO3)2.6H2O

Heating the solution like this allows the decomposition of NiCO3 hydrates or hydroxides?

Laboratory of Liptakov - 24-11-2024 at 12:24

In short, such proportions that the baking soda is in excess over the reacting nickel nitrate. For example, by 10% by weight. Because baking soda is much cheaper than nitrate, which needs to be used as much as possible in the production of NiCO3.
Decompositions on hydrates and hydroxides was not examinated at heating.... :cool:

pdb - 27-11-2024 at 08:09

Solution 1
Displacing AG bicarbonate with hydrochloride
2CH7N4.HCO3 + 2HCl --> 2CH7N4.Cl + 2H2O + 2CO2
Freebasing aminoguanidine
2CH7N4.Cl + 2NaOH --> 2CH6N4 + 2NaCl + 2H2O

Solution 2
Dissolution of nickel perchlorate
NiO + 2HClO4 --> Ni(ClO4)2 + H2O

Combine 1 & 2
Complexing aminoguanidine to nickel perchlorate
Ni(ClO4)2 + 2CH6N4 --> Ni(CH6N4)2(ClO4)2

Replace the HCl with HClO4 if the chloride complex has too low of a solubility. I feel like nickel oxide is more readily available than the carbonate or nickel metal itself.

I attempted this protocol with strictly stoichiometric proportions. Solution 1 was brought to a boil under magnetic stirring. Upon adding solution 2, the solution turned gray-brown immediatly, and a greenish deposit appeared—CH7N4.Cl or what? After 5 minutes of boiling, the beaker was placed in an ultrasonic bath, which produced nothing until the temperature dropped to around 30°C. At that point, a brick-red precipitate appeared along with red needles on the surface.

In all my experiments with uNAP, I noticed that ultrasonication was ineffective as long as the solution temperature had not dropped to around 30°C. Can everyone confirm this?

Hey Buddy - 27-11-2024 at 10:58

Yes, it is supposed to be 20 C. It also is disrupted if the temp is really low, like when an ice bath is used. The target temp is 20 C and there shouldnt be any needle crystals. The appearance of needle crystals probably means the transmission of sonication is not effective. Needle crystals should be unable to form.

Axt - 27-11-2024 at 12:36

I would think the initial "green/brown" would be something more akin to a basic nickel perchlorate precipitating (not knowing anything of the properties of Ni(OH)ClO4). Did it redissolve?

How did you make the Nickel perchlorate solution? using NiO + HClO4? I've never done this, but it will go through a basic nickel perchlorate intermediate if it works.

Are the successful ultrasonicated precipitates using the bare solution or immersing a beaker in the ultrasonic bath? That may be your issue.

pjig - 27-11-2024 at 20:22

Is this axt that helped developing water gels?

Axt - 27-11-2024 at 22:35

Offtopic Watergel http://www.sciencemadness.org/talk/viewthread.php?tid=3214

Ok, curiosity got the better of me this is what works and what doesn't.

The method as posted works, but the problem is you cannot use the stoichiometric quantity to dissolve the NiO, it's just too hard to get in solution even when run hot and concentrated. I was left with a lot of NiO unreacted. Taking the prep to the end, pouring in the NaOH resulted in an immediate dump of the brick red precipitate but heavily contaminated with oxide.

Here's the better way,

Use the total acids needed to dissolve the NiO, this provides the excess needed to get the NiO into solution.

1.5g (0.02mol) nickel oxide and 11.5g (0.08mol) 70% perchloric acid in 20ml water.

Heat with stirring on 150 degree hotplate (solution temp 75 rising to 90) until a slurry with no black oxide left. Dilute and redissolve with 50ml water for a clear emerald green.

Add 5.44g (0.04mol) aminoguanidine bicarbonate in 50ml, this will neutralise with the excess acid, you've now a dirty green solution of Ni(ClO4)2 and 2CH6N4.HClO4 in 100ml water.

A slight excess 3.74g (0.05mol) 25% ammonia is added, it turns dark purplish blue.

If left stand Ni(CH6N4)2(ClO4)2 precipitates out as brick coloured needles. This takes maybe 10 minutes. Use NaOH instead and its instant and less controllable. Mixing was all done at room temp.

pdb - 28-11-2024 at 02:35

This time, the precipitation of uNAP took only 5-6 minutes with ultrasound. After filtration, I observed something I’ve noticed before: if the washing with water is prolonged too much, the precipitate develops a gray film within a few minutes. I suppose this is the decomposition by water mentioned by others? I don't have any IPA on hand; I need to get some.

[Edited on 28-11-24 by pdb]

Hey Buddy - 28-11-2024 at 07:52

This time, the precipitation of uNAP took only 5-6 minutes with ultrasound. After filtration, I observed something I’ve noticed before: if the washing with water is prolonged too much, the precipitate develops a gray film within a few minutes. I suppose this is the decomposition by water mentioned by others? I don't have any IPA on hand; I need to get some.

[Edited on 28-11-24 by pdb]

Yes

Comparison of uNAP with other primary explosives

pdb - 6-12-2024 at 04:39

First of all, I must say that so far I have not been able to observe DDT with samples of a few milligrams (< 5 mg): all I get is a "noisy deflagration," with no mechanical effect on the aluminum foil. DDT requires slight confinement or a dose of around ten milligrams.

Next, I conducted my usual comparison test with two other primaries: a rubber tube 5-6 mm in length is glued to the surface of a 1 mm thick aluminum sheet, then filled with 40 mg of primary compacted by hand. A small pellet of NC is used to seal the tube and transmit the flame.

