Sciencemadness Discussion Board - Nickel aminoguanidine diperchlorate

Nickel aminoguanidine diperchlorate

Pages: 1 2 3

ManyInterests - 2-11-2024 at 21:52

You can crush up match heads and mix the powder with an acetone solution of NC to make a thick porridge. Then dip your nichrome wire in that. It works very well, and I use it when I do VOD measurements with ionisation probes and an oscilloscope. The fluffy NC ones are less labour intensive since all I need to do is to snip off a piece of wire with two leads and put one end into the 3d printed plastic cup I mentioned earlier. Then stuff in a small piece of gun cotton and insert the cup into the cap. It is then fired by a couple of batteries through a one dollar boost converter. This makes an arc from one lead to the other across the cut end of the wire.
These don't work for VOD measurements however, since the arc triggers the scope before the the CJ-zone even arrives at the first probe.

I was thinking of using ground up matches. I have a small container of match powder that I ground up a long time ago. I was thinking of water, but I didn't think of acetone. I will definitely do that. Your setup is quite interesting. What I have done is something a lot simpler. The majority of the time I use an RF module with a high voltage/amperage tolerance (up to 2A and 30V). I connect it with 24V from AAA batteries (16 in series) and very long lead wires (I don't even remember how long, but several meters) to allow a great deal of distance between the module and the charge, and the transmitter allows me to be even further away still.

But in terms of measuring effect, I just use test plates using cheap fence brackets that I get for around 40 cents a piece. I use them exclusively for both consistency sake and for saving money since other plates are just too expensive.

ManyInterests - 5-11-2024 at 17:34

OK so my nickel carbonate has arrived in the mail. As I bought it from a chemical supplier and not a ceramic company, I can probably assume that it will be quite pure, but I will need to make sure I follow all the steps.

But before I do that, I have some other projects to finish first. Such as building the press and to do a second recrystalization of my RDX to insure that all the bicarbonate and alkalinity has been removed, as it is it is quite acid free from the first recrystalization but still might have some hard to remove bicarbonates that are giving the wash water a slight alkaline quality that stays no matter how much I rinse it, hence why a 2nd recrystalization is needed (without any other stuff than hot acetone and cold crash water). As I want to make it is as clean and pure as possible for detonator test.

[Edited on 6-11-2024 by ManyInterests]

[Edited on 6-11-2024 by ManyInterests]

pjig - 6-11-2024 at 07:21

Had a quick question, slightly off topic but relevant to your statement. Process of re-crystallization of rdx (and petn alike) you describe a crash method, vs a slow crystallization of cooled down acetone. What sensitivity and purity gains or losses are to be achieved by either method. ?

Microtek - 6-11-2024 at 09:16

The RDX forms very small crystals if crash precipitated (acetones solution of RDX added to water while stirring). Larger crystals are obtained by either adding water dropwise to the acetone solution, or by cooling the hot, saturated acetone solution. In the latter method some of the RDX will remain dissolved in the cold acetone. I like the method involving water added to acetone since it allows fine control over the crystal size by adjusting the rate of addition of the water.

ManyInterests - 9-11-2024 at 14:41

Small crystals are what I am looking for, since I am going to see how I can maximize the amount of secondary I can load into my caps, and I need very small crystals for that.

Right now I am almost finished with my press setup. I am actually quite proud of it and I hope it is able to press to very high pressures. I will picture it once it is fully finished.

In terms of pressing the secondary, I am not worried about a detonation (especially with RDX) but I am still worried about the uNAP. I will need to tamp it manually before putting it on the press.

Edit: I forgot to post this yesterday. My press works, but I need to improve it. The wooden dowels are actually ineffective since they always break when I try to press them. I need a taller block to make sure that I can press on them with a metal press

Microtek - 10-11-2024 at 14:24

The size of approximately spherical particles does not affect the packing efficiency. If you want to maximize the volume fraction of secondary in your caps, you should use a multimodal powder (a powder consisting of two or more different sizes). However, there are other considerations that might make a fine powder more desirable in a cap, such as lower sensitivity, smaller critical diameter and better detonability.

ManyInterests - 10-11-2024 at 16:55

I was able to press four RDX caps and one melt-cast ETN cap to fairly high density. I will need to get a better rod and setup to hold the cap as I press. The pressure I can exert with that homemade press is considerable since I some some deformation of the cap body, but I need a better setup to hold the cap in place and a better rod that fits better into it, so that my next caps will be better. But the ones I made currently will work.

I decided that this press is too much for the primary, however, which I will load and press lightly by hand. As you said, pressure sensitivity and friction sensitivity of uNAP is minimal and I don't need to press too hard anyway. The press will work to give a much higher density to the secondaries, which is what is important.

Also I said I would use 100mg of uNAP, which is excessive, but I decided that experimenting with 25, 50, 75, and 100mg might be better to see if there is a real need to go that far with the stuff.

Microtek - 12-11-2024 at 14:10

Using more primary than strictly necessary is not a bad thing. A more assertive initiation will usually result in a better output.

ManyInterests - 16-11-2024 at 16:59

OK, I am prepping up for my first synthesis. I have the ultrasonicator and the stuff measured out. My measurements might have been mildly inaccurate, but they should still be mostly OK. the video only mentions decanting and not filtering, so I plan on scooping out the stuff after decanting.

I will still work to decant after the initial heating step even though I am using lab grade nickel carbonate. You never know. I'll post results as soon as I am finished ultrasonicating.

Edit: I am ultrasonicating it now... but some of the nickel carbonate came through... it didn't settle at the bottom. I hope it will be OK

[Edited on 17-11-2024 by ManyInterests]

ManyInterests - 16-11-2024 at 17:45

OK, first synth! Some errors were made

1: I think my ultrasonicator water was a little too warm. Either way I put in too much.
2: I didn't properly decant the nickel carbonate. It isn't due to impurity, it is something that is going to happen regardless. It didn't show like in Dugan Boomfax's video, but it is something I need to be more wary of.

That is what I have. Either way. I got... something. The yield is probably not a lot, but it is something, I hope. It is pictured below.

uNAP failure

pdb - 17-11-2024 at 07:51

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.

ManyInterests - 17-11-2024 at 08:39

Quote: Originally posted by pdb

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

Quote: Originally posted by Laboratory of Liptakov

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

Quote: Originally posted by pdb

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

Quote: Originally posted by pdb

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

Quote: Originally posted by pdb

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.

Quote: Originally posted by pdb

red needles appeared on the surface and nowhere else.

Red needles is NAP.

Quote: Originally posted by pdb

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

No. Oxygen decomposes aminoguanidine.

ManyInterests - 17-11-2024 at 16:48

Quote: Originally posted by Etanol

Quote: Originally posted by pdb

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

Quote: Originally posted by pdb

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.

Quote: Originally posted by pdb

red needles appeared on the surface and nowhere else.

Red needles is NAP.

Quote: Originally posted by pdb

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

Quote: Originally posted by ManyInterests

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

Quote: Originally posted by Axt

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

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

Quote: Originally posted by pdb

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

Quote: Originally posted by Etanol

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

Quote: Originally posted by pdb

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

Pages: 1 2 3