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Author: Subject: Nickel aminoguanidine diperchlorate
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[*] posted on 12-4-2024 at 03:51


Quote: Originally posted by Nemo_Tenetur  
Last week I tried the synthesis from nickel perchlorate (itself synthesized from commercially available nickel nitrate and soda, the precipitate was filtered, washed and redissolved in perchloric acid) and aminoguanidine perchlorate (prepared from commercially aminoguanidine bicarbonate and perchloric acid).

I´ve always used less than the theoretical amount perchloric acid, in both cases some insoluble carbonate / bicarbonate remained at the bottom of the vessel even if stirred over night.

Then I decanted the solutions from the insoluble impurities, the aminoguanidine perchlorate solution was yellow. I combined the solutions by dropwise addition of the nickel perchlorate solution to an excess aminoguanidine perchlorate solution and heated the reaction mixture until bubbles appear, then hold the temperature for several minutes and let it cool again to room temperature.

No visible reaction, no precipitate, nothing even after two days.

Disappointing.

Maybe the solutions were not concentrated enough or maybe the heating was not enough? Maybe the bubbles were simple carbon dioxide instead almost 100 degree centigrade water vapors? I didn´t use a thermometer to check the temparature, this was a mistake.

Is this reaction so temperature and/or concentration sensitive that slight alterations lead to a zero yield?



The reaction is very sensitive to water, what mass of water and reactants did you use? You should use no more water than will dissolve your reactants at an elevated temperature. I also believe the formation of the complex more readily occurs at lower pH.
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[*] posted on 12-4-2024 at 04:44


Quote: Originally posted by Nemo_Tenetur  
Last week I tried the synthesis from nickel perchlorate (itself synthesized from commercially available nickel nitrate and soda, the precipitate was filtered, washed and redissolved in perchloric acid) and aminoguanidine perchlorate (prepared from commercially aminoguanidine bicarbonate and perchloric acid).

I´ve always used less than the theoretical amount perchloric acid, in both cases some insoluble carbonate / bicarbonate remained at the bottom of the vessel even if stirred over night.

Then I decanted the solutions from the insoluble impurities, the aminoguanidine perchlorate solution was yellow. I combined the solutions by dropwise addition of the nickel perchlorate solution to an excess aminoguanidine perchlorate solution and heated the reaction mixture until bubbles appear, then hold the temperature for several minutes and let it cool again to room temperature.

No visible reaction, no precipitate, nothing even after two days.

Disappointing.

Maybe the solutions were not concentrated enough or maybe the heating was not enough? Maybe the bubbles were simple carbon dioxide instead almost 100 degree centigrade water vapors? I didn´t use a thermometer to check the temparature, this was a mistake.

Is this reaction so temperature and/or concentration sensitive that slight alterations lead to a zero yield?



Add water ammonia by drop after mixing Ni(ClO4)2 and AGu*HClO4 to pH=7.5...8:
Ni(ClO4)2+2AGu*HClO4+2NH3=>Ni(AGu)2(ClO4)2 (solid)+2NH4ClO4 (solution)
Then cold it to 0...5 Celsium.
Very nice and fast reaction:)
Long heating is not required in this method.

[Edited on 12-4-2024 by Etanol]
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[*] posted on 13-4-2024 at 14:00


I would be wary of using ammonia for adjusting pH. I think you risk substituting some of the aminoguanidine ligands.
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[*] posted on 13-4-2024 at 21:30


I feel that will partially created Diamine nickel perchlorate. Which is relatively weak salt on energy.



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[*] posted on 13-4-2024 at 21:50


Quote: Originally posted by Microtek  
I would be wary of using ammonia for adjusting pH. I think you risk substituting some of the aminoguanidine ligands.