The last three pictures show the result: on the left, AgN3; in the middle, uNAP; on the right, nitrobenzenediazonium perchlorate. It seems fair to say that the first two produced similar results, which means a new, perhaps different, test will be needed to distinguish between them. And as usual, nitrobenzenediazonium perchlorate takes the crown.

Based on this test (which would need to be repeated for confirmation), uNAP could be an interesting alternative to AgN3 because it has similar power but reportedly lower sensitivity according to comments in this thread (I have not personally tested its sensitivity). However, AgN3 has the advantage of high bulk density.

Laboratory of Liptakov - 6-12-2024 at 08:22

I see a lot of work done in the field of primary perchlorates. Of course, a weak aluminum foil is a meaningless test. Because, for example, an activated mixture of Pb(NO3)2 + Pb(H2PO2)2 (1:1) can tear the foil to pieces with just one small grain of 1 mg or less. But the initiation effect of this mixture in a detonator does not work even at 100 mg.
For this reason, your test on a 1 mm aluminum sheet + 40 mg of primary substance is important. The results look relevant. If your nitrobenzenediazonium perchlorate (NBDP?) had an easier preparation (and availability of precursors) than uNAP, it would be a miracle in the field of primary perchlorates.....Hats off once again for the work done....... :cool:

pdb - 6-12-2024 at 09:04

If your nitrobenzenediazonium perchlorate (NBDP?) had an easier preparation (and availability of precursors) than uNAP

In fact, its preparation (diazotization using NaNO2) is easier than that of NAP; the real difference lies in the difficulty of obtaining or synthesizing the precursors HClO4 and 3-nitroaniline. By the way, when I first mentioned it in 2003 on RS, I named it DPNA after its french name (diazoperchlorate de méta-nitroaniline). At least it's a bit easier to pronounce than NBDP ;-)

Hey Buddy - 6-12-2024 at 21:45

First of all, I must say that so far I have not been able to observe DDT with samples of a few milligrams (< 5 mg): all I get is a "noisy deflagration," with no mechanical effect on the aluminum foil. DDT requires slight confinement or a dose of around ten milligrams.

Next, I conducted my usual comparison test with two other primaries: a rubber tube 5-6 mm in length is glued to the surface of a 1 mm thick aluminum sheet, then filled with 40 mg of primary compacted by hand. A small pellet of NC is used to seal the tube and transmit the flame.

The last three pictures show the result: on the left, AgN3; in the middle, uNAP; on the right, nitrobenzenediazonium perchlorate. It seems fair to say that the first two produced similar results, which means a new, perhaps different, test will be needed to distinguish between them. And as usual, nitrobenzenediazonium perchlorate takes the crown.

Based on this test (which would need to be repeated for confirmation), uNAP could be an interesting alternative to AgN3 because it has similar power but reportedly lower sensitivity according to comments in this thread (I have not personally tested its sensitivity). However, AgN3 has the advantage of high bulk density.

I haven't experienced any of the problems or difficulties you have experienced in prep or use of NAP. I don't know what the differences are due to. There must be some difference. I have been making the material regularly for more than a year. I participate in a group, it is popular there. I know maybe 5 or so people that use NAP variants in that group. They don't have any differences in their product. There is no instance of deflagration in my experience. I think there is something different in your product that is drastically changing results. There shouldn't be any deflagration at all. It detonates aggressively on the slightest touch above 270 C. It repeatedly transfers detonation in only a few hundred micrograms. I produce small 1 g batches regularly. They are always the same.

Axt - 7-12-2024 at 07:02

I'm guessing pdb is referring to a loud POP as "loud deflagration"? as that's what I get if it's directly ignited. There is very few things more vehemic than the diazonium perchlorates to direct ignition.

Lab is correct though, there is no test that I know of that predicts initiating efficiency short of hitting it with the spit of a fuse in a detonator. Cyanuric triazide shown is a potent initiator but the feeblest when just ignited (although generally it melts a bit before ignition causing detontion, not in this case), and I trust the reports about NAP.

Here's a couple vids, the sound on the digital cam is muffled it's much louder in person but you can tell the difference between a fffp a pop and a snap, these were all 5mg. The diazonium salts were recorded 20 years ago on an old analogue tape recorder it had much better sound.

[Edited on 7-12-2024 by Axt]

Attachment: CTA DPPE NAP compress.mp4 (6.4MB)
This file has been downloaded 181 times

Axt - 7-12-2024 at 07:05

Diazonium salts as comparison.

Attachment: diazonium-salts_704x576.mp4 (3.6MB)
This file has been downloaded 86 times

Hey Buddy - 7-12-2024 at 12:55

I'm guessing pdb is referring to a loud POP as "loud deflagration"? as that's what I get if it's directly ignited. There is very few things more vehemic than the diazonium perchlorates to direct ignition.

Lab is correct though, there is no test that I know of that predicts initiating efficiency short of hitting it with the spit of a fuse in a detonator. Cyanuric triazide shown is a potent initiator but the feeblest when just ignited (although generally it melts a bit before ignition causing detontion, not in this case), and I trust the reports about NAP.

Here's a couple vids, the sound on the digital cam is muffled it's much louder in person but you can tell the difference between a fffp a pop and a snap, these were all 5mg. The diazonium salts were recorded 20 years ago on an old analogue tape recorder it had much better sound.

[Edited on 7-12-2024 by Axt]

I've tried to explain the crystal size makes a large difference in performance of NAP. Using standard crystal NAP will always give a lower performance, it isnt the ideal morphology. This is the purpose of the use of the ultrasonicator. It precipitates nano crystals. They have entirely different performance and sensitivity than standard NAP. They are practically different materials.

