Sciencemadness Discussion Board - Nickel aminoguanidine diperchlorate

I tried the reaction again, but this time with stoichiometric amounts and the yield was much better (68%). The reaction also did not produce the previous unwanted side product. Still plenty of yield optimising required. One of the issues is that the product is very soluble in water so I am going to start trying some different solvents.
Strange that the patent had such an obvious error.....

That’s a good idea. Please keep us updated. From watching videos my understanding is that it is not only soluble but in time the water destroys the product and a black mass results. You don’t want that, we don’t want that, nobody, I mean nobody wants that!!!

Microtek - 24-2-2022 at 10:30

Regarding the molar ratios, remember that it bis(aminoguanidine)nickel diperchlorate so you need two moles of AQ per mole of nickel perchlorate. I don't know why you say that the product is very soluble in water, mine is not, although it does react with water.
I think maybe the AQ ligands are sufficiently labile that they are replaced (partially?) with H2O. At any rate, the complex loses the red colour and turns a pale tan that then darkens to blackish.
I looked at one of the papers that the patent references. It's about complexes of aminoguanidines and nickel, and one of the things they talk about is that some of the compounds are very readily oxidized by atmospheric oxygen. This may account for the black colouring.

[Edited on 24-2-2022 by Microtek]

B(a)P - 24-2-2022 at 14:08

Thanks Microtek that helps a lot.
I have redone my calculations based on it being (bis)aminoguanidine and can now assess my yield properly.
I had noticed when I was washing the product with water I could see crystals very quickly disappearing, I thought they were going into solution rater than decomposing, the decomposition explains why I could not get it back out of solution.
I had also read the about the oxidation by atmospheric oxygen that you reference, which I was convinced was the big killer on my yield. I had proposed to try and do the reaction in an atmosphere or argon to avoid this, but I think in the first instance I will try again with the correct stoichiometric amounts based on the product being (bis)aminoguanidine and as little water as possible.

B(a)P - 9-3-2022 at 20:32

So the rain has finally eased allowing some further testing of this product.
I don't have the means to accurately assess friction, though I have not been able to set it off using friction.
I have a crude impact tester with a 2 kg weight and the material was set off reliably from a drop height of 5 cm. For comparative purposes I get 3 cm for mercury fulminate.

400 mg was loaded into a brass cavity 4.5 mm ID with 0.5 mm walls at 1.23 g/cm³.
Fuse was inserted and packed in place with NC.
The target was 30 mm mild steel RHS with 1.5 mm walls.
The results can be seen in the attached.
I was hoping to get full penetration. I was also a bit disappointed with the density that I could achieve. More to come when I can improve the density.

Edit - corrected an error in the cavity dimensions.

[Edited on 10-3-2022 by B(a)P]

Microtek - 10-3-2022 at 02:35

When preparing this material, I recommend continuing the stirring throughout the 4 hour precipitation period. This way you get uniform small crystals rather than the relatively long needles that are usually obtained if you let it sit undisturbed. This might help with the loading density, as well as the impact sensitivity.

Laboratory of Liptakov - 10-3-2022 at 11:05

400 mg was loaded into a brass cavity 0.45 mm ID with 0.05 mm walls at 1.23 g/cm³.

400mg in cavity inner diameter 0,45 mm ....? Wall 0,05 mm...?...
It is diameter syringe needle....

...?

B(a)P - 10-3-2022 at 13:53

Quote: Originally posted by Laboratory of Liptakov

400mg in cavity inner diameter 0,45 mm ....? Wall 0,05 mm...?...
It is diameter syringe needle....

...?

Ha ha ha, good catch. If I got that performance out of that diameter I would have been very happy. The correct dimensions are 4.5 mm ID and 0.5 mm walls.

[Edited on 10-3-2022 by B(a)P]

Laboratory of Liptakov - 11-3-2022 at 07:20

Brass wall 0,5 mm and ID 4,5 mm is good result for examined compound. Into 1,5mm steel. Basic ratio between ID and thickness of steel is 3:1.
It is base for measurement. Similarly as ID 6 mm (examined compound) and 2 mm steel target. Also 3:1.... :cool:

B(a)P - 21-3-2022 at 16:00

So the rain has finally eased allowing some further testing of this product.
I don't have the means to accurately assess friction, though I have not been able to set it off using friction.
I have a crude impact tester with a 2 kg weight and the material was set off reliably from a drop height of 5 cm. For comparative purposes I get 3 cm for mercury fulminate.

400 mg was loaded into a brass cavity 4.5 mm ID with 0.5 mm walls at 1.23 g/cm³.
Fuse was inserted and packed in place with NC.
The target was 30 mm mild steel RHS with 1.5 mm walls.
The results can be seen in the attached.
I was hoping to get full penetration. I was also a bit disappointed with the density that I could achieve. More to come when I can improve the density.

This was tried again with a finer crystal size.
The same cavity dimensions, loading weight and target material were used. This time the achieved loaded density was 1.62 g/cm³. Not a lot of difference was observed in the outcome. The smaller piece on the left is loaded at 1.23 g/cm³ (previous attempt) and on the right 1.62 g/cm³. The higher density cap seemed to have slightly more penetration, though more was expected. Without some replications this can not be seen as significantly different.

MineMan - 21-3-2022 at 21:54

You should be able to get a density of 1.8-1.9.

MineMan - 21-3-2022 at 22:21

You should be able to get a density of 1.8-1.9.

B(a)P - 22-3-2022 at 01:19

You should be able to get a density of 1.8-1.9.

I pressed the nickel aminoguanidine diperchlorate to approximately 50 MPa, which is about as far as I can go with my setup. What pressure would you need to achieve that kind of density?
Obviously this depends on crystal size. I tried continuous stirring to reduce size. The only other thing I can think of is to increase the reaction temperature more rapidly, then cool rapidly to make the crystals form faster.

Microtek - 22-3-2022 at 07:02

I just tried pressing mine. I don't have a way to easily measure the pressure I'm exerting, but I would estimate perhaps 100 kg on a 7mm coloumn of NAP. This would be about 20 MPa. The density I got was 1.96 g/cc.
I'm not sure that it is advantageous to press it to such high densities however.

Are you contemplating using this material as a secondary or as a single material cap filler? Personally, I would rather fill my caps with PETN, RDX or HMX and then use 50 mg NAP to set it off. Even more preferably, I would separate the NAP (or other primary) from the rest of the explosive filler and keep it in the fuse insert.

Diachrynic - 25-3-2022 at 06:53

Regarding the synthesis, there is also this video: https://www.youtube.com/watch?v=aqdKN4KBqjM

He mentioned in a comment:

Quote:

I made that Ni 2Agu perchlorate by dissolving nickel acetate 1M and ammonium perchlorate 2M first in just enough cold (room temperature) water, added all the Agu bicarbonate 2M at once, then heated on water bath with mixing, when the max. temp reached (slightly below 100°C, the bicarbonate dissolved with effervescence), I left it for 5 minutes, then removed from the bath and left stand for a few hours. The crystals appear slowly, gradually on standing. Then filtered and washed. The whole process was not optimized. I found if a small amount of acetic acid is added, the yields were higher.

This is useful since no perchloric acid is needed, but the yields are lower, I estimate around 40-50% of the theory based on used nickel.

B(a)P - 25-3-2022 at 18:14

I just tried pressing mine. I don't have a way to easily measure the pressure I'm exerting, but I would estimate perhaps 100 kg on a 7mm coloumn of NAP. This would be about 20 MPa. The density I got was 1.96 g/cc.
I'm not sure that it is advantageous to press it to such high densities however.