Substituting with ammoia?
I have already prepared the subs with this method. Its color, solubility and explosive properties are identical to the NAP.
May be, Ni hexaammine perchlorate is formed in excess NH3, I don't check it.
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[*] posted on 14-4-2024 at 16:08


Gotta ask , is the initiation properties of nap reliable as something like azides ? Common method of cap manufacture (dense secondary base charge , medium pressed secondary, followed by a primary lightly pressed initiated by either ematch or fuse.
Can NAP function in that det orientation? Or as other “det trains “needs an intermediate 50/50 mix of primary and secondary to achieve this ddt transfer to the high density secondary base?
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[*] posted on 14-4-2024 at 19:45


Quote: Originally posted by pjig  
Gotta ask , is the initiation properties of nap reliable as something like azides ?

Yes


Quote: Originally posted by pjig  
Common method of cap manufacture (dense secondary base charge , medium pressed secondary, followed by a primary lightly pressed initiated by either ematch or fuse.
Can NAP function in that det orientation?

Yes

Quote: Originally posted by pjig  
Or as other “det trains “needs an intermediate 50/50 mix of primary and secondary to achieve this ddt transfer to the high density secondary base?

Not required.

Have a read through this thread I think Hey Buddy has tested the effectiveness of initiation. I have also done this on a small scale and it performs well. No need for any special primary secondary mixing.
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[*] posted on 14-4-2024 at 20:11


Awesome! Ty for the quick response. I thought I read that back a ways in the thread, but couldn’t find it anywhere….
NAP is very energetic like azides. Single crystal dets. Remarkable for such a simple synth.
It begs the question why it isn’t used more in an industry standard . Wondering if its down falls are potential toxic gas in the byproducts of decomposition. Seems like the material isn’t hydroscopic , maybe incompatibilities with other things (metals or secondaries)
Maybe it’s the low density, or Chrystal long needle’s sensitivity, or issues with packing in a det cap that may present a problem.
What pressures and or techniques are utilized to work with this primary . Maybe a visit with the IPA version will be a better fit for dets.

[Edited on 15-4-2024 by pjig]
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[*] posted on 14-4-2024 at 21:46


Quote: Originally posted by pjig  

It begs the question why it isn’t used more in an industry standard

I think it decomposes under the influence of moisture and CO2.
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[*] posted on 14-4-2024 at 22:34



Quote:

Chrystal long needle’s sensitivity


If you stir it continually during precipitation, it will form a powder rather than crystals.

Regarding decomposition when exposed to CO2 and moisture, I think you are right. But LA does this as well...

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[*] posted on 15-4-2024 at 00:36



Add water ammonia by drop after mixing Ni(ClO4)2 and AGu*HClO4 to pH=7.5...8:
Ni(ClO4)2+2AGu*HClO4+2NH3=>Ni(AGu)2(ClO4)2 (solid)+2NH4ClO4 (solution)
Then cold it to 0...5 Celsium.
Very nice and fast reaction:)
Long heating is not required in this method.

I read that the crystals were tested for detonation properties. After a new method of preparation. Using ammonia water is a breakthrough in NAP preparation technology. It simplifies the whole process. Great job, Etanol.
Even ammonium perchlorate we obtain....:D...Absolut useful reaction.




[Edited on 15-4-2024 by Laboratory of Liptakov]




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[*] posted on 15-4-2024 at 07:34


Damn! This is just getting better by the day! lol
I am going to give the ammonia process a run . I took the beaker off the hot plate after the 7.5 min and let it cool undisturbed , if left on hot plate it would have cooled much slower , maybe not a problem and left to stir during rechrystalization phase. Or pull off the hot plate and stir on a cold surface .
Yes I’ll do the ammonia process at this point , (at the boiling point or the point where the reaction starts to cool?) also what is your method of testing for ph….paper , pen , probe, tongue :P
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[*] posted on 15-4-2024 at 07:43


Well I assumed that this newer process would offer a safer material for packing caps. What density would be suitable for the “old h2o method “ vs the new finer form of material?
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[*] posted on 16-4-2024 at 01:04