Attachment: NAP vs uNAP.mp4 (7.3MB)
This file has been downloaded 88 times

pdb - 7-12-2024 at 15:07

@Hey Buddy: the initial difficulties came from the fact that NiCO3 is not common in my country, whereas NiO is readily available. So, I ordered oxide, and while waiting for delivery, I conducted tests using impure NiCO3 because the synthesis from Ni(NO3)2 and NaHCO3 apparently produces a mixture with hydroxide and basic carbonate. I also wanted to use NH4OH, as others in this thread have done, instead of HClO4.

From now on, I use the cold method with NiO, HClO4, and NaOH to neutralize the acid and induce precipitation under ultrasound. The yield is around 55%.

The product obtained, which seems to have the characteristics of the uNAP described by other members (first pic -length of pic is about1.5 mm), does not exhibit DDT for quantities of at least up to 5 mg. This is demonstrated in the attached video.

10 mg are weighed on aluminum foil (with a 5 g tare for better balance precision). Then, the material is divided into 3 charges by hand and eye estimation: each pile should weigh between 2.5 and 3.5 mg. They are then ignited one by one. The photo shows that after unfolding, the aluminum foil is not pierced anywhere.

The last sequence in the video shows the same test with a DPNA charge, estimated to be between 0.5 and 1 mg.

I don’t see an explanation for the absence of DDT. In your video, do you get the same effect with direct flame contact?

Attachment: 3 x uNAP + 1 x DPNA.mp4 (5.7MB)
This file has been downloaded 79 times

Hey Buddy - 7-12-2024 at 17:03

I don’t see an explanation for the absence of DDT. In your video, do you get the same effect with direct flame contact?

It is common for primary explosives to not detonate from open top heat. I think bottom heating is a higher resolution examination of a material in minimum mass DDT capability. Closer to as it would be when confined in a device during actual use. There are tetrazoles that wont detonate on open top heat. Bottom heating reveals the minimum mass necessary to cause a detonation transition. Some materials are incapable of detonating by bottom heat in low mass, and so it is a useful comparison. The Al foil is useful as a witness medium because it is resilient to perforation unless a detonation takes place at such small mass.

pdb - 8-12-2024 at 01:47

Quote: Originally posted by Hey Buddy

I think bottom heating is a higher resolution examination of a material in minimum mass DDT capability.

OK, so the explanation lies in the testing method. Although the bottom heating test is widely used on this forum, in my opinion, it is biased for evaluating DDT. Heating samples of different energetic materials to their explosion temperatures will result in detonation much more often than if they were exposed to a flame.

I’m not saying this test should be abandoned, but there should at least be a distinction between h(eat)DDT and f(lame)DDT. In this case, uNAP exhibits hDDT but not fDDT, unlike some other primaries. However, these differences no longer matter when the charge is confined, as in a detonator.

Laboratory of Liptakov - 8-12-2024 at 02:27

A clear example is ETN, which ignites and burns with a long, narrow flame when heated from above. It almost always detonates when heated from below on alu foil.... :cool:

Hey Buddy - 8-12-2024 at 08:07

We are discussing two different examinations of a material with different purposes for the types of examinations.

Top and bottom heating are two ways to examine the response in a material to heat stimuli. Most materials (primary and secondary explosives), show a different behavior depending on the way they are exposed to the heat stimuli.

In regards to top heating, it is a better method to use an ember from the end of a wooden punk or a hot wire, with small surface area rather than a gas pressure torch flame that can move or throw the material. Gas torches also have a range of temperature depending on the distance of the material to the heat source and the speed at which it is introduced to the heat. A burning ember transfers no heat until it is very close to the material, so it is more of consistent way to probe with heat. A burning ember is a closer analogue to the spit of a fuze or hot bridgewire. The configuration of the material when exposed to top heat affects its behavior to stimuli response. There is still a minor confinement effect going on beneath the material where it sits on the medium being heated from above. If the material is pushed down into a depression even slightly, it affects the response again. If the material is enclosed like in a tube or a washer, it affects the response further.

So top heating can be used to compare responses between materials as long as testing conditions are constant, but shouldnt be compared to bottom heating, or used as the determination of the minimum masses to detonate a primary explosive. It is more accurate (IMO) to test minimum detonating masses on a foil where their ability can be witnessed, or even better, as they are loaded into a device, such as a detonator.

The behavior of a material exposed to top heat doesn't have much correlation to how it will behave when presented to the end of a fuze spit or bridge wire while confined in a detonator body. Top heating can't reveal minimum firing masses because materials will sometimes not detonate from top heating, but the same material will detonate and transfer detonation to a secondary, if the same mass were loaded into a detonator.

Bottom heating (can potentially) reveal the minimum possible mass that will result in a detonation of a material. In this case, Foil or another medium is only used to verify detonation is taking place. When the mass becomes so low that it no longer detonates, it will no longer perforate a foil. By comparing materials in the same way, their minimum detonation masses can be evaluated.

Secondary explosives can be examined in the same way to approximate their minimum critical diameters. Such as ETN. Even if a secondary doesn't detonate from heating but merely decomposes or deflagrates, it will usually reveal different response between top and bottom heat.

I hope that long response makes more clear my opinion. You can use any tests, to any standard you want. This is just the way I do it, or that I think about the matter. Ultimately, these are only preliminary examinations. In application, they have to be validated in the particular detonator designs they are intended for. The detonator design, particularly the interface from heat stimuli to primary, and interface from primary to secondary, dramatically influences the behavior of the detonator.

Attachment: iNAP_Ember_Response.mp4 (2.6MB)
This file has been downloaded 102 times

[Edited on 8-12-2024 by Hey Buddy]

pdb - 8-12-2024 at 11:31

I hope my reply will be shorter....