Are you contemplating using this material as a secondary or as a single material cap filler? Personally, I would rather fill my caps with PETN, RDX or HMX and then use 50 mg NAP to set it off. Even more preferably, I would separate the NAP (or other primary) from the rest of the explosive filler and keep it in the fuse insert.

Thanks very much for trying the density and reporting back. I have found that I was not actually applying the pressure that I thought, as my press was bottoming out on the blast guard. After modifying the guard I have just tried again and got 2.01 g/cm³ by applying to approximately 50 MPa.
The purpose of what I am doing is just to see the effects on performance by modifying loading pressure with this compound.

Quote: Originally posted by Diachrynic

Regarding the synthesis, there is also this video: https://www.youtube.com/watch?v=aqdKN4KBqjM
This is useful since no perchloric acid is needed, but the yields are lower, I estimate around 40-50% of the theory based on used nickel.

Thanks for the link. I had not seen that video. It appears he is doing essentially the same as I posted above (first post). He makes nickel perchlorate from nickel acetate and ammonium perchlorate, then his procedure is more or less the same from then on.

B(a)P - 20-5-2022 at 13:25

I have my press guard reconfigured and now it is working perfectly. I repeated the above test, but this time managed to press to 2.01 g/cm³. Here is the result.
On a side note I have also been trying the lithium equivalent, but with no success thus far. I will report back if I manage to create anything of interest.

Laboratory of Liptakov - 20-5-2022 at 23:56

Good work, wall is 2 mm ? Inner diameter cavity 6 mm ?. If yes, it it good result..... :cool:

B(a)P - 21-5-2022 at 00:17

The target had 1.5 mm walls and the cavity is 4.5 mm ID. I note that in this instance I inadvertantly placed the detonator over the join in the RHS. In previous tests i had avoided the join.

Laboratory of Liptakov - 31-5-2022 at 22:02

It are basically same ratios. Good results. Only the variable value according to the law of proportions comes into play. When the strength (behavior) of a material varies significantly according to size. This is given by the final size of the atom and molecule... :cool:

PellePeloton - 27-6-2022 at 04:46

Just a small cautionary note: Try to avoid the smoke!

I did some work at our university with this compound (which is very nice, except for this one thing) in an ordinary hood. The quantities were 30 - 100 mg and visibly the hood was capable of sucking the smoke completely from the charges.

However, every night after the tests I had a sore throat very much like after ozone exposure. Also a minor feeling of not getting oxygen out of air... not difficulty in breathing but a strange and very unpleasant feeling.

After the third time this happened I came to think about the reaction products... the compound is ever so slightly oxygen negative, so the result is guaranteed to contain CO and metallic nickel... the nickel is atomic having the ultimate surface area, and the products cool very fast as the gas cloud expands. I have no knowledge or even estimate how much nickel tetracarbonyl is formed, but a little goes a long way.

The slight feeling of drowning lasted for a year, but is now completely vanished. I am not allergic to nickel.

B(a)P - 27-6-2022 at 19:18

Sorry to hear that this happened to you and thanks for passing on the warning. Glad to hear that you got over it eventually, a year is a long time to be suffering such symptoms. I have always worn respiratory protection when working with nickel compounds because of their toxicity. I will be extra careful after hearing this.

Hey Buddy - 1-12-2022 at 21:24

I was hoping to get some advice. Im leaning towards this nickel complex but before I commit to getting into the habit of reduction of nitroguanidine to aminoguanidium, I want to make sure there isnt a guanidium freebase complex equivalent. If there were say, Ni(Gu)3(ClO4)3 it could very well have primary explosive capability but it would negate the need to reduce nitroguanidine which would simplify precursory steps. In this hope, I will try to see if I can find something in guanidine. I have figured out the freebasing procedure as of tonight. GuNO3 is freebased in denatured alcohol by heating to 68 C and adding stoich NaOH then filtering without wash. The freebase guaniidine disappears the moment water touches it.

I was hoping someone more familiar with the guanidine salts could help me with the next part. So far I plan to use metal chloride, then mix Ammonium perchlorate/KClO4, (m)cl2, Gu in stochiometry for target compound. If KClO4 is used with chlorides then the KCL has low solubility in ethanol and acetone. I have a huge collection of metals I could try, but Im not sure about what solvent to try reaction in, or if there would be a more logical reagent? I can prepare anything, I would rather use a ClO4 salt as opposed to HClO4 because it is possible and simplified. If you have any ideas or recommendations please advise. Im on standby until I can decide the solvent and I cant decide. SHould I just use water? I have no idea what target complex solubility will be.

[Edited on 2-12-2022 by Hey Buddy]

Laboratory of Liptakov - 2-12-2022 at 02:22

Certainly there are procedures (within the investigation of xy - guanidine) that no one has tried yet. Maybe you will be able to make something useful, new, hitherto unknown. As the first in the world. But in that case, you also have to come up with a procedure. Also the first in the world. I'm afraid your question is just that case. That is, how to simplify the procedure and achieve reliable DDT without the preparation of aminoguanidine.
(I repeat again: Amateur chemists are some of the most lazy scietist)

In exept of B(a)P

I consider myself one of the laziest researchers ever. That's why I invented Lithex. Which is a primary-secondary substance designed for the biggest chemical slackers. Lithium perchlorate, hexamine and 5 drops of water are mixed in a pan. It evaporates at 175 Celsius. And substance is in the world.

[Edited on 2-12-2022 by Laboratory of Liptakov]

Hey Buddy - 2-12-2022 at 08:38

Ha, yes! But if there is a primary located in a simple guanidine, it will make everyone's life easier.
The zinc reduction of NQ is a mess and low yield where as the electro reduction on lead is much higher yield and cleaner, but requires the reduction cell be made with a diaphragm and electolyte. So this step of reduction to aminoguanidine is a bottle neck. Likewise, if you go the other direction and use hydrazine for ANQ, it is a bottleneck and the ANQ yield is relatively low with a good bit of material loss to diaminoguanidine etc.

Both directions, aminoguanidine <= and => ANQ have good primary explosive salts but take extra steps. Lazy chemists should be happy if there is guanidine primary explosive complexes. It is likely there is.

Guanidine is freed from the nitrate in 10 minutes with NaOH in alcohol and then dries quickly. I have three batches from last night. Works great, low losses. I will make some more and some metal perchlorates and waste some of it to try to find a good route. I will start with nickel perchlorate and let you know which method works if a primary explosive is found that detonates unconfined like AGuNi salt.

B(a)P - 2-12-2022 at 12:19

LL not sure if I should be offended or not?

Hey Buddy check out the patent I referenced at the start of this thread. I think it has some info relevant to what you are trying to achieve.

Laboratory of Liptakov - 2-12-2022 at 12:36

Hey Buddy, great info, thanks.....Guanidine free base is possible drying and storage...?...Good message. I am curious on any result on this field.
B(a)P.....Your holes in metal are excelent...Howgh...said Sitting Bull.

Hey Buddy - 2-12-2022 at 13:02

Quote: Originally posted by Laboratory of Liptakov

.....Guanidine free base is possible drying and storage...?..

I will make a new thread about this in pursuit of guanidium complexes from the freebase so I dont drown B(a)Ps thread with offtopic.

BaP thank you for patent advice.

