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LardmanAttack
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[*] posted on 10-1-2020 at 21:53
NHN synthesis not working


I've been wanting to make and experiment with NHN for a while now and I finally was able to get nickel metal. So I made Nickel nitrate first from the metal and then got the nitrate from that, and then dissolved it in ethanol, then extracted freebase hydrazine from hydrazine sulfate using NaOH and extracted that with ethanol, then added it to the solution. It didn't really do anything at first, then some precipitate started to form as I poured more in, but then it seemed to dissolve?! and then the solution remained green, I added in a bunch of hydrazine and this happened a couple other times until it was way too dilute to work anymore. I'm really disappointed that it didn't work as i've been looking forward to this for a while. And I can't attempt it again until I make more Nickel nitrate, hydrazine, and possibly distill some more ethanol.
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Microtek
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[*] posted on 11-1-2020 at 00:13


Why do you use ethanol as the reaction medium? Most reported syntheses I have seen uses aqueous solutions. In your place, I would simply react hydrazine sulfate with a stoichiometric quantity of NaOH in aqueous solution (the Na2SO4 will most likely not interfere, and will be removed when you filter off your product). Also, you should probably add the nickel nitrate to the hydrazine, not the othe way round (to maintain an excess of hydrazine at all times). The addition should also be done dropwise I think (not clear on whether you did that or not). The addition is preferably done at ca. 65C, did you do that?

[Edited on 11-1-2020 by Microtek]
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wessonsmith
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[*] posted on 11-1-2020 at 13:45


Here is the NHN synthesis video.

https://youtu.be/rPxdDSUGxo4
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LardmanAttack
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[*] posted on 12-1-2020 at 13:38


Interesting, I wonder if it didn't work due to leftover acid from the nickel nitrate synthesis? or the fact that I had it dissolved in ethanol instead of just an aqueous solution.
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LardmanAttack
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[*] posted on 12-1-2020 at 13:41


Quote: Originally posted by wessonsmith  
Here is the NHN synthesis video.

https://youtu.be/rPxdDSUGxo4


Any particular reason you add the second solution of nickel simultaneously with the hydrazine? Also whats the best method for making the hydrazine solution?
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wessonsmith
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[*] posted on 12-1-2020 at 14:55


Quote: Originally posted by LardmanAttack  
Quote: Originally posted by wessonsmith  
Here is the NHN synthesis video.

https://youtu.be/rPxdDSUGxo4


Any particular reason you add the second solution of nickel simultaneously with the hydrazine? Also whats the best method for making the hydrazine solution?


The reason for the separate Nickel / Hydrazine additions is to prevent an over-concentration of nickel vs hydrazine. It's essential to produce it the way I do; otherwise, you won't get the beautiful free-flowing powder.

Unfortunately, I haven't been able to produce hydrazine in a concentrated enough form to make NHN. I bought my Hydrazine monohydrate from eBay.
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LardmanAttack
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[*] posted on 16-1-2020 at 01:37


So I was successfully able to make NHN by adding the concentrated nickel solution to the hydrazine solution. It's performance as an explosive isn't great, so i'll likely test out the dextrinated method to see how much it improves from there. Nonetheless I am satisfied that it worked.

[Edited on 16-1-2020 by LardmanAttack]
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ShotBored
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[*] posted on 16-1-2020 at 10:05


My experience working with Nickel catalysts was that a green solution indicates the presence of Nickel (II) species. So you successfully reduced the nickel metal but if you had the formation of Nickel (II) Hydroxide (from the NaOH/Hydrazine solution) then that would easily dissolve in acidic conditions like you saw. Had the same thing happen to me when I was making a Tetrakistriethylphosphite Nickel complex.
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wessonsmith
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[*] posted on 16-1-2020 at 11:49


Quote: Originally posted by LardmanAttack  
So I was successfully able to make NHN by adding the concentrated nickel solution to the hydrazine solution. It's performance as an explosive isn't great, so i'll likely test out the dextrinated method to see how much it improves from there. Nonetheless I am satisfied that it worked.

[Edited on 16-1-2020 by LardmanAttack]


Was your NHN a fine powder or was in chunks / large grains? Also, did you use a 65C reaction temp?