I fully agree that a burning splinter disturbs the sample less than a blowtorch jet. But in this specific case, I just wanted to make a quick video showing behaviors I was already familiar with, hence the faster choice of using the blowtorch I had on hand. Using a burning splinter wouldn't have changed the demonstration.

Besides, this is just a hobby for me, and one that I've pursued for a long time. The xNAP interests me as a curiosity, not as a means to make detonators, as I already have my own recipe for those. So, I'm not trying to make any elaborate correlations between these tests and xNAP's suitability for detonator compositions.

In fact, I limit myself to comparing primaries based on two criteria: their fDDT and their power (dent in a metal plate). Nothing else (except, of course, safety and storage), and that’s enough to keep me entertained.

Hey Buddy - 8-12-2024 at 12:20

I hope my reply will be shorter....

I fully agree that a burning splinter disturbs the sample less than a blowtorch jet. But in this specific case, I just wanted to make a quick video showing behaviors I was already familiar with, hence the faster choice of using the blowtorch I had on hand. Using a burning splinter wouldn't have changed the demonstration.

Besides, this is just a hobby for me, and one that I've pursued for a long time. The xNAP interests me as a curiosity, not as a means to make detonators, as I already have my own recipe for those. So, I'm not trying to make any elaborate correlations between these tests and xNAP's suitability for detonator compositions.

In fact, I limit myself to comparing primaries based on two criteria: their fDDT and their power (dent in a metal plate). Nothing else (except, of course, safety and storage), and that’s enough to keep me entertained.

Understood. I always appreciate your work. I am referencing your R Salt paper you translated in another project right now. --I did not intend to frame your research but share what I think about the topic of testing procedures. I assumed the response was invited. Apologies if out of line.

Axt - 9-12-2024 at 10:05

I'm just reiterating and reaffirming the discussion on page 7-8 here but I tried ultrasound and 800rpm precipitation. If anything the stirred solution was slightly but negligibly smaller, I was rooting for the ultrasound as I like the novel but at least in this setup (ie. 100ml beaker placed in the bath) it doesn't seem worth the trouble. It would be interesting to try it with other precipitates though like NTO which shows very different crystal forms.

Etanol - 10-12-2024 at 00:34

Quote: Originally posted by Hey Buddy

Hmm, I'm also used to evaluating DDT using the upper heating.
I repeated the tests with my NAP (without ultrasonic), which detonated from 15-20 mg at top heating.
I have to admit that with this method of testing (bottom heating), weighing less than 0.5 mg seems to be detonated. Less than 0.5 mg of the NAP makes a dent on 0.1mm aluminum foil or a hole in the 0.015 mm foil.

[Edited on 10-12-2024 by Etanol]

pdb - 12-12-2024 at 08:44

Inspired by Axt's experiments, I wanted to see what strong stirring would do during the synthesis of DPNA in a diluted solution. By pushing my stirrer to its maximum, 1200 rpm according to the manufacturer, I obtained a reduction in crystal size, but no change in their needle form. This is nothing like the sand-like grains obtained with a very concentrated solution, which have the advantage of forming a free-flowing powder that is less sensitive to mechanical stimuli compared to the needle version.

Axt - 12-12-2024 at 09:46

You should have revived the old diazonium topic for that pdb, but I like how you got it free flowing I remember that being an issue back then. Mine was always the matted needle clumps.

What microscope are you using pdb? Mine struggles with reflected light images, it's a celestron pentaview. I'm not sure if it always struggled, I cannot remember but it seems to be a software issue with the auto camera settings.

Bringing things back on topic here's an image of NAP from one of them cheap digital microscopes you see all over ebay and aliexpress. I used vantablack as background on a slide, I thought it would be blacker but I like the slight shadow as it gives it depth.

pdb - 12-12-2024 at 13:33

Very beautiful image! In my opinion, with similar power, color and crystallography must have their say when collecting primaries...

I use a cheap Bresser microscope with poor lighting.

Hey Buddy - 12-12-2024 at 22:12

You should have revived the old diazonium topic for that pdb, but I like how you got it free flowing I remember that being an issue back then. Mine was always the matted needle clumps.

What microscope are you using pdb? Mine struggles with reflected light images, it's a celestron pentaview. I'm not sure if it always struggled, I cannot remember but it seems to be a software issue with the auto camera settings.

Bringing things back on topic here's an image of NAP from one of them cheap digital microscopes you see all over ebay and aliexpress. I used vantablack as background on a slide, I thought it would be blacker but I like the slight shadow as it gives it depth.

This is what Im using, a cheap chinese "1500x" product. Your images are lot better than what I could produce. I would be curious what an iNAP image would look like on your equipment.

[Edited on 13-12-2024 by Hey Buddy]

Axt - 13-12-2024 at 00:36

Quote: Originally posted by Hey Buddy

To clarify the 6 picture montage above was taken on the celestron pentaview, only the pic directly above was on the cheap "1500x" scope, with emphasis on the quotation marks. They of course aren't 1500x unless you count opening it in an image editor and zooming into a few pixels. The montage pics are all at 40x, if you zoom in too far everything starts looking the same and you cannot see an average size.

I had a look back through the first pages of this thread. I wouldn't be able to directly replicate what you are doing, at least not without too much hassle. Perchlorate salts and nickel carbonate aren't available on this side of the world.

I guess there's 3 things that come to mind that could be going on in order of likelihood. 1] It's purely modifying the crystal morphology into something less sensitive, its well known that small changes in morphology can have a dramatic effect on sensitivity. 2] It's oxidising the alcohol to acetone and creating a hydrazone derivative by condensation with the AGu C-NH-N=C(CH3)2, partially replacing the AGu ligands. 3] IPA is able to outweigh the dilute AGu and replace part of the ligands. Alcohols can form ligands and Ni(EtOH)6(ClO4)2 is a known complex but this is very unlikely in aqueous solvents.