Ni(ClO4)2*6H2O from NiSO4 + 2KClO4

Hey Buddy - 10-4-2023 at 07:17

I've been working on this complex recently. I have prepared Ni(ClO4)2*6H20 via double decomposition from 2KClO4 + NiSO4 heated in dH2O until dissolved. KClO4 is soluble in 100ml H2O to around 12 g @ 70 C and 22 g @100 C. K2SO4 is precipitated with saturated solutions to a small degree. The nickel sulfate dissolves easily, the limiting material is the potassium perchlorate. Minimal water is best to ease precipitation of Ni(ClO4)2 later. After all the perchlorate and sulfate are dissolved in the minimal amount of water, the solution is cooled and then ~double the equivalent volume of 90% isopropanol is added which precipitates the rest of the potassium sulfate. Remaining in solution is Ni(ClO4)2. Boiled down to minimal volume the perchlorate crystallizes out on cooling and dried. I have been using this technique on the 100g scale in 1L vessels. I was very pleased that Ni(ClO4)2 can be prepared this way because it makes use of inexpensive KClO4 as the source of perchlorate and cheap isopropanol.

I am still learning about NAP. I'm using the "improved AGu" method of reduction from SM to derive AGu. It reacts well with this nickel perchlorate to give a red reaction and the final NAP product in H2O at a 5 min boil. I have noticed that there seem to be different grades of NAP that have different sensitivity and brissance. Apparently the darker red, the greater sensitivity and brissance. The lighter red (almost a reddish orange) detonates on confinement and partially detonates unconfined but doesn't appear to detonate fully.

I have also noticed during the reaction, that a black solution forms in the reaction mixture after settling on cooling. The black mixture floats in the middle with NAP layer both underneath and above it. I have been filtering the NAP early within around 20 minutes of cooling rather than waiting the 4 hours suggested by the patent. I was afraid that this black solution would degrade the product. I'm not sure what this solution is, I think it may be a further reaction with residual water in the solution. I will try this reaction in alcohols to see if it affects yield or prevents black solution.

B(a)P - 11-4-2023 at 01:27

I have found the same thing both with the 'grades' of NAP and the black precipitate. In my experience the lower grade material you describe degrades over time while the presumably more pure material appears to be stable when stored for at least a year in a sealed container.

Solvent interaction on NAP

Hey Buddy - 12-4-2023 at 17:20

I have just tried a few tests with alcohol solvents preparing NAP. The results were interesting so I will add here.

First two images are NAP patent procedure in terms of ratios and volume but I replaced H2O with 91% Isopropanol. The mixture begins as turquoise but then changes to a red then at completion a brown black. The color change began at bp of isopropanol ~82 C.

The next four images are NAP reaction in commercial denatured alcohol solvent. The alcohol was brought to boil and there was no reaction. The volume of alcohol (11ml) reduced over 5 minutes with no noticeable reaction. More alcohol was added to replace evaporated level. And as no reaction proceeded 10ml dH2O was added which immediately initiated a reaction which then proceeded through turning tan/brown, then reddish. At the end of the reaction the (presumably) NAP separates and drops to bottom with a clear layer above. There is no black layer in this denatured alcohol method. When water is used as the solvent there is a black color in solution and when isopropanol is used the black appears to mix with the product and create a dark red/brown/black product.

Are there other solvents of interest? MeOH or Acetone?
I am also curious for other experimenters, how is the NAP coming out of solution for you? Is it dropping out immediately or forming slowly over the 4 hour sitting period? I ask this because all of my tests have resulted in immediate precipitation at conclusion of boiling. These pictures were all taken following removal from heat, Im allowing them to stand 4 hours now.

[Edited on 13-4-2023 by Hey Buddy]

Update:
I just looked at these samples again after theyve been sitting at room temp for a few hours, the 50:50 denatured alcohol/added-H2O solvent test is still free of black solution and the material is in a granular form with large grains visually. The isopropanol is a black/brown sludge.

[Edited on 13-4-2023 by Hey Buddy]

Update:
First image is comparison of the two materials on coffee filter paper. The denatured alcohol version is very granular and has homogenous color. I thought it looked kind of less vibrant color red but in the second photo you can see its actually a shade lighter and deeper red tone than a previously made sample shown in the vial. You can clearly see in the second picture the grainy consistency from denatured alcohol/water reaction. normal consistency is powder.

[Edited on 13-4-2023 by Hey Buddy]

Is this color similar to what others are finding or is this color darker or lighter?

[Edited on 13-4-2023 by Hey Buddy]

The only other colors Ive seen for comparison are the videos from energetic heretic aka tetrazole lover. Its hard to tell what saturation of hue he is getting. He has one picture that looks crazy red.

[Edited on 13-4-2023 by Hey Buddy]

UPDATE:
Its now the next morning and the samples have been dried. I tried burn tests of the samples. Again, I was surprised. The nice red color sample burns unconfined by flame underneath. It turns black. It does not deflagrate or detonate. I'm a bit puzzled as to what is going on here. Direct hot ember doesnt burn it either.

The less homogenous brown/black material from 91% isopropanol detonates ferociously in mg proportions without confinement. And also detonates confined, which is logical.

I dont know what happened. I assumed for granted the red material was very pure and the black material was contaminated. I assumed the black material would probably have performance issues. The experimental case was opposite. The black material DDT so powerfully. I think it is more brissant than samples previously made by patent instruction. It is much more powerful than SADS or lead azide. I could feel the pressure energy in my skin from a few feet away. And that is only from a small pinch. Incredible stuff.

[Edited on 13-4-2023 by Hey Buddy]

Just did a follow up test on the black material with 40 mg dropped loosely in a plastic vile, with 50% head space. The plastic vile was pressed into dirt and a fuze was inserted. Detonation was quite powerful for such a small load. I could see dirt was fired into the air and the ~40mm hole made had small shreds of plastic about the width of a fingernail clipping inside.

[Edited on 13-4-2023 by Hey Buddy]

Update:
This isopropanol NAP detonates ETN without problem and has very excellent flame DDT sensitivity. It can be detonated by direct visco contact without any prime or thermite plug such as Zn/CuO (although Im sure a prime would increase reliability). I have had no failures to DDT in fuze tests and at this time the original batch of black material is exhausted. Black NAP did not detonate a plastic vile of 15 g PETN. That test was a large plastic vile of PETN with a small 8mm vile of black NAP, side-primed onto the PETN vile with black tape. The NAP was lightly tamped in the vile. That test resulted in a failure to detonate the PETN. Im going to try to replicate isopropanol version and then scale up to 5g.

[Edited on 13-4-2023 by Hey Buddy]

Hey Buddy - 13-4-2023 at 19:54

I attempted to scale up the isopropanol method, using an equal ration of solvent but increased all portions from patent to 3x. I got a red paste this time with less isopropanol boiling off at boil. Im going to first see if this batch high-orders then try to replicate a brown/black version again, test a couple variations until I find consistency that is highest yielding and high power. Will follow up.

B(a)P - 13-4-2023 at 21:48

The colours that you are getting look ver close to what I have observed when doing this synthesis. I can also confirm that I get crystals coming out of solution as soon as it starts to cool down. In fact I have noticed that yield seems to decrease if you leave it the suggested 4 hours. I generally filter as soon as it has cooled to about room temperature. Looking forward to seeing how you go with the isopropanol.

Microtek - 14-4-2023 at 02:53

The black coloring is from decomposition of guanidine derivatives. It is one of the few drawbacks of this material that it decomposes if it is dissolved in water. For this reason there is a balance to be found between adequate time to form the complex and too much time which will degrade your product.

Hey Buddy: Please don't scale up production of primaries, even relatively safe ones such as this.

Hey Buddy - 14-4-2023 at 08:13

Hey Buddy: Please don't scale up production of primaries, even relatively safe ones such as this.

That's a sound warning. Unfortunately, it's too late for me.