[Edited on 16-1-2020 by wessonsmith]
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XeonTheMGPony
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[*] posted on 17-1-2020 at 05:26


Quote: Originally posted by wessonsmith  
Quote: Originally posted by LardmanAttack  
So I was successfully able to make NHN by adding the concentrated nickel solution to the hydrazine solution. It's performance as an explosive isn't great, so i'll likely test out the dextrinated method to see how much it improves from there. Nonetheless I am satisfied that it worked.

[Edited on 16-1-2020 by LardmanAttack]


Was your NHN a fine powder or was in chunks / large grains? Also, did you use a 65C reaction temp?

[Edited on 16-1-2020 by wessonsmith]


Off topic:

Where did you get your grenade fuses from? been trying to find such things for ages
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wessonsmith
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[*] posted on 17-1-2020 at 05:33


Quote: Originally posted by XeonTheMGPony  
Quote: Originally posted by wessonsmith  
Quote: Originally posted by LardmanAttack  
So I was successfully able to make NHN by adding the concentrated nickel solution to the hydrazine solution. It's performance as an explosive isn't great, so i'll likely test out the dextrinated method to see how much it improves from there. Nonetheless I am satisfied that it worked.

[Edited on 16-1-2020 by LardmanAttack]


Was your NHN a fine powder or was in chunks / large grains? Also, did you use a 65C reaction temp?

[Edited on 16-1-2020 by wessonsmith]


Off topic:

Where did you get your grenade fuses from? been trying to find such things for ages


https://www.cannonfuse.com/store/pc/American-Visco-Cannon-Fu...

I use the green

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LardmanAttack
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[*] posted on 18-1-2020 at 13:35


Quote: Originally posted by ShotBored  
My experience working with Nickel catalysts was that a green solution indicates the presence of Nickel (II) species. So you successfully reduced the nickel metal but if you had the formation of Nickel (II) Hydroxide (from the NaOH/Hydrazine solution) then that would easily dissolve in acidic conditions like you saw. Had the same thing happen to me when I was making a Tetrakistriethylphosphite Nickel complex.


Wow, that actually makes a lot of sense, I don't even know how I didn't think of that, I guess next time, I'll filter it off and put it in a freezer to extract the majority of the NaOH and NaSO4 before using.
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XeonTheMGPony
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[*] posted on 19-1-2020 at 08:01


Quote: Originally posted by wessonsmith  


I use the green


Sorry I meant the grenade style fuze.
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wessonsmith
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[*] posted on 19-1-2020 at 08:04


Quote: Originally posted by XeonTheMGPony  
Quote: Originally posted by wessonsmith  


I use the green


Sorry I meant the grenade style fuze.


If you mean the fuse heads that are from used M67 Practice Grenades that I repurposed in my videos.

https://www.oldsargesdropzone.com/index.php?main_page=produc...



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XeonTheMGPony
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[*] posted on 19-1-2020 at 09:34


Sadly do not ship to Canada, guess I'll have to make the shit from scratch! Use the old Japanese hit initiators.
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wessonsmith
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[*] posted on 20-1-2020 at 12:37


A light dusting of NHN powder at the bottom of an open plastic container. Watch how the single spark slowly falls and ignites the powder. 960 FPS. Even launches the heavy wooden chair off the ground.

https://www.youtube.com/watch?v=eeRUnAByyYs

[Edited on 20-1-2020 by wessonsmith]
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Rosco Bodine
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[*] posted on 17-2-2020 at 11:35


To avoid the requirement for hydrazine hydrate, I am thinking it may be workable to convert more commonly available hydrazine sulfate to hydrazine nitrate, precipitating and filtering out the sulfate value as the low soluble calcium salt, or alternately the barium salt, or perhaps strontium salt, to leave hydrazine nitrate in solution.

Then react the hydrazine nitrate solution with a soluble nickel salt like nickel acetate or nickel nitrate. The soluble nickel salt could be gotten from the commonly available nickel basic carbonate, dissolved in acetic or nitric acid.