MineMan - 18-12-2024 at 16:12

Why no love for the copper QN diperchlorate? It only DDTs when confined, according to reports and is also less sensitive according to reports but actually more brisant when confined.

During the reaction could copper oxide form making it more sensitive?

I am just shocked that primary is not getting more attention as the synth states it is done at room temp and immediately precipitates. A user posted a few years ago showing it was more brisant than NAP.

I wonder if CAP could also be made uCAP, or not because it precipitates quite quickly according to reports.

One advantage is since it needs confinement to detonate, it would be safer for researchers to handle as any stray ignition will allow 1 gram to deflagrate in an open cup instead of detonate like NAP, potentially saving a hand.

Laboratory of Liptakov - 19-12-2024 at 05:34

Mineman and I have the same opinion in terms of the properties of primary substances. That is, for an amateur researcher it is more advantageous (much safer) to use deflagrating primary substances in air. Which are detonatable only in a closed metal cavity. Other researchers prefer instantly detonating substances in paper or plastic cavities. It is a matter of opinion.
One camp is researchers who do not mind storing instantly detonating substances. Where 1g can cause permanent hearing damage. The other camp is researchers who refuse to store even 1g of such a substance. That is me, MineMan, and we are certainly not alone in this opinion. After 1 month of storing 0.1g of SA-DS, I disposed of this popular substance. I could not accept the fact that I was storing an instantly detonating primary substance. From this fact arised CHP, Lithex, Cu8 and others substances. .... :cool:

MineMan - 19-12-2024 at 10:01

Mineman and I have the same opinion in terms of the properties of primary substances. That is, for an amateur researcher it is more advantageous (much safer) to use deflagrating primary substances in air. Which are detonatable only in a closed metal cavity. Other researchers prefer instantly detonating substances in paper or plastic cavities. It is a matter of opinion.
One camp is researchers who do not mind storing instantly detonating substances. Where 1g can cause permanent hearing damage. The other camp is researchers who refuse to store even 1g of such a substance. That is me, MineMan, and we are certainly not alone in this opinion. After 1 month of storing 0.1g of SA-DS, I disposed of this popular substance. I could not accept the fact that I was storing an instantly detonating primary substance. From this fact arised CHP, Lithex, Cu8 and others substances. .... :cool:

CAP, according to reports will detonate in a plastic cavity, even in 20mg quantities. But open in the air or a jar, it has been reported that even 1 gram deflagrates. The question is could it be made into uCAP, would need someone’s opinion like micotek. From the pictures I saw the grains look like small sugar. Maybe .1mm. The color of beauty rivals NAP.

But yes that is my philosophy LL, and not only for researchers but industry as well, why not be as safe as possible, when it is easy??

Microtek - 20-12-2024 at 14:44

I experimented a little with CAP, but found that it lost its potency over time. It may be that it was improperly dried or that some impurity made it less storage stable, but I never investigated further. Then I got distracted by the carbohydrazide complexes.

Explosive Socks - 20-12-2024 at 14:59

Hello
I'd be grateful for some sources for CAP synthesis
I'm having trouble finding the abovementioned topic about CAP
Thank you gentlemen

Etanol - 20-12-2024 at 15:27

Quote: Originally posted by Explosive Socks

Hello
I'd be grateful for some sources for CAP synthesis
I'm having trouble finding the abovementioned topic about CAP
Thank you gentlemen

Apparently, this refers to copper-aminoguanidine-perchlorate complex.
Analogy Nickel Aminoguanidine perchlorate (NAP) =>Copper Aminoguanidine Perchlorate (CAP).
The copper complex is dangerously unstable and for this reason cannot have practical application.
It decomposes with the release of nitrogen in hot water.
Violet substance is not a CAP, but mainly an intermediate product of the decomposition. Next, the decomposition occurs to yellow copper monoxide.
Even if it is possible to synthesize the CAP in a cold solution, based on its thermal instability, it can spontaneously explode when drying or storage.
The problem of this substance is a combination of Cu(2+) and -N-NH2, not anion ClO4- or IO4-.

Thank you. But apparently this is Fake. Copper aminoguanidine perchlorate cannot exist.
When trying to synthesize, aminoguanin perchlorate slowly oxidizes copper perchlorate in a Cu2O in an hot acidic environment and instantly does this in a slightly alkaline environment.

[Edited on 20-12-2024 by Etanol]

Hey Buddy - 20-12-2024 at 17:57

Quote: Originally posted by Explosive Socks

Hello
I'd be grateful for some sources for CAP synthesis
I'm having trouble finding the abovementioned topic about CAP
Thank you gentlemen

The author of this granted permission to share:

"...I performed the copper synthesis, and even though it doesn't posses the performance of the nickel variants, I would argue it is the easiest of them all to make (with the exception of the precursor copper perchlorate, which I want to share a simple method of manufacture with (since I already had ammonium perchlorate)).

How I make ACP and the copper perchlorate for it.
To make the copper perchlorate: I used electrolysis. I made a divided cell using a terracotta pot to hold the anodelyte, in it is 200ml of distilled water, 35g NH4ClO4 (all mixed together beforehand), and of course a copper pipe for the anode. For the cathodelyte, I simply used epsom salt, dH2O, and a stainless steel cathode. Run the cell for 5 hours at 1.5A.
At this point there is a nice solid blue solution in the pot, filter it to get any particles out, and you're left with a roughly 16% (estimated) solution of copper perchlorate.