--This material seems a little tricky in alcohol. I have now replicated the isopropanol brown/black sludge (I probably should not have described it that way because it is more of a dark brown/red/violet/gray, not so much black). Anyways, I was able to recreate it and in this batch, it is certainly degraded in performance. It's only partially DDTing. Not even damaging foil.

I also made an additional batch that was removed from boil (boiling in isopropanol is somewhat tricky because its boil is not obvious like water), this reaction was removed before turning dark, it is mostly red but not as vibrant red as previous batches in past. It detonated at full power. This is in contrast to the sample made earlier, which was very red, (made in denatured alcohol with H2O added after boiling). That sample is entirely inert. It doesnt DDT at all. It simply decomposes to a sooty mass over flame.

So all in all:
-NAP is extremely powerful.
-It can be made in water or alcohol, likely other solvents.
-It is sensitive to time of boil, solvent type and molar ratios of reactants.
-It's possible to make inert NAP in both dark and light red forms.
-It's possible to make NAP that detonates secondary explosives in both dark and light red forms.
-It seems likely that a red product is desirable, and a darker product is decomposition. It is possible to make red product that is inert. It's not recognized what is causing inertness in that case.
-***The black liquid typical of water solvent does not appear in alcohol solvents. This is the main difference between an H2O solvent and alcohol reactions. It isn't known if there is even a benefit of using Alcohol instead of water. Experiments of equivalent molar reactions in water and alcohol could reveal any benefit of using alcohol solvent, based on yield. It seems possible that alcohol solvent may increase yield but it needs further investigation. In this experiment, producing inert material confused results a little bit, adding another layer of mystery.

Unknown:
-Do alcohols react with complex during boil?
-Exact molar ratios for maximum product.
I tried some isopropanol experimentation with near 2x excess Ni(ClO4)2 and it increased yield versus the stoichiometric ratio.
-How much boiling is appropriate with isopropanol? Alcohol boiling is a bit subtler than H2O so it has to be removed from stirring and visually checked to identify when the boil starts. Appropriate time of boil may be less than 5 minutes for alcohols. The reaction can be removed from heat during boil to choose the time of completion based on visual color change. Reaction continues mildly for minutes when removed from heat. A quench might help stop reaction at desired color point exactly.
-It's unknown how long a darker product lasts. There are at least two reports of light red product remaining effective for a year and another over a year, so it seems red product is desirable.

I'm very satisfied with this primary. It is much more powerful than lead azide and seems to be more flame responsive. Its preparation is very efficient being a simply prepared complex. It would be interesting to see if bicarbs of AGu and Ni could be reacted with NH4ClO4 as the ClO4 ion source. That would further simplify precursors.
I like it
I ordered a few kg of AGu bicarb.

[Edited on 14-4-2023 by Hey Buddy]

H2O vs IPA

Hey Buddy - 14-4-2023 at 18:25

Everything used in the test is mirrored. The difference between the two is only the solvent. dH2O is used as solvent in one reaction, 91% isopropanol is used in the other.
Reagents used are:
1.38 g Aminoguanidine Bicarbonate .010 mol
1.85 g Ni(ClO4)2*6H2O .005 mol
15ml dH2O/91% IPA

The PID hot plates were preheated to 119 C. Stirring was set to 200 rpm and the respective reagents loaded into beakers along with solvents.
I refer to the reactions as "H2O" and "IPA" for shorthand.

1:49 The H2O begins to bubble and foam, IPA does not
2:14 H2O begins to change color, IPA remains
3:07 IPA begins to change color
3:37 Boiling is observed for H2O. 5 minute countdown started
7:14 Both H2O and IPA are very red in color
8:37 5 minute countdown complete, H2O and IPA removed from heat
24:25 H2O and IPA are poured out onto filters

Differences observed were
-IPA was noticeably hotter by handling the beaker than H2O through the 24 minutes of cooling.
-IPA appears to have precipitated a greater volume of material
-IPA has 2 colors of material, H2O has one very homogenous color

I will add the yields later and test their detonatability. Judging from this test, how consistent and uniform the H2O product is in appearance, H2O is the way to go.

[Edited on 15-4-2023 by Hey Buddy]

UPDATE:
It is now the next day and both samples were dried for around 10 hours at 60 C. The H2O reaction yielded 1.185 g. The IPA reaction yielded 2.600 g. Now comes the mystery part. The H2O reaction product does not detonate nor deflagrate unconfined, it is unreactive. The IPA reaction product deflagrates unconfined similar to DDNP. This is in contrast to previous batches I've made which had nuanced preparation differences, both H2O and IPA products in past have full immediate detonation unconfined.

I would assume the reagents are probably impure and introducing unknown contaminanation. These tests are done with in-house prepared reagents. I have ordered some AGu and will repeat the test with that. I really dont want to buy Ni Perchlorate so hopefully that's not the contaminant. I will test if Ni and AGu bicarbonate can be reacted with ammonium perchlorate as well. Which if successful, would be ideal. For my case, if nickel perchlorate can't be produced without HClO4 it makes the production route less attractive to me than for instance lead azide. Especially with sabanajeff oxidation route, and the volumes of data on lead azide. It's a very simple preparation route of only lead acetate, hydrazine sulfate and 50% nitric acid. It's downside is toxicity and slightly under responsive to flame. I like the simplicity of SADS, but its under powered and reverts to silver and Mercury Fulminate which is a bit sensitive. You can't both have cake and eat it too I suppose.

[Edited on 15-4-2023 by Hey Buddy]

Laboratory of Liptakov - 14-4-2023 at 22:41

Interesting work. Hey Buddy, the Nickel aminoguanidine diperchlorate is hygroscopic ? A lot or a little? Or at all? Thanks... :cool:

Hey Buddy - 15-4-2023 at 08:30

Quote: Originally posted by Laboratory of Liptakov

Interesting work. Hey Buddy, the Nickel aminoguanidine diperchlorate is hygroscopic ? A lot or a little? Or at all? Thanks... :cool:

I havent tested this but Ive had samples lay exposed to air for a weeks with no apparent moisture ingress or visible change.

Laboratory of Liptakov - 15-4-2023 at 13:06

Thanks Buddy. Good message.... :cool:

Herr Haber - 16-4-2023 at 07:30

I really dont want to buy Ni Perchlorate so hopefully that's not the contaminant.
[snip]
I will test if Ni and AGu bicarbonate can be reacted with ammonium perchlorate as well. Which if successful, would be ideal. For my case, if nickel perchlorate can't be produced without HClO4 it makes the production route less attractive to me than for instance lead azide.

[Edited on 15-4-2023 by Hey Buddy]

I'm pretty sure Ni perchlorate can be found at Onyxmet and Chemcraft if you change your mind.
I am fine with DLA too, but hydrazine / sodium azide is trickier to find than Ni(ClO4)2

Microtek - 16-4-2023 at 08:19

LL: NAP is not hygroscopic at all, in my experience.

NAP advancement

Hey Buddy - 10-5-2023 at 16:00

I've been experimenting with methods of production of NAP. My interest has been to simplify its preparation and understand it's character further.
I am happy to say that this material has a lot of variation in its product and that isn't a detraction but a strength. It's possible to modify sensitivity somewhat depending on purity, form etc.

I have found a route which prepares very high purity NAP in high yield. The nickel ion source is nickel carbonate and the perchlorate source is ammonium perchlorate.
In my opinion, this route prepares the purest form of NAP other than using HClO4 directly. The added bonus is that with this route, each respective material can be simply purchased and mixed in correct stoichiometry as needed.
Without capping agents or crystal modifications, this method produces entirely high purity, Blood-red, needle-shaped crystals. These crystals seem to be more sensitive than other forms. This is opposed to NAP derived from Ni(ClO4)2*6H2O. which seems somewhat different in product. This also differs entirely from Ni(ClO4)2 produced from NH4ClO4 or KClO4.