Quote: Originally posted by pjig  
at the boiling point or the point where the reaction starts to cool?) also what is your method of testing for ph….paper , pen , probe, tongue :P

neutralisation AGu*H2CO3 with HClO4
mixing of Ni(ClO4)2 and AGu*HClO4 solutions
heating to 80-90C (boiling is not necessary)
add NH3 with pH paper control
(evaporation of NH3 excess)
slow cooling with fast stirring
filtering
drying
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[*] posted on 16-4-2024 at 02:21


And the NH3 (or NH4OH) is added to water at 80 C..?...I estimate some splashing liquid. Final solution should be pH neutral..?..Thanks...:cool:
(Edit: Etanol sure a lot years using as probe own tongue)

[Edited on 16-4-2024 by Laboratory of Liptakov]




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[*] posted on 16-4-2024 at 11:43


Quote: Originally posted by Etanol  

neutralisation AGu*H2CO3 with HClO4
mixing of Ni(ClO4)2 and AGu*HClO4 solutions
heating to 80-90C (boiling is not necessary)
add NH3 with pH paper control
(evaporation of NH3 excess)
slow cooling with fast stirring
filtering
drying


What yield do you get with this method? Have you compared slow cooling to fast cooling?
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[*] posted on 16-4-2024 at 15:34


Quote: Originally posted by Laboratory of Liptakov  

Final solution should be pH neutral..?

Very weakly alkaline, I think.
It is difficult to immediately catch the pH drop by drop. But it is easy to evaporate the excess ammonia.

Quote: Originally posted by B(a)P  

What yield do you get with this method?

About 80-90%. I collected and evaporated the spent solution (NH4ClO4 + AGu*HClO4). A little red crystals formed and there was almost no green Ni(ClO4)2 or Ni(OH)2.

Quote: Originally posted by B(a)P  

Have you compared slow cooling to fast cooling?

Fast cooling forms dust and agglomerates.
Slow cooling forms visible crystals. Fast stirring and mechanical crushing break them into convenient powder with good bulk density.
NAP is well soluble in hot AGu*HClO4 solution, but poorly soluble in cold.
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[*] posted on 20-4-2024 at 20:07


IPA method;
I have Found and confirmed that fast cooling does create a very fine particulate. Hopefully not a disadvantage. Usually finer material equals less sensitivity. After solution was heated for 7.5 minutes it was pulled and kept on stirring on a cool surface.. Stirring was continued for one hour then material was filtered with IPA. Not sure the solution needed to be stirred for that long while going to ambient temp.
Is the better method to do what I did , pulling off hot plate and continuing stirring, or turn off hot plate and let cool slowly while stirring , or discontinue stirring (with IPA) .
Is there a advantage to using ph control with NH3 at this point for improvement in Chrystal formation and yield?

[Edited on 21-4-2024 by pjig]
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[*] posted on 23-4-2024 at 10:14


Quote: Originally posted by pjig  
IPA method;
Is there a advantage to using ph control with NH3 at this point for improvement in Chrystal formation and yield?

Without NH3, method with HClO4 don't work. Yield is null.
In your method, from AGuCO3+Ni(ClO4)2 or AGuCO3+NiCO3+NH4ClO4, NH3 is not required.

[Edited on 23-4-2024 by Etanol]
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[*] posted on 26-4-2024 at 06:50


I see. Thank you for clarifying. The IPA process is substantially a more desired product, in both particle size as well as returns , being a higher yield..
Is there any experimenting done with different percentages of alcohol, including absolute alcohol? Wondering if there is a need for a small percentage of water to take insoluble material into solution.
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[*] posted on 27-4-2024 at 17:23


Quote: Originally posted by pjig  
I see. Thank you for clarifying. The IPA process is substantially a more desired product, in both particle size as well as returns , being a higher yield..
Is there any experimenting done with different percentages of alcohol, including absolute alcohol? Wondering if there is a need for a small percentage of water to take insoluble material into solution.


When first experimenting with this material, I attempted the patent procedure substituting denatured alcohol for water and was unable to achieve reaction within 5 minute boiling interval. I should also mention that I attempted the reaction with propylene glycol and it reacted to form a red oil product. I did not test its character.

