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Hey Buddy
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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]
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Microtek
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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.
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Hey Buddy
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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]
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Hey Buddy
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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.
![20231209_185959[1].jpg - 1.7MB](http://www.sciencemadness.org/talk/files.php?pid=689305&aid=100272)
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]
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MineMan
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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?
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Hey Buddy
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Quote: Originally posted by MineMan  | 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?
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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.
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MineMan
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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.
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Etanol
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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]
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Hey Buddy
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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.
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pjig
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Can pottery grade Nico3 be used as is or must it be purified 1st before use?
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Etanol
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I mean, are you sure that NiCO3 reacted all before cooling the solution?
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Hey Buddy
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I believe it is mostly reacting. It's a somewhat low yielding complex.
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Etanol
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I noticed that when the NAP dissolves in hot distilled water, isoopropanol or ethanol, it does not decompose completely. The equilibrium occurs and I
can crystallize the undecomposed part of the NAP. It seems the synthesis needs an excess of AGu*HClO4.
Have you tried to use Ni(OH)2 instead of NiCO3 yet?
I think to do this in two stages through Ni(OH)2.
The first stage:
boiling AGuCO3+NH4ClO4 => AGu*HClO4
I have already done this and was able to get aminoguanidine perchlorate in pure form. This is also a very energetic substance.
2 stage:
Add Ni(OH)2 and boil until it almost completely dissolved.
filter a hot solution from no-reacting Ni(OH)2
cold filtered solution in water-ice mix to 0C
filter NAP
Use the solution of AGu*HClO4 for new synthesis
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Hey Buddy
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I would imagine there are methods to be found that will increase yield. I prefer the NiCO3/AP/AGuHCO3 method because all that needs to be synthesized
is AGu. Everything else can be purchased OTC, where as NiOH can be made, but is not exactly OTC. Carbonates can be bought from ceramic supply shops.
Compared to something like preparing sodium azide to lead azide or NTz, NAP is a magnitude simpler, despite low yields. Therefore I accept low yields
in trade for expedient prep and availability.
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pjig
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Hey buddy,
Are you using pottery grade Nico3, Without the need of purifying, just as is? I assume you’re using guanidine nitrate as the starting material for
the aminoguanidine.
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Etanol
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I prepare NiCO3 from chemically pure NiSO4*7H2O and baking soda.
I think the difference will be in the reaction speed only.
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pjig
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So I assume pottery grade nic03 will work as is …? Saving the double decomp. Of the sulfate …. One less step to gain the end result
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Hey Buddy
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| Quote: Originally posted by pjig | Hey buddy,
Are you using pottery grade Nico3, Without the need of purifying, just as is? I assume you’re using guanidine nitrate as the starting material for
the aminoguanidine. |
Yes guanidine nitrate-->--NQ-->AGuHCO3 and cheap ceramic glaze sourced NiCO3. 300 micron ammonium perchlorate. I used to try Ni(ClO4)2 from SO4
but it was unnecessary processing and difficult to purify.
I should also mention for record, I have attempted every commercially available carbonate in experimentation, besides lithium, Sodium and calcium.
None of them complex in the same way as the Nickel. The other carbonates produce negligible materials. The cobalt carbonate may produce a complex that
is diluted in the filtrate, but I havent attempted to experiment with boiling it down to precipitate it. I have not been interested in replicating
that procedure from the patent because it is additional processing while the NAP is very suitable with minimal processing.
[Edited on 19-3-2024 by Hey Buddy]
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Etanol
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upd
Product properties from NiSO4-NH3 complex are different
[Edited on 20-3-2024 by Etanol]
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pjig
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Thanks for the reply. Much appreciated as always. I have aminoguanidine bicarbonate. And the more guanidine nitrate in larger quantities. I am
interested in making the nitroguanidine as well as the aminoguanidine salt as a precursor. What is the preferred method you used to reduce the
aminoguanidine salt?
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pjig
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Seems like there should be an easier way to aminoguanidine bicarbonate than nitrating guanidine nitrate to nitro guanidine , then reducing it to the
aminoguanidine bicarbonate.
What value in the industrial world is aminoguanidine bicarbonate? What is it used for ?
[Edited on 30-3-2024 by pjig]
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EF2000
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| Quote: Originally posted by pjig | Seems like there should be an easier way to aminoguanidine bicarbonate than nitrating guanidine nitrate to nitro guanidine, then reducing it to the
aminoguanidine bicarbonate.
What value in the industrial world is aminoguanidine bicarbonate? What is it used for?
[Edited on 30-3-2024 by pjig] |
Look at the thread by Engager: Synthetic routes to tetrazole compounds based on OTC materials. The other route is reacting calcium cyanamide with hydrazine sulphate to get
aminoguanidine sulphate, then adding sodium bicarbonate to precipitate bicarbonate. See chapter 1, step 3 in the linked thread.
Calcium cyanamide is available as fertilizer in some places, also can be made from urea and calcium oxide.
Wroom wroom
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pjig
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Awesome!! Thank you for finding that post . I searched for it but couldn’t remember what thread it was in. It’s a nice piece of work , very
detailed .
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B(a)P
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I have been doing some testing recently using water as a solvent and starting with aminoguanidine bicarbonate and nickel perchlorate for this reaction
and trying to maximise yield. As has been discovered already the volume of water used and the time in contact with water reduces the yield. In my
recent experiments I have also tried reducing the reaction temperature. The original method in the patent calls for the reactants to be taken to
boiling and held there for 5 minutes before leaving at room temperature for 4 hours. I have found that the reaction will go to completion as low as
85C. My best yield achieved so far was approximately 80%. The reaction mixture was taken to 85C then immediately removed from the heat to achieve this
yield. If the temperature is any less than this, unreacted aminoguanidine bicarbonate persists in the product. I should also note that I left the
reaction mix at room temperature for only 1 hour before filtering and rinsing with IPA.
One drawback of this method is that you need a second stirrer. If you simply remove your reaction vessel from the heat and discontinue stirring the
crystal size of the product is undesirably large.
I have noticed that the reaction commences at around 45C. For my next batch of experiments I intend to try taking the reactants to 50C and holding it
there for a period of time to see if the reaction will go to completion and if yield can be further improved. I suspect the yield will not be as good
due to the additional contact time with water, we shall see.
I would be interested to hear feedback from anyone else that has experimented with reduced temperatures for this reaction. I would also be keen to
hear what yields others are obtaining using different starting materials, particularly nickel carbonate.
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Nemo_Tenetur
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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?
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