Previous preparations, such as Ni perchlorate via NiSO4 have considerable surface contamination by sulfate ion which appears to modify crystal to be less mechanically sensitive and spheroidal, which may be desireable or not.
Other preparations of Ni perchlorate as a precursor have been found to be entirely unnecessary and in fact, less efficient and lower yielding than the method of simply mixing correct ratios of NiCO3, NH4ClO4 and AGuHCO3, followed by heating.

NiCO3 can be bought from ceramic supply stores world wide. It is used as a glaze component in kiln fired pottery. Here in the USA, I have found it around $20/lb and it is widely available from many suppliers.

I am still experimenting with crystal modification but was very satisfied with this method of production. In my opinion with this method, NAP becomes the most desirable primary explosive as it yields well, is high performance, and its preparation is simpler than even SADS once this method is used.
With ammonium perchlorate production being possible at home, the various routes to Aminoguanidine and carbonates available as ceramic glaze components, this is the most home-lab practical primary, in my opinion.
In testing, I have found NAP to be the swiss army knife of primary explosives, being very capable. All of the excitment i've read on SM about this complex is justified.
I believe it could easily displace legacy primaries and will no doubt, in amateur production, displace current primaries, only a matter of time.
I've found nothing comparable.

B(a)P - 10-5-2023 at 17:24

Well done Hey Buddy! Agreed with your sentiments on the ease of production and performance. Looking forward to seeing your nickel carbonate route when you have it optimised.
The best yield I got with the nickel perchlorate / aminoguanidine bicarbonate route was about 50%, very curious to see your yields via nickel carbonate.

MineMan - 10-5-2023 at 18:02

Those are giant crystals! Great work Hey buddy

Diachrynic - 10-5-2023 at 21:36

I'm curious for a proper writeup, since if you have NiCO₃, you can make the acetate from it directly and use the preparation via that. It will be interesting what gives a higher yield (and especially if some reagent has to be in excess).

These microscope images are old, but still fairly pretty:

The corresponding nitrate has a totally different crystal morphology, and the sulfate on account of being quite insoluble in water doesn't form good crystals at all. It would be nice to find a salt that is as pretty and crystalline as the perchlorate, but without being energetic - it would make for a good beginner friendly experiment in coordination chemistry.

Microtek - 10-5-2023 at 23:29

You can avoid the formation of long needle crystals (which, while pretty, are less safe and more difficult to process) by maintaining stirring throughout the precipitation phase. It's probably possible to tweak the morphology by adjusting the RPM of the stirrer.

Hey Buddy - 11-5-2023 at 07:28

You can avoid the formation of long needle crystals (which, while pretty, are less safe and more difficult to process) by maintaining stirring throughout the precipitation phase. It's probably possible to tweak the morphology by adjusting the RPM of the stirrer.

I saw that you mentioned this earlier in the thread and can confirm. RPM adjustment on cooling does change crystal size. At 200 rpm Im finding about the same size as with IPA.

I've tried some different crystal modifications:
-Propylene Glycol solvent: reacts with complex, red/brown syrup results.
-CMC: prevents complexation
-Dextrin: prevents complexation
-CMC: added after complexation, diminishes yield, impractical, short blocky crystals
-Dextrin: added after complexation, diminishes yield, long needle crystals are still formed
-Isopropanol solvent 90%: changes time of boil of reaction, lower boiling point, longer reaction time, complex crystallizes as a paste/powder with a lighter salmon color, apparent reduction in mechanical sensitivity

IPA yields are about +40% over H2O solvent. Beginning with a 1 g AGu reaction, H2O results .97 g, IPA results in 1.38 g

There is always green nickel remaining in filter after reacting stoichiometrically in H2O, IPA appears to leave less Ni in filter. Ni may benefit from reduction to less than stoichiometric in order to reduce unreacted Ni in product.

[Edited on 11-5-2023 by Hey Buddy]

Hey Buddy - 11-5-2023 at 07:42

Quote: Originally posted by Diachrynic

I'm curious for a proper writeup, since if you have NiCO₃, you can make the acetate from it directly and use the preparation via that.

That is the beauty of it, AcO simply adds unnecessary ions and requires preparation from other precursor. CO3 leaves as CO2 and works directly. I don't believe there is much benefit in yield from AcO vs CO3, possibly opposite. Regardless, because NiCO3 is readily available world wide as glaze material, it can be bought as a cheap source of Ni ion, then used directly without conversion to NiAcO. (If one wants to avoid AcO preparation, that is)

[Edited on 11-5-2023 by Hey Buddy]

MineMan - 11-5-2023 at 11:54

What is the IPA method?

I think cooling speed is the best way to modify crystal size. Should be able to crash out in a few seconds and basically dust.

MineMan - 11-5-2023 at 11:57

The acetic acid from the acetate helps the yield… for the copper complex the reaction will not work without the acetate. Maybe another acid can be used, I don’t know.

Hey Buddy - 11-5-2023 at 13:49

What is the IPA method?

I think cooling speed is the best way to modify crystal size. Should be able to crash out in a few seconds and basically dust.

IPA instead of water as solvent. It increases yield but changes material. There doesn't seem to be much of a difference other than IPA makes powder that is lighter colored vs darker crystals at lower yield with water. IPA or water solvent both explode at same velocity as far as I can tell. At least enough to detonate secondaries. --The only thing I've changed from earlier methods is that I'm now boiling solvent first, then adding reactants after boil is reached. Im doing that to control boiling times for record, so differences can be compared.

Hey Buddy - 11-5-2023 at 13:57

The acetic acid from the acetate helps the yield… for the copper complex the reaction will not work without the acetate. Maybe another acid can be used, I don’t know.

In my opinion, acetates have been used because the acetate anion is soluble and doesn't complex. Nickel acetate isnt available as a commercial product in quantity, and so it has to be prepared from a nickel source. In that case Nickel perchlorate could be prepared and used instead of the acetate. I wasn't sure how a carbonate and bicarbonate would behave against a perchlorate but it works well. The metal carbonates are available in commercial quantities because of the ceramics industries, so NICO3 for instance is available at as low as $15/lb, whereas acetate must be prepared or purchase at premium. I can do a comparison between acetate and carbonate and perchlorate salts for yield, but in terms of efficiency and simplicity, its hard to beat NiCO3.

NAP: NiCO3 procedure

Hey Buddy - 17-5-2023 at 14:21

I've conducted some tests on NAP production from NiCO3 and have drawn some conclusions. These are my findings. Hopefully free of errors...

This reaction has a lot going on, especially if other solvents are used besides H2O. I believe the solvents are all interacting with the reaction as it takes on the complex. Excess ClO4 salt and Bicarb have been attempted in this effort to identify any differences, but it was found that ClO4 in excess diminished yield and seemed to alter reaction route. Excess Bicarb results in a blackened solution which is variable with the amount of time in boil. Too much boil time reduces product, too little boil time leaves reagents unreacted in solution. The black solution resulting from excess bicarb typically has a metallic sheen on the surface like a bismuth rainbow, and has been described in the beginning of the thread with the original patent procedure. That procedure uses > 2x excess AGu bicarb. The use of stoichiometric quantities in these reagents reduces the black solution and it doesn't present itself in the same way when using this procedure.