Now for the ACP:
Measure out 12g of the copper solution made above, put it aside.
Measure out 1.5g of aminoguanidine bicarbonate, make sure the material is as fine as possible (no clumps, moves freely) add to this 10g of distilled water, and stir well.
Now add the measured out copper solution to the AGBC solution (while the still stirring), start a timer. (all done at room temp)
At the end of 5 minutes, pour the solution thru a coffee filter, then rinse it a couple times with some IPA to cleanse any unreacted material and rid most of the water.

THe resulting crystals are tiny, dark violet, pour very well, but I don't press them, merely put them in the end of a plastic straw initiated with an electric match. In the open the powder just tends to burn, but with slight confinement, it will DDT. I've been using between 50-100mg..."

MineMan - 20-12-2024 at 19:49

Quote: Originally posted by Explosive Socks

Hello
I'd be grateful for some sources for CAP synthesis
I'm having trouble finding the abovementioned topic about CAP
Thank you gentlemen

[Edited on 20-12-2024 by Etanol]

Do you have a source on this? Because it is not noted in the paper too which I unfortunately do not have a link on.

MineMan - 20-12-2024 at 20:05

I can’t find the post via the search engine. But someone in the last 5 years did a sand crush test of NAP vs CAP and CAP came out on top with higher brisance. I believe they also compared the sensitivities. Does anyone remember this post, I want to say it was twell, but maybe he just showed interest in these compounds.

I remember LL commenting on how it was a quality well done test.

I thought it was stand alone post, but maybe in a topic.

Laboratory of Liptakov - 21-12-2024 at 01:25

Let me remind you that if you already have Cu(ClO4)2, it is enough to mix it with 20% hexamine. This will give you a high-performance substance designated as LL8. Later designated as Cu8. Hexamine is certainly more accessible than aminoguanidine carbonate. However, for research purposes (in the sense of basic amateur research), CAP or NAP is just as interesting as Cu8.
http://www.sciencemadness.org/talk/viewthread.php?tid=158259
:cool:

[Edited on 21-12-2024 by Laboratory of Liptakov]

Laboratory of Liptakov - 22-12-2024 at 13:44

Damn.....All the videos from the DUG channel are gone. There were nice tutorials on NAP and also on R - salt and much more. Too bad. But that happens sometimes with chemistry channels on YouTube.
https://www.youtube.com/@duganashley1337/featured

underground - 22-12-2024 at 14:44

https://odysee.com/@DuganAshley:e?view=content

Damn.....All the videos from the DUG channel are gone. There were nice tutorials on NAP and also on R - salt and much more. Too bad. But that happens sometimes with chemistry channels on YouTube.
https://www.youtube.com/@duganashley1337/featured

Laboratory of Liptakov - 23-12-2024 at 01:59

Thanks for the link, Underground. Unfortunately, the videos on this platform are almost worthless to me. Automatic translation doesn't work there.

ManyInterests - 24-12-2024 at 20:45

I am going to make my PbO2 anode tomorrow (everything is ready, I hope nothing goes wrong) to make perchlorates so I can have a steady supply of very pure ammonium perchlorate, but given just how cold it is outside I don't think I can do an electrolysis at the moment, this means I need to improvise to get this out of the way.

I got 20g of lithium perchlorate in order to make Lithex, but I learned that I can make ammonium perchlorate from it using ammonium carbonate. So I used 5g of my LiClO4 to make 2.8g of ammonium perchlorate (I made some mistakes) that should be pure enough for anything.

I will be trying again for uNAP. I will try Dug's formula as is before doing anything else since I am certain that my previous attempt failed was due to impurites of my ammonium perchlorate. Right now I am very confident in this perchlorate for it to work properly.

If anything else happens... I will have to try alternatives.

Laboratory of Liptakov - 25-12-2024 at 02:00

Follow procedure when preparing Lithex. Stainless steel flat pan (absolutely clean), stainless steel planchet, temperature 150 - 155 Celsius. Never use teflon... :cool:

ManyInterests - 6-1-2025 at 19:24

And I finally did it a second time. This time I do believe my ammonium perchlorate was pure enough to have a noticeable reaction difference. I also barely (and I mean BARELY) had any nickel carbonate left over to the point where I wasn't sure even if decanting was necessary since I only saw a singular speck of green.

I ultrasonicated it for 10.5 minutes. The temp rose from 20C to 32C during that time, but it looks like amazing. I love it! I really, REALLY hope I got a working product this time around.

ManyInterests - 7-1-2025 at 08:24

It failed. I tried to light some up on aluminum foil and it didn't detonate or even burn. I used a jet lighter to generate more heat and it failed the same way my first batch did.

I honestly am at a loss as to what is going wrong. The ammonium perchlorate IS pure this time. Why it is failing is beyond me. I will need some help...

Edit: I looked up the ultra sonicator frequency. It might be in 40kHz and not 42kHz. I am not sure if the difference is what is causing the problem... but at any rate I think I might want to try the iNAP method instead of ultrasonication. The energy output is not the same, but with 50 or 100mg loadings that should still be effective.

At any rate, I have nothing to lose by trying iNAP.

[Edited on 7-1-2025 by ManyInterests]

Microtek - 7-1-2025 at 10:07

Have you used other methods to succesfully make NAP?

ManyInterests - 7-1-2025 at 10:50

I wasted no time in trying again with iNAP. I used a the same proprotions (0.86g of ammonium perchlorate, 1g of aminoguadine bicarbonate, and 0.43g of nickel carbonate) and around 40ml of isopropyl alcohol (91%) that I brought to a boil first then added everything and I boiled with strong stirring in a mostly sealed borosilicate jar for 5 minutes and 15 seconds.