I am continuing to experiment with variations of the material. Overall I have found that IPA product is less sensitive to impact but also somewhat less powerful when unconfined, likely due to native density of the morphology, being a powder. I havent had any problems with pressing the material. I have experienced failures to transfer heat to initiate DDT in some cap designs using secondary, then primary, then a high temp pyrogen between fuze and primary. I found more success with that initiation train plasticizing the pyrogen with nitrocellulose and dipping the end of the fuze. This seems to give longer duration of heat output on the side of the fuze rather than a short spit from the end axis of the fuze.
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[*] posted on 29-4-2024 at 21:18


With e match There is a pretty energetic ignition. Any failures with this approach? Or need for boosting ignition beyond commercial ematch?

[Edited on 30-4-2024 by pjig]
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[*] posted on 4-5-2024 at 18:03


Quote: Originally posted by pjig  
With e match There is a pretty energetic ignition. Any failures with this approach? Or need for boosting ignition beyond commercial ematch?

[Edited on 30-4-2024 by pjig]


I have been really working on this material. I have found another variation recently in the past week. Im still researching the particulars, because the procedure is a bit sensitive to variables, giving mixed results.

I begin with the standard process for H2O solvent. After 5 minutes of boiling, I decant the reaction fluid leaving behind unreacted solids. The reaction fluid is then placed in a larger cool water bath and sonicated at 42kHz for 10 minutes. The resulting product is a highly dense powder. Possibly nano. Not really sure. It appears smaller crystal than any comparative powder I have.

This powder is considerably more brisant than any other morphology tested. I would consider it a technologically different material. I would compare its brisance to AgNTz or PbNATz. It can achieve clean punctures on Al foil at masses less than 1 mg. This is not possible with even larger slow crystallized morphology NAP, although they do detonate as single crystals, They don't really puncture Al foil.

In terms of sensitivity, crystal NAP is by far the most mechanically sensitive. It is sensitive to impact and friction within range expected in primary explosives. It is pretty sensitive.

IPA NAP (iNAP) is friction insensitive and possibly two to four times less impact sensitive than crystal NAP. Perhaps less, I dont have an apparatus but i have tested this comparison by hand a few dozen times.

Ultrasonicated NAP (uNAP) is ever so slightly less impact sensitive than crystal form, practically the same. It is insensitive to friction compared to crystal NAP. I was unable to detonate uNAP with a 4 lb mallet with pressure and repeated rubbing on top of concrete. While it detonates with a slight tap.

So far in ematch firing of material, it appears that iNAP fires well on ETN with around 25 mg or more. Below that, I have had some failures but I have since updated ematch configuration and it appears to be firing very well in the new configuration into lead blocks, so I will be testing again at sub 25 mg masses. uNAP fires at very small masses. At 25 mg it leaves a considerable impression in lead block at a firing diameter 3.25 mm. Ematches work very well with NAP in any of its forms. E matches directly fire iNAP at lower masses. Still testing blasting cap fillers to determine minimum loads.

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[Edited on 5-5-2024 by Hey Buddy]
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[*] posted on 7-5-2024 at 20:26


That is very interesting, using frequency to reduce particle size. Very clever! As for ematch, it is usually a pretty energetic form of ignition . Almost enough to detonate plutonium… :P
Well not quite, but enough to start most primaries.
Are your ematch 25 mg primes very reliable for petn or etn ?
And you’re attempting to find reliable minimal amounts for initiation …….
I’m thrilled to see what new findings you come up with


[Edited on 8-5-2024 by pjig]
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[*] posted on 26-5-2024 at 13:33


Any new findings for the threshold ddt amount for the NAP? 25mg seems a little high compared to other primaries like azides . Azides boast a .5~10 mg ddt ability on their initiation qualities. Pretty low compared to most primaries on the market

[Edited on 27-5-2024 by pjig]
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