Yield is ~.91 g which is low compared to other procedures, a 100% yield would be 2.96 g, but the simplicity of this procedure is the real advantage. All of these reagents can be purchased or prepared in large quantity. In terms of crystal quality and consistency, I've found the stoichiometric ratio of 1 AGu/1 ClO4/.5 Ni gives the best, consistent results. Yield can be increased around +40% from use of 91% isopropanol instead of water. Ethyl also works with similar results, other solvents likely have effects on reaction, yield and product. IPA changes crystal morphology and end product color but is still an effective explosive.

NAP 405.76 g/mol
NAP temp of explosive decomposition ~270 C
NAP can detonate as single crystals
I've found NAP to be more mechanically sensitive than ETN or SADS, but less sensitive than lead azide. I have found it to be more impact sensitive than friction sensitive.

AGuHCO3 136.11 g/mol
NH4ClO4 117.49 g/mol
NiCO3 118.7 g/mol

The basic proportions are stoichiometrical and proportioned from AGu bicarb mass, which is considered as the critical reagent:

AGuHCO3 1.00 g
NH4ClO4 0.86 g
NiCO3 0.43 g

25 ml - 30 ml H2O are brought to a boil. If using a small diameter beaker, such as 2" diameter, then you can get away with 25 ml H2O. Larger diameter beakers cook off water too quickly and need a greater starting water mass, something closer to 30 ml or even more depending on your beaker surface area.

When water has achieved boil, all reagents are dumped in at once. The reaction turns lime green and begins to off gas NH3 and CO2 immediately. Some foaming and rise in volume happens. The foaming subsides and the solution turns to a darker green. The total boil time is 7.5 minutes. I have tested this procedure at 30 second boil intervals from 5 minutes to 15 minutes and have found in the case of H2O/IPA, 7.5 minutes boil to be the optimal in resulting yield.

At the conclusion of the 7.5 minute boil, the reaction is removed from heat and left to cool at ambient temperature. If large red crystals are desired, use H2O solvent and allow it to sit undisturbed during cooling. If small red crystals are desired, continue stirring throughout cooling. IPA solvent will cool without stirring as a powder. Cooling is necessary only to near ambient temperature. Leaving the reaction to sit overnight in solution decreases yield. Four hours is the patent recommendation, I have used an hour to around two hours of cooling before filtering. I have been washing the material on filter only to the extent of rinsing out remaining material from the beaker with water and pouring this remainder and water over the filtered crystals. I typically dry the finished material overnight at 60 C. NAP is still explosive when damp, but dampness reduces explosive intensity and sensitivity.

Overall I've found the complexation to be very sensitive to any change, with variable results, it certainly seems that IPA may be slightly less impact sensitive than H2O solvent reactions. That is just speculation and needs further testing. It's still impact sensitive.

I purchased NiCO3 from Clay King in USA
https://www.clay-king.com/glazes_ceramic_pottery/raw-materia...
That price is average but i've since found it as low as $15/lb

AGuHCO3 was ordered through Alibaba
NH4ClO4 was ordered from pyrochemsouce

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

[Edited on 18-5-2023 by Hey Buddy]

Laboratory of Liptakov - 17-5-2023 at 22:48

Great detail science work, Buddy...... :cool:

MineMan - 17-5-2023 at 23:11

Hey buddy. I think you’re using too much water. Water seems to destroy this compound

underground - 18-5-2023 at 04:49

So i guess the use of IPA solvent is the way to go since yields are increased.

Edit: Tetrazolover in his improved version use a mixture of AminogPerch and NiPerc

[Edited on 18-5-2023 by underground]

Hey Buddy - 18-5-2023 at 08:06

Hey buddy. I think you’re using too much water. Water seems to destroy this compound

I assumed that water destroyed the complex too, but it's not that straight forward. The theory was that water destroys product and this is the black color. By using proportional AGu, it eliminates this black liquid effect for the most part. Using 25 ml is based off of bringing the water to a boil, then adding reactants. During the boil some of the water is lost. 25 ml starting volume, is enough to maintain a solution through the boil. 20 ml is too little and will cause it to crystallize out of solution while heating on the hotplate. This effect is magnified if a wider beaker is used. At such small volumes, minor changes, such as beaker surface area, have dramatic effect on the course of reaction. Even if the product jumps out of solution, from evaporation of solvent, it is still useable, still explosive, but it changes the form of the material. By keeping it in solution, the form is controlled and repeatable. I don't believe that the water is destroying the product. Water does seem to diminish product if the material is left in solution for a long time.

Hey Buddy - 18-5-2023 at 08:19

Quote: Originally posted by underground

So i guess the use of IPA solvent is the way to go since yields are increased.

Edit: Tetrazolover in his improved version use a mixture of AminogPerch and NiPerc

[Edited on 18-5-2023 by underground]

I think the effect of solvent is interesting, but I'm not sure if it's necessarily better. It's a bit beyond my ability to analyze whats going on accurately. I can only speculate. IPA does certainly increase yield, but it does alter the complex. In my opinion, consistent production of the same product is more important than altering the material for yield. I also don't know the long term effect of IPA produced material, I have some in storage for a month now, some in open air too. But will it last years? I dont know. Some other solvents may increase yield even further than IPA.

There are surely many tricks to increase yield. --From the start, AGu the limiting critical reagent. Preparation of other Ni substrates like acetate or perchlorate is possible, but in my judgement, with the use of NiCO3, this primary explosive becomes easier to produce than even HMTD, or SADS assuming that AGu preparation is done. It is definitely a magnitude simpler than azides by any route, and it outperforms azide in all categories in my opinion. In the picture of the materials from post, it is basically all that's needed for several pounds of primary explosive, all the materials are less practically hazardous than NaN3 or even concentrated H2O2. And they should be shelf stable for long duration. Maybe yields can be increased but I think the simplicity outweighs the gain in yields from adding additional operations and effort, in my opinion that is.

MineMan - 18-5-2023 at 08:53

Indeed. I don’t recall an issue with product forming too early with low volumes of water. But I do recall the best yields with less water.

Anyways. It’s time you explore the copper salt. More powerful and less sensitive.

MineMan - 18-5-2023 at 08:55

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

Hey Buddy - 18-5-2023 at 12:26

Anyways. It’s time you explore the copper salt. More powerful and less sensitive.

It would be interesting to see character of other unknown metals. The patent only really describes Ni, Cu, and Co. Maybe see what it does with cuprammine as a solvent? That would make for a simple prep. The ceramic stores seem to have a lot of carbonates which I would assume could just replace Ni. Looking at them in another tab I'm finding Mn, Mg, Li, Sr, Ba.

MineMan - 18-5-2023 at 15:45

I don’t know enough of why the metal anion makes such a difference, there must be a way to model this. I think some of the rare earths would be most interesting. Dense and we are just finding their value in pyrotechnics, themrobarics and flare mixtures.

Update on IPA solvent NAP

Hey Buddy - 19-11-2023 at 19:54

6 month update:
Several samples of water solvent (W) NAP and IPA NAP were stored in sealed containers in a garage for 6 months. They were exposed to temps up to 95 F (35 C) during ambient storage. One of the W NAP samples seemed to undergo a slight darkening to darker red color almost brown. That sample was tested with a burn test and appeared to have weakened in explosive force. Another sample of W IPA did not appear to change color and that sample appeared to have no changes over storage for 6 months on firing power. The IPA NAP sample had no change in appearance or firing power for 6 months.

I have been firing RDX caps with the IPA NAP at <10 mg with reliability. The IPA NAP also appears much less sensitive to hammer blow than the WNAP. I dont have an apparatus to compare force, but from crude judgement, the IPA appears to detonate around the same hammer blow force as ETN, very close.

