nickel hydrazinium nitrate

Primary resistant to impact
 
Nickel hydrazine nitrate is a potential primary explosive that shows good resistance to impact, while still being easily initiated by flame.
This means that the complex salt may likely be safer to handle than other primaries.

The sensitivity to impact (the hammer drop height value at which the sample has a 50% chance of detonation) is 84cm. It is resistant to friction up to 10N, resistant against electrostatic discharge, but is sensitive to flame and will explode in contact with a red hot wire.

Another advantage, small amounts of the compound do not need confinement to detonate. Nickel hydrazine nitrate shows excellent initiating power for a primary. The detonation velocity 7km/sec.

One note of warning, nickel hydrazine perchlorate is dangerously sensitive to friction. An accident involving only 5 grams cracked a fragment off a laboratory table and resulted in severe injury.

Here is a video:
http://wn.com/Nickel_Hydrazine_Nitrate

Here is the accident involving the perchlorate:
http://pubs.acs.org/cen/science/88/8834sci1.html


PREPARATION:

1. Take Nickel nitrate (green emerald salt) saturate hot water with it...then add for 1 volume of this 1 volume of ethanol (80-99%) is fine.You have now a green ethanolic solution of Ni(NO3)2.

2. Perform the same mix but with concentrated hydrazine...use i.e. 80% NH2-NH2 what equals NH2-NH2.H2O the monohydrate....take one volume of this and add one volume ethanol. Alternatively, react hydrazine sulphate with Ca/Ba hydroxide, and filter Ca/BaSO4 off to be left with a solution of hydrazine. Theoretically, 0.57 grams of calcium hydroxide will completely react with each gram of hydrazine sulfate present.

3. Take the whole hydrazine batch and add dropwise under stirring the green alcoholic Ni(NO3)2 solution. A deep blue (saphire) precipitate appears which upon agitation turns lila pinkish. Continue adding the nickel nitrate solution until no more precipitate occurs. It is not a bad idea to filtrate the precipitate from time to time to ascertain whether a green coloration persists (if it does, then stop adding the nitrate solution). While mixing and precipitating, heat the mix a bit so as to adjust the addition speed in a way you can hold the mix (<50°C) (with this phrase i am not sure what he meant - surely the precipitation is works better at lower temperatures?)
The complex salt filtrate is insoluble in ethanol/water which helps fast and smooth precipitation.You get plenty of precipitate and yield is close to 100%.
Make sure the nickel nitrate solution is added in excess so as to completely use up the hydrazine.

4. Once filtered (and possibly washed with 50% EtOH/H2O0, dry on a radiator (60°C max), and after a few hours/days one gets a solid clay like cake. This can be broken ground into small pieces/dust (no risks of explosion as long as you don't hit it with a strong hammer blow...grinding with a spoon is riskless). After grinding allow to dry one more day. After this the complex salt has turned into a pale white dust that burn fiercely and bright white when lit (like nitrocellulose). When wrapped in Al foil, and thrown into a fire, one gets a powerful detonation (whereby the Al foil acts as a weak confinement)




nickel hydrazinium nitrate is described as "hydrolytically stable", which means that it is not vulnerable to moisture (like tetramine copper nitrate is).

The interesting thing about Nickel Hydrazinium Nitrate (NHN) is that it is supposedly somewhat less sensitive to mechanical impact than RDX. Despite this, NHN still easily explodes by being ignited with flame, whereas RDX only burns (moderately fast like a flare) when lit on fire. This resistance to mechanical impact is unusual for a primary explosive. Usually compounds which easily explode when ignited are also mechanically sensitive to detonation.

An interesting thing about nitroglycerin is that while it is very sensitive to mechanical impact or friction, a burning match will actually be extinguished if dropped into a small puddle. Nitroglycerin can even be burned like a candle using a wick without an immediate explosion (do not try this, it is very dangerous). When nitroglycerin was once used in blasting caps, some other primary (such as mercury fulminate) had to be used to first detonate the nitroglycerin, since nitroglycerin itself does not reliably detonate from electrical ignition.

Usually, ideal primaries are ones which detonate easily from flame, but are less sensitive to mechanical impact or friction. This makes them easy and reliable to detonate, but also safer to handle.
 
 

An aqueous solution of nickel nitrate was prepared, containing 8% Ni(NO3)2 by weight. 50mL of the solution was poured into a steel container, which was then heated to 65degC.  Separately, 100mL of distilled water was warmed and maintained at around 60degC. Gradually over the period of 30 minutes, 7cm3 of hydrazine sulfate was added into the steel container, simultaneously together with 50mL of the water that had been separately prepared, the remaining water was discarded. The hydrazine sulfate used was somewhat wet to begin with. The color of the reactants in the steel container changed from a bluish tint to purple over the course of the reaction. The reaction was stirred for an addition 10 minutes, maintaining the temperature at 60degC. After cooling to 20degC, the purple colored product was filtered out over two layers of coffee filter paper, washed once with 50cm3 distilled water. The moist caked solid was then partially dissolved in >98% alcohol (50mL ethanol was used), then the alcohol was allowed to evaporate out on an electric hot plate set to only 60degC. The evaporation should be carried out in the dark, but with plenty of ventilation. About 5 hours are required for complete evaporation. From this procedure, about 11 grams of nickel hydrazinium nitrate is obtained, which is a 90% yield. Heating of the reactants/reaction is not in any way necessary, as similar yields were obtained at room temperature, but the product obtained from heating shows better physical properties, as the salt is of a more crystalline form. The crystalline form has a density of about 0.89 g/cm3. The nickel hydrazinium nitrate thus obtained, when gradually heated, explodes at 219degC. The compound appears thermally stable even up to 200degC. Sensitivity (50% probability of explosion using 2kg drop hammer from variable heights) value of 84cm. Velocity of detonation: about 7km/sec.

 

The co-crystallization of NHN with silver azide, such that the resulting clathrate contains 10% by weight of AgN3, increases the drop height sensitivity to a value of 66cm. Even such a clathrate containing only 2% silver azide is not much less sensitive, having a drop height value of 68cm. As a side note, cobalt hydrazinium nitrate, which can be similarly prepared, is even more sensitive, having a sensitivity drop height value of 59cm. The cobalt salt also explodes at a lower temperature, 188degC. Interestingly, however, the cobalt salt is actually somewhat less sensitive to friction than NHN.

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