What are the kinetics of the reaction and favorable reaction pH value I do not know, but it would seem pH could probably be adjusted basic using aqueous ammonia that would gradually escape from the reaction mixture or be bound to any excess nitrate value. If such a different reaction scheme is workable it would eliminate need for freebase hydrazine as a required precursor and simplify the process for providing an alternative to that less common and more expensive reagent.
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wessonsmith
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[*] posted on 17-2-2020 at 11:46


Quote: Originally posted by Rosco Bodine  
To avoid the requirement for hydrazine hydrate, I am thinking it may be workable to convert more commonly available hydrazine sulfate to hydrazine nitrate, precipitating and filtering out the sulfate value as the low soluble calcium salt, or alternately the barium salt, or perhaps strontium salt, to leave hydrazine nitrate in solution.

Then react the hydrazine nitrate solution with a soluble nickel salt like nickel acetate or nickel nitrate. The soluble nickel salt could be gotten from the commonly available nickel basic carbonate, dissolved in acetic or nitric acid.

What are the kinetics of the reaction and favorable reaction pH value I do not know, but it would seem pH could probably be adjusted basic using aqueous ammonia that would gradually escape from the reaction mixture or be bound to any excess nitrate value. If such a different reaction scheme is workable it would eliminate need for freebase hydrazine as a required precursor and simplify the process for providing an alternative to that less common and more expensive reagent.


pH 6-7 for the entire reaction. It would be an interesting idea to try.

[Edited on 17-2-2020 by wessonsmith]
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Rosco Bodine
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[*] posted on 17-2-2020 at 11:50


Maybe a magnesium acetate buffering could facilitate the near neutral reaction.

Ha! I'll bet Microtek is already trying this to see ! ;) :P

With too many of the ancient wizards that visit here dropping like flies at the end of worldly mission, hopefully in rapture in a lover's arms departing, their angel arrives ..

Until that time for me ...somebody has to take up the slack around here for all the wizards apprentices. :cool:

Every Good Boy Deserves Favour.jpg - 30kB

Additionally I am thinking that if the contemplated scheme would work, the addition of aqueous ammonia, or perhaps NaOH instead, would probably be the needed component for hydrazine freebasing in situ to subsequently provide complexation of a soluble nickel salt to form the low solubility Tris hydrazine nickel nitrate. This would require something in excess of 3 equivalents of NH3 or NaOH to form NH4NO3 or NaNO3 byproduct and 3 equivalents of free hydrazine hydroxide in situ.

The scheme would probably work best to do the hydrazine nitrate plus ammonia or NaOH in one pot, and then to that mixture in excess of theory, gradually add the nickel nitrate solution.

On second thought, the reverse order of addition may work better because of oxidation losses of the free hydrazine. It should work either way, either order of addition, but a benefit of adding the hydrazine value to the nickel nitrate solution would be the free hydrazine would be sequestered by complexation bound to the nickel, and not be vulnerable to air oxidation that destroys hydrazine. Hydrazine is an active reducing agent and has a high affinity for Oxygen of the air, or dissolved oxygen in water which is exactly why it is used as an Oxygen scavenger in boiler water in steam plants.

In my minds eye, the reaction would likely proceed okay in the more basic range probably some above 7 pH, but not too much basic because then the base would displace the complexed nickel from the nitrate instead of the complexed nickel staying where it is desired. It would likely be a reversible equilibrium there where pH could be manipulated to a "sweet spot" value optimum for best yield of the tris hydrazine nickel as the nitrate desired.

[Edited on 2/18/2020 by Rosco Bodine]
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wessonsmith
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[*] posted on 18-2-2020 at 05:19


The only caveat for this new direction in NHN production would be if it also can be done at an elevated temperature. To properly make NHN one needs a temp range of 65-70°C.
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Rosco Bodine
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[*] posted on 18-2-2020 at 10:03


Those temps or even higher should be no issue for nitrates or hydrazine.

Not sure about how the solubilities or reactivity might play well or not play well together, but it is possible that density improvement for the NHN could occur in a reaction mixture in the presence of a chelating agent like glycine or in the presence of a competing complexing agent like ammonia which should gradually be displaced by the lower solubility higher mole weight hydrazine complex. Exploiting some interesting equilibrium shifts in the reaction mixture could enable a slowing of the formation of the NHN that could result in larger mesh crystals having higher bulk density.
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wessonsmith
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[*] posted on 18-2-2020 at 10:59


Quote: Originally posted by Rosco Bodine  
Those temps or even higher should be no issue for nitrates or hydrazine.