Due to the increased yield from IPA solvent, along with these obsevations, I think the IPA version may be more desirable over all. I am much more confident pressing with the IPA variant over normal NAP due to apparent decrease in handling sensitivity. I have no idea what accounts for the apparent desensitization. I thought at first it was morphology, but I now suspect the IPA complexes and it's a different molecule.

[Edited on 20-11-2023 by Hey Buddy]

B(a)P - 19-11-2023 at 20:11

6 month update:
Several samples of water solvent (W) NAP and IPA NAP were stored in sealed containers in a garage for 6 months. They were exposed to temps up to 95 F (35 C) during ambient storage. One of the W NAP samples seemed to undergo a slight darkening to darker red color almost brown. That sample was tested with a burn test and appeared to have weakened in explosive force. Another sample of W IPA did not appear to change color and that sample appeared to have no changes over storage for 6 months on firing power. The IPA NAP sample had no change in appearance or firing power for 6 months.

I have been firing RDX caps with the IPA NAP at <10 mg with reliability. The IPA NAP also appears much less sensitive to hammer blow than the WNAP. I dont have an apparatus to compare force, but from crude judgement, the IPA appears to detonate around the same hammer blow force as ETN, very close.

Due to the increased yield from IPA solvent, along with these obsevations, I think the IPA version may be more desirable over all. I am much more confident pressing with the IPA variant over normal NAP due to apparent decrease in handling sensitivity. I have no idea what accounts for the apparent desensitization. I thought at first it was morphology, but I now suspect the IPA complexes and it's a different molecule.

[Edited on 20-11-2023 by Hey Buddy]

I have not tried your idea of using IPA as a solvent, though I did at one point compare filtering within an hour of reaction completion and leaving it to sit overnight. For batches left sitting over night I found that the yield decreased and the product was not storage stable as you describe for you (W) NAP. I observed the batches that were left over night to increase in volume over time, become less powerful and change/darken in colour to brown.

Hey Buddy - 19-11-2023 at 20:30

That is very interesting. In the brown sample in my case, it was filtered after an hour. Like I usually do and was beautiful red appearance. Browning seemed to take place on that sample sometime during hot summer months.
Another thing about these AGu complexes in the patent, IIRC the cobalt complex cited was the Nitrate, not perchlorate. I missed this somehow, thinking it was also the perchlorate. In that case, I may attempt some nitrates and check the cobalt perchlorate. I think zinc should be checked too. I dont have any zinc carbonate. I do have some cobalt though... Has anyone attempted nitrates or other metal perchlorate analogues yet? I havent adventured any further than the Ni so far.

Diachrynic - 19-11-2023 at 23:54

In my experience, a sample, made as described on page one of this thread, that is from water, does not change at all for over three years. No change in color or anything else, stored at ambient temperature.

Has anyone attempted nitrates or other metal perchlorate analogues yet?

I have prepared the nickel nitrate version, which is also a very nice red, with a different crystal shape. It is flammable, when heated it melts into a brown liquid then burns, but nothing else was tested. The copper nitrate version was a pretty purple, which wasn't tested at all. They likely aren't really energetic however. Alongside these I also made the nickel sulfate and copper sulfate version, but these are not energetic at all, obviously. All of these are simple to prepare though.

The copper perchlorate version has been evaluated in this YouTube video by EnergeticHeretic: https://www.youtube.com/watch?v=YFO37dtkKEg

Hey Buddy - 20-11-2023 at 15:28

I found some Zn & Pb AcO also cobalt. Left is lead, pink is cobalt, salmon color is just an IPA NAP batch I needed to make for detonators and Zn is on right. They appeared to successfully complex as they gave NH3 smell and precipitated product. I used water solvent for the experiments. Pb was difficult to detect NH3 so it may not have complexed. Will find out soon. Will get back out tonight to try Ba(NO3)2 and Sr(NO3)2. Those are just white, Id assume they will complex white. Will see...

[Edited on 20-11-2023 by Hey Buddy]
Co AGu Perchlorate appears to be non energetic, which I find hard to believe. Suspect there may be issues with the cobalt source. Zn also doesnt seem to fire much but Im waiting to dry overnight before more testing. Same with Ba/Sr nitrates. The nitrates do make some popping when wet which is good. It's not as energetic as wet NAP, but will have to wait until dry before its character can be revealed. Pb seemed to react but it did not explode. It appeared to turn to oxide on flame. Ba/Sr both fizzed and bubbled quite a bit on addition so Im hoping theres something energetic there.

Is calcium or potassium worth checking? They seem unlikely. Ca would probably be hygroscopic. K would probably not be energetic. Still, perhaps KClO4 test. If that could complex into a primary it would be pretty handy...

[Edited on 21-11-2023 by Hey Buddy]

What about Boric acid? I think boron can make some really strange complexes and boric acid is soluble in water.

[Edited on 21-11-2023 by Hey Buddy]

MineMan - 21-11-2023 at 02:44

Curious for the boron!

Hey Buddy - 21-11-2023 at 06:57

Sr/Ba(AGu)2(NO3)2 are not energetic
Zn, Co(AGu)2(ClO4)2 not energetic
Pb appears to not have complexed and reverts to oxide. Will attempt to check KClO4, Ca ClO4 and Boron ClO4 hopefully today

Really wondering why there was no luck with Co. It should react to form an energetic syrup with either nitrate or perchlorate according to patent. I used AAV1 method for all of these. I reviewed the Cobalt carbonate source. From ceramic supply store. Should be no issue even with trace mineral contaminants. May repeat test with longer reaction time or different solvent...

[Edited on 21-11-2023 by Hey Buddy]

Ahh, I missed translation on patent. Filtrate of cobalt is concentrated to render syrup. I suppose the pink filtered material is inert discard.--Ni is definitely looking to be preferable.

[Edited on 21-11-2023 by Hey Buddy]

Potassium and boron go into a transparent solution. only crystallize on refrigeration. Boron barely yields, not enough for practicality. Potassium looks not energetic and turns orange color on burning.

[Edited on 22-11-2023 by Hey Buddy]

Microtek - 22-11-2023 at 03:58

I agree that it is almost inconceivable that Co(AGu)2(ClO4)2 should be non-energetic. One thing to test would be to convert the CoCO3 to perchlorate via reaction with HClO4. That way you can be more confident that the recovered complex is not a carbonate based one...

Hey Buddy - 22-11-2023 at 06:46

I agree that it is almost inconceivable that Co(AGu)2(ClO4)2 should be non-energetic. One thing to test would be to convert the CoCO3 to perchlorate via reaction with HClO4. That way you can be more confident that the recovered complex is not a carbonate based one...

Yes, apparently, It's in the filtrate. I shouldnt have wrote these are "not energetic". What I should have specified was "using method AAV1 from patent, the apparent product for these attempts were non-energetic." There should be energetic products I think for the zinc and cobalt, but the method used for NAP probably has to be altered to yield a product. On the cobalt, patent instructs boiling filtrate down to syrup. I suppose what was recovered from filter in these cases is unreacted material.In that case, It's not as desireable to me as NAP because of the extra processing steps. I think the only primaries more efficient in production are arguably SADS and Hg(CNO)2. NAP, especially in IPA solvent is so efficient, relative to input operations and time, assuming AGu is already prepared, very efficient. IPA even decreases drying time relative to water. You can batch and fire NAP in a couple hours.

[Edited on 22-11-2023 by Hey Buddy]

Microtek - 22-11-2023 at 13:02

Yes, NAP is very hard to beat. However, have you tried putting the finished NAP in water? I did that to see if recrystallization was possible, and the NAP was destroyed over the course of hours, producing more of the black solution.