As you can see, there were some chunks of unreacted nickel carbonate that I removed (I had powdered the carbonate earlier by hand). Maybe one issue is that the mixture as I added it were mostly apart in chunks and not 100% powdered. But they all dissolved over time (the aminoguanadine was in hard chunks that I broke up with a dowel afterward in the same cup.

But there is a lot more unreacted nickel carbonate than I thought. Maybe 0.43g is far too much of an excess?

ManyInterests - 7-1-2025 at 12:48

I had waited for several hours to try a little... and it does not appear to have any result.

Maybe it is not my ammonium perchlorate. I am realy, really curious as to why it is failing consisently in such abysmal ways. I am at a loss. I did everything exactly as specified but still not even a slight burn?

Edit: I am really baffled as to what is wrong.

[Edited on 7-1-2025 by ManyInterests]

Etanol - 7-1-2025 at 13:56

I ultrasonicated it for 10.5 minutes. The temp rose from 20C to 32C during that time...

Edit: I looked up the ultra sonicator frequency. It might be in 40kHz and not 42kHz. I am not sure if the difference is what is causing the problem...

It doesn't matter.

Ultrasonic is not a magic wand. This will not force a reaction to proceed that cannot proceed due to low temperature and/or low solubility of the reactants.

Try replacing isopropyl alcohol with ethyl alcohol or increasing the water content in the mixture of isopropanol and water. The temperature should not be below 90-100 degrees! If the mixture contains carbonate, this is an indispensable condition. Until the carbonate of aminoguanidine and nickel has decomposed into carbon dioxide, NAP will not form.

[Edited on 7-1-2025 by Etanol]

ManyInterests - 7-1-2025 at 14:43

So let me write the steps according to your instructions to make sure I understood you.

1: mix the components and make sure they're as finely powdered as possible
2: Get a 70% isopropyl alcohol solution and not 91%. It must be at a rolling boil before anything else is done and heat is at maximum at all times.

If water is used instead, it also must be at a rolling boil at all times.

3: after boiling, keep it covered and let it boil until all the reaction is done. Well over 5 minutes, and the cover cannot completely tight, it must allow some air to get out to let the CO2 leave.

after that, it is decant and ultrasonicate (if making uNAP) or just pour on a coffee filter to dry out (if iNAP).

How much time do you believe it would need to be boiling? 10 minutes? 30 minutes?

[Edited on 7-1-2025 by ManyInterests]

Etanol - 7-1-2025 at 18:28

1.ok
2.ok
3.ok +If possible, turn on the ultrasonic in the 3rd step. This will accelerate the dissolution of nickel carbonate.

How much time do you believe it would need to be boiling? 10 minutes? 30 minutes?

15 ... 90 minutes. It depends on many factors. Keep the solution in a boil until most of nickel carbonate is dissolved and the solution becomes red-black.

4.Filter a hot solution to remove the rest of the nickel carbonate.

5.Evaporation the hot solution to a concentration of about 10%.

6.Turn on the ultrasonic again and cool the solution to 0C.

7.Filter NAP.

[Edited on 8-1-2025 by Etanol]

ManyInterests - 7-1-2025 at 19:10

So it will be for a uNAP since iNAP does not call for ultra sonication. So I will update my steps (I am autistic and I prefer to have everything in a step-by-step format as it is easier to follow), and I will do it with a water solvent... unless you also want to ultrasonic the iNAP...

1: Measure the components, mix, and grind as finely as possible. Set aside

2: Measure out around 25ml-30ml of distilled water (for the 1:0.86:0.43 proportions).

3: Bring the water to a boil, once it is at a boil, start the stirring and dump all the ingredients in at once

4: Cover the jar, but let it be a little loose as to allow some steam to leave.

5: Keep the boil and stirring for a minimum of 15 minutes, the main thing to look for is the color and the dissolution of the nickel carbonate.

6: Decant and heat again uncovered to evaporate the solution further

7: ultrasonic it. Around 10 or 15 minutes?

8: cool down to 0C

9: filter out the final product and let it dry.

Am I on the right track?

Microtek - 7-1-2025 at 23:39

I think the best change will be to replace the NiCO3 with a soluble nickel salt. If the carbonate sometimes works for producing NAP it is DESPITE being a really bad choice. I simply cannot believe that you don't have access to any acid (HCl or H2SO4 or HNO3) that will dissolve the carbonate. Also dissolve the aminoguanidine bicarbonate in acid (don't use more acid than the stoichiometric amount for either of the dissolutions).

Etanol - 8-1-2025 at 01:38

7: ultrasonic it. Around 10 or 15 minutes?

8: cool down to 0C

Step 7 and step 8 are simultaneous.
Ultrasonic modifies the size and shape of the grains as it fall out.

I think the best change will be to replace the NiCO3 with a soluble nickel salt. If the carbonate sometimes works for producing NAP it is DESPITE being a really bad choice. I simply cannot believe that you don't have access to any acid (HCl or H2SO4 or HNO3) that will dissolve the carbonate. Also dissolve the aminoguanidine bicarbonate in acid (don't use more acid than the stoichiometric amount for either of the dissolutions).

Nickel nitrate forms a complex [Ni(AGu)2](NO3)2, but not NAP. I did it.
I think HCl and H2SO4 salts are not allowed in this synthesis.

The only use of the nickel sulfate is a two-step synthesis of the [Ni(NH3)6](ClO4)2, then its reaction with aminoguanidine perchlorate. It is important! the aminoguanidine perchlorate be prepared before adding the [Ni(NH3)6](ClO4)2, rather than attempting to prepare it from ammonia perchlorate and aminoguanidine carbonate in the presence of the [Ni(NH3)6](ClO4)2.