Not sure about how the solubilities or reactivity might play well or not play well together, but it is possible that density improvement for the NHN could occur in a reaction mixture in the presence of a chelating agent like glycine or in the presence of a competing complexing agent like ammonia which should gradually be displaced by the lower solubility higher mole weight hydrazine complex. Exploiting some interesting equilibrium shifts in the reaction mixture could enable a slowing of the formation of the NHN that could result in larger mesh crystals having higher bulk density.


With the current production method I use, Dextrin is used to increase the bulk density of NHN from 0.9 g/cm³ to 1.2 g/cm³ and produces an avg crystal size of 13 µm, which is fairly small. The smaller the crystal size, the better with NHN.

[Edited on 18-2-2020 by wessonsmith]
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Rosco Bodine
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[*] posted on 18-2-2020 at 11:41


The use of dextrin, gelatin, PVA, methylcellulose other modifiers is done with other primary explosives to produce a range of greater bulk densities and mesh crystal sizes that can be optimized for a particular use. Stirring speed, intensity of turbulence and reaction temperature are also factors affecting crystal size. The same generality is probably true for NHN which is low solubility and tends to form small crystals, that would be even smaller without any dextrin if the dextrin functions similarly as in the precipitation of other primary explosives. If the smaller the better, then lower reaction temperature and not using any dextrin would be "better" if the process for NHN behaves the same as for example lead azide or silver azide, that can even form as extremely fine colloidal particles. Particle size for a particular use is generally an intermediate mesh, and high bulk density, having crystals not too small and not too large.

I would have to review to be sure I remember this right, but I think I recall reading somewhere a figure of 80 microns for NHN being about right...but it could be silver azide on that ...I am not certain.


[Edited on 2/18/2020 by Rosco Bodine]
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[*] posted on 18-2-2020 at 12:36


Quote: Originally posted by Rosco Bodine  
The use of dextrin, gelatin, PVA, methylcellulose other modifiers is done with other primary explosives to produce a range of greater bulk densities and mesh crystal sizes that can be optimized for a particular use. Stirring speed, intensity of turbulence and reaction temperature are also factors affecting crystal size. The same generality is probably true for NHN which is low solubility and tends to form small crystals, that would be even smaller without any dextrin if the dextrin functions similarly as in the precipitation of other primary explosives. If the smaller the better, then lower reaction temperature and not using any dextrin would be "better" if the process for NHN behaves the same as for example lead azide or silver azide, that can even form as extremely fine colloidal particles. Particle size for a particular use is generally an intermediate mesh, and high bulk density, having crystals not too small and not too large.

I would have to review to be sure I remember this right, but I think I recall reading somewhere a figure of 80 microns for NHN being about right...but it could be silver azide on that ...I am not certain.


[Edited on 2/18/2020 by Rosco Bodine]


With NHN high temperature is a must. Without high temperature, the NHN produced is amorphous in nature whereas the
materials prepared at 65◦C are granular, free-flowing. 13 µm is the average particle size of NHN according to literature and observation. I used to make NHN without dextrin and it didn't perform as well.

NHN produced at 65°C
65c NHN.jpg - 985kB

NHN produced at 25°C
25c NHN.jpg - 632kB




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Rosco Bodine
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[*] posted on 18-2-2020 at 14:06


There is no contradiction in what you have observed. The concentration of a reaction mixture and rate of addition, generally are inversely proportional and act counter to increasing crystal size while temperature increase promotes larger crystals.

Greater dilution, slower addition, longer reaction time, higher temperature, and more turbulence to keep precipitates suspended instead of forming "sand dunes" on the bottom of the reactor promotes crystal growth to larger size, and generally the reverse of those factors results in much smaller crystals.

You could try 90 C and see what results at half the concentration with half rate of addition and 4 times longer reaction time with increased turbulence if needed...to see if there is any difference. But a disadvantage is that yield can suffer when a reaction is not being optimized for yield but for a specific physical form for the product. So what is an optimal synthesis can be a tradeoff to find what is most practical.

[Edited on 2/18/2020 by Rosco Bodine]
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