Hey Buddy - 22-11-2023 at 19:36

I have not attempted to break it down in water. I suppose I should check the IPA for any difference in character versus standard. --In general It seems very reactive in complexation, different solvents and additives are altering physical characteristics. I attempted CMC and dextrin when first testing NAP, CMC appeared to alter the complex. Because of this sensitivity, it might be possible to look for an NAP variant that has less intensity of water remediation. Example: Glycol solvent makes a red fluid product which doesn't crystallize which I would venture to guess is a liquid form primary explosive.

Also parlon binder is water proof. Of course nitrocellulose too. Pelletization with homogeneous binder or surface encapsulation of a pellet with water proof binder will definitely prevent water reaction.

[Edited on 23-11-2023 by Hey Buddy]

Ok, I placed a sample of IPA NAP in water. In sinks to bottom on addition in a salmon colored dusting and in the water above it, I can see faint wispy black trails where the sample sank. The black trails are very minimal so far, they appeared only on addition. Waiting to see...

[Edited on 23-11-2023 by Hey Buddy]
Color changing before my eyes. Only a few minutes in, already turning dark and colorless. I think the perchlorate and water sensitivity issues are basically no-go for governmental consideration. For me, Im too impressed all around with it. Water sensitivity doesnt phase me. I do think there could possibly be found a variant with more water resilience. I will just start working on a waterproof pellet to affix to the end of fuze/resistance wire.

[Edited on 23-11-2023 by Hey Buddy]

Microtek - 23-11-2023 at 03:27

I think the water sensitivity is caused by aminoguanidine being a quite labile ligand in this complex. Free aminoguanidine is known to be unstable, and solutions of it turn black on standing. I agree that since NAP seems to be only sensitive to liquid water, it really isn't a problem, and could even be seen as a positive - detonators could be rendered insensitive (to the level of the secondary) by flooding if you needed to dispose of them.
Still, for some applications higher stability may be preferable, and there is also the matter of atomized nickel, or possibly nickel carbonyl released on detonation.

Hey Buddy - 24-11-2023 at 14:24

The IPA NAP sample in water has now turned green. It still has the same powder form but has changed color. Another sample seems unreactive and insoluble in acetone. In that case, Parlon/chloropolymers and nitrocellulose should work well with this material.

Update, it reacts with acetone. Changing color. The reaction is slower than water but that could be an issue for binders, Will have to test.

[Edited on 24-11-2023 by Hey Buddy]

Hey Buddy - 9-12-2023 at 17:12

A pink sample of IPA NAP powder was placed in a bowl of water, it reacted with the water forming a green substance. The water evaporated slowly. Once dry, It formed a red crystal with a green deposit also remaining. The crystals detonate on flame. I assume it has reverted to regular NAP. This brings to question:
1) When NAP reacts with water, does it revert back to the red crystal after drying?
2) Is NAP destroyed by reaction with water, or does the material remain explosive?

I haven't followed up on experiments lately. But this was an interesting thing. The boric acid reaction was also left standing for several weeks and has since precipitated additional boron complex, but I havent had opportunity to test it on a flame.

Update: I scraped some of the boron complex with a popsicle stick and held a flame to it. It pops. This was done in the wet state out of the beaker. Then I messed up by using alcohol to try to get the last bit of material out. The alcohol seems like it may have contaminated the original colorless sample, it looks slightly green/white after exposure to alcohol. I scraped some of this material onto a popsicle stick wet and lit it. It burned and appears to react to flame. Sample is drying now. Will check on it in an hour. I used Boric acid:AGu:NH4ClO4 at a molar ratio of 1:2:2. Powders were dumped all at once into ~ 25 ml boiling water and boiled 5 min. Then allowed to sit and cool in beaker for several weeks. Not sure when the material began to precipitate. There was immediate precipitation of a small fraction and after a day of sitting, the beaker was neglected. Will update on dry reaction to flame...

[Edited on 10-12-2023 by Hey Buddy]

Update: boron is not energetic...too bad

[Edited on 10-12-2023 by Hey Buddy]

MineMan - 12-12-2023 at 01:02

That’s a real bummer, why did it pop then?

Any other metals you can think of?

Why is it always the heavy metals and transition metals that work well?

Hey Buddy - 12-12-2023 at 11:23

That’s a real bummer, why did it pop then?

Any other metals you can think of?

Why is it always the heavy metals and transition metals that work well?

I think it may have been an interaction with the wood, or something in the wood that popped. Not sure. I was hopeful, but even if it were desirable it's really low yield. I think the IPA nickel is very good though. I will work on feasibility some binder loads into pellets parlon and NC.

MineMan - 23-12-2023 at 23:28

Mix in 1 percent micron graphite powder! Will reduce ESD and friction. Never nano graphite!!! Only use micron.

Graphite is actually one of the most energy dense fuels. I think it’s underexplored as both a fuel for AN mixtures and for making compounds safer

))

If you want to know what nano graphite does DM me.

Etanol - 7-3-2024 at 08:52

I've conducted some tests on NAP production from NiCO3 and have drawn some conclusions. These are my findings. Hopefully free of errors...

https://www.sciencemadness.org/whisper/files.php?pid=684200&...

I repeated the synthesis with the same ratios and boiled the mixture for not 15 minutes, but for more than 2 hours. But I still could not dissolve the entire NiCO3.
Have you been able to do this before cooling the mixture? In your photo, the red light appeared in a hot state or only when it is cooling?
Something is wrong with this patent and a formula of substance.
Maybe 3 mol aminoguanidine molecules are required for 1 mole of Nickel?
Maybe formula is Ni(AGu)3(ClO4)2 or aminoguanidine decomposes?

I filtered a hot mixture and after cooling I received beautiful transparent red crystals.
The dried substance has excellent sensitivity to fire. I love it.
20 mg explode with a bright flash, but for some reason without brisant.

upd
I made a mistake in assessing the mass. The measured portions were approximately 5-10 mg.
20 mg detonates, leaving a dent in an iron bank.
Unfortunately, I confirm your words. I could not recrystallize my substance from distilled water. It decomposes into grey-green Ni(OH)2.
Very sad.
It seems that there is always an excess of aminoguanidine in the solution. For this reason, 2.5 mols aminoguanidine are taken in the German patent, not 2 mol, per 1 mol NiCO3 or Ni(ClO4)2.

[Edited on 8-3-2024 by Etanol]

Hey Buddy - 8-3-2024 at 18:20

I'm somewhat confused tracking what you are saying, but the method I've used recently is to:
25-35 ml dH2O brought to boil
1 g AGuHCO3 .86 g NH4ClO4 .43 g NiCO3 stirred together , then dumped in at once.
Boil while stirring for 5-7 minutes
Remove from heat and allow to cool to room temperature
Filter off water and dry

I prefer to use 91% isopropanol instead of water, it gives a pink powder that in my experience is very consistent and more impact/friction insensitive. It is done exactly the same, the water is just switched to 35 ml+ 91% IPA. I have noticed the pink powder seems less sensitive to fuze. I use electric starters or fuze with nitrocellulose/KClO4/Al or Ti to give better heat transfer.

pjig - 10-3-2024 at 08:40

Can pottery grade Nico3 be used as is or must it be purified 1st before use?

Etanol - 10-3-2024 at 09:17

I'm somewhat confused tracking what you are saying,

I mean, are you sure that NiCO3 reacted all before cooling the solution?

Hey Buddy - 11-3-2024 at 16:12

I believe it is mostly reacting. It's a somewhat low yielding complex.

Etanol - 11-3-2024 at 21:12