[Edited on 8-1-2025 by Etanol]

ManyInterests - 8-1-2025 at 03:35

Quote:

I do have nickel nitrate. I also have an ample supply of HCl and H2SO4. I can distill some HNO3 whenever I need.

But as Etanol said, it is not a viable route.

Quote:

Step 7 and step 8 are simultaneous.
Ultrasonic modifies the size and shape of the grains as it fall out.

How would I do them at the same time? I can add ice cold water to the ultrasonic cleaner and (I think, I need to confirm) that the ultrasonic cleaner is also temperature controlled that can also cool down the water. I need to confirm that. But the solution will be hot once I start the ultrasonic.

Etanol - 9-1-2025 at 05:18

I do have nickel nitrate. I also have an ample supply of HCl and H2SO4. I can distill some HNO3 whenever I need.

You can prepare Ni(ClO4)2 from NiSO4 and NaClO4 in hot ethyl alcohol:
NiSO4+2NaClO4=Ni(ClO4)2+Na2SO4
Separately, prepare aminoguanidine perchlorate by boiling ammonium perchlorate and aminoguanidine carbonate in water until carbon dioxide and ammonia no longer evolve.
Then, merge the two solutions together and adjust the acidity by adding aqueous ammonia or NAOH. NAP is formed.

How would I do them at the same time?

Gradually change the hot water in the ultrasonic cleaner to cold water, then add ice.

[Edited on 9-1-2025 by Etanol]

[Edited on 9-1-2025 by Etanol]

Axt - 12-1-2025 at 01:34

It's true that the chloride complex has as limited a solubility as the perchlorate, been there tried that. Mixing a 100mL solution of the chloride derived from 1.5g NiO results in immediate precipitation of the chloride. Precipitation from a mix of chloride and perchlorate NiCl2 ⇌ 2NaClO4 results in a precipitate with notably less explosive vehemence then the perchlorate alone.

On the other hand a complex that is precipitated from a mixed solution of nitrate and bromate Ni(NO3)2 ⇌ 2NaBrO3 is extremely vehemic, as or more so than the perchlorate. Although I say nothing of the stability/sensitivity/compatibility. Bromate is more innocuous and readily available here.

I have never tried to actually precipitate the nitrate complex alone, has anyone had experience with that?

Axt - 13-1-2025 at 06:09

I've run a few mixed salt reactions now, this is the results.

Ni(CH6N4)2(ClO4)2 ⇌ 4NaCl
When held into flame only weak intermittent pops, pretty much inert.

Ni(CH6N4)2(ClO4)2 ⇌ 4NaNO3
Deflagrates mildly on ignition, much like the pure nitrate.

Ni(CH6N4)2(NO3)2 ⇌ 2NaNO3 ⇌ 2NaBrO3
Detonates violently is tiny amounts, more vehemic than the perchlorate, only slightly less vehemic than Ag nitrotetrazolate.

Ni(CH6N4)2(NO3)2 ⇌ 2NaCl
Deflagrates mildly, only slightly less energetic than the pure nitrate complex.

Conclusion: The solubilities seem to be Bromate < Nitrate < Chloride < Perchlorate

ps. Yes I invented the word "vehemic" as there is no word in the english language to describe what I need, but I'm sure it makes sense in the context for which it is written.

pdb - 13-1-2025 at 07:35

ps. Yes I invented the word "vehemic" as there is no word in the english language to describe what I need, but I'm sure it makes sense in the context for which it is written.

Funny, where did you get inspiration from ? Because 'véhément' exists in French as an adjective, and means (talking of a person) 'Someone who demonstrates passion and great expressive and impetuous strength'.

Axt - 13-1-2025 at 09:41

Oh it is a word here too, well without the dots or dashes or whatever the fuck they are

Vehement and vehemently, but surprisingly not vehemic (see it has a red squiggly line if you type it) so it's now assigned in my mind to a compounds ability to self-accelerate to detonation unconfined.

Fulminic is the archaic term but its draws too many connotations now, being coopted by a certain acid.

ManyInterests - 14-1-2025 at 18:34

OK, so in the next few days I will be trying again. I already listed out my steps, but since you say that cooling to 0C is necessary, I found a way. Not only will I be using ice cold water (cooled to the point of just starting to solidify into ice) while ultrasonicating, what I also do is have my ultrasonicator done outside. It is a very cold outside where I live, so the ambient temperature will be helping.

As for heating it, I will NOT just the jar with a lid, I will use a beaker with a watch glass atop it, mostly covered, but it will be given the space to allow the CO2 to leave. Maybe I will be using slightly more water as I will let it boil for a full 20 to 25 minutes with strong stirring. I need to make sure it doesn't run completely dry since that can be very dangerous. letting it boil for 5 minutes didn't lose a lot of water I must say, but I never did it for 25 minutes.

Microtek - 15-1-2025 at 11:35

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.

Etanol - 16-1-2025 at 13:10

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 am glad that you succeeded. Was gas bubbles observed during synthesis? Be careful with this substance. It can present a surprise.

Microtek - 16-1-2025 at 13:43

Quite a lot of bubbling was observed since aminoguanidine bicarbonate was used as described in the patent so the carbonate was obviously given off as CO2. What do you mean about it presenting a surprise? It sounds as if you have some experience with it, but a few posts up, you said that it could not exist.

Etanol - 16-1-2025 at 23:06

Quite a lot of bubbling was observed since aminoguanidine bicarbonate was used as described in the patent so the carbonate was obviously given off as CO2.

No, I mean N2, as a sign of the decomposition of aminoguanidine.