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Melgar
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Detonation of erythritol tetranitrate (ETN) with heated aluminum
I'm not sure if this is normal, but ETN seems to have a special reaction with aluminum, in that it detonates when in contact with it and heated to
boiling. I tried heating tiny pieces of ETN on various materials steel, aluminum, and glass) and the stuff actually detonated when in contact with
aluminum, though not the other two. So far this has been a very reliable way to detonate it, although the timing would not be nearly as accurate as
with a blasting cap. ETN can even be detonated by wrapping it in aluminum foil and putting a chunk of black powder underneath it to provide the heat.
This would also explain why reports have indicated ETN can be detonated with flash powder, since flash powder tends to have a lot of aluminum in it.
Of course, flash powder isn't all that stable, but I'm willing to bet thermite would detonate it, especially if a little extra aluminum was used.
Anyone have any experience with this?
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User
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Quite interesting.
Did you notice any different behaviour between rapid heating e.g. with BP, or by slow heating on a burner or hotplate?
What a fine day for chemistry this is.
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Melgar
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Ah right. Yes, when heating ETN with aluminum, there was a rapid bubbling and a change in color (to orange) immediately preceding the detonation.
I'm quite certain this orange color was from nitrogen oxides, although I did not repeat the experiment due to the extremely loud noise generated by
said detonation coupled with the fact that I have neighbors. It was a very small amount though, perhaps the size of the head of a pin. It turned the
aluminum foil it was being heated on to a large number of tiny flakes, so I couldn't examine the surface of the aluminum.
When heated on non-aluminum materials, ETN first melted, then boiled, then went "poof", shooting a noiseless jet of flame up as it combusted all at
once.
My current working theory is that there is a highly exothermic reaction between ETN and aluminum at high temperatures, which releases enough energy
quickly enough to create detonation conditions.
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hissingnoise
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| Quote: | | It was a very small amount though, perhaps the size of the head of a pin. |
Surely that small quantity going off wouldn't disturb neighbours if you have any kind of walls between you.
But since you've discovered this interesting principle, the next logical step would be to devise a detonator which uses Al flakes dispersed in ETN
without recourse to a primary.
A small quantity of BP could be pressed onto the mixture to ensure ignition.
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User
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That indeed is what i thought.
Would you mind performing some test with Al powder.
I have some erythritol somewhere what better to do with it than eat it, oh wait.. I could also toss it in a nitrating bath.
This would indeed, if made reliable be better than working with primary's.
What a fine day for chemistry this is.
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chief
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Why not discharge a capacitor through an Al-wire (which is in contact with the stuff) ...
==> That way no timing-problem any more ... (if it works)
If done right and functioning the capacitor could be throwaway, near the charge,
==> so no thick wires etc. necesary
The discharge-contact could be made via eg. a reed-relais (50 ct. a piece) ... remotely controlled by some thin wire and a 9V-Battery ...
Only: Would it be safe to have the Al over long periods in the ETN ? Maybe it would have to get a thin layer of paint or paraffine to prevent any cold
reactions ...
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The_Davster
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The next step is to make sure the detonation does not occur between ETN and Al when stored for a while....
Perhaps also dissolve some ETN in acetone and leave in contact with Al, and separately, copper.
Perhaps repeat the experiment on Mg, see if the electropositivity of the metal has an effect.
Are you sure your ETN is acid free? Synthesis method?
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gregxy
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Maybe it is just that Al is a better conductor of heat
so the ETN heats more rapidly (or the foil is thinner etc).
Was the heating done under controlled conditions?
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Melgar
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Process for making ETN:
mix half and half fuming nitric acid and H2SO4 in a beaker in an ice bath
add erythritol bit by bit (slowly) while stirring until the liquid starts to thicken
add a little bit more nitric acid (like 10% of original volume) and see if the temperature goes up indicating incomplete nitration
if not (it didn't) let it sit for a half hour or so, then dump whole beaker into about 5X its volume of water
neutralize with ammonia, carefully, in ice bath
when pH is basic, filter crystals out of solution (crystals smelled strongly of ammonia)
rinse with distilled water, then let dry
I made two batches, one which was crystallized from ethanol, and one that wasn't. Both had the same reaction with aluminum. The uncrystallized ones
are very pale yellow chunks and the the crystallized ones are white crystals.
The piece I detonated was maybe a little bigger than a pinhead, but it was as loud as a gunshot... not sure i want that noise to be coming from my
house on a regular basis.
However, I have detonated ETN three times by wrapping in aluminum foil and heating it with some sort of fire. (One with black powder, one with
alcohol flame, and another I just threw in some coals from a campfire, carefully of course!) I also detonated it once by just putting a bit on top of
some foil and heating it over a flame.
My thought for reliable detonation was to put a little bit of aluminum-rich thermite on top, then detonate it by igniting the thermite. Another
thought was to bend aluminum wire in a U-shape, then notch the base so that part gets the hottest when you run current through it. Then pack ETN
powder around it. Theoretically, it would also be possible to melt ETN and pour it around the wire, but I don't plan on trying that any time soon
unless I have a death wish. Still, I could heat a tiny bit of ETN in a water bath and see if that heat is enough to detonate it, which it almost
certainly isn't. Maybe use a higher-BP solvent bath and try that, just to see what my factor of safety is.
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Rosco Bodine
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The materials compatability for such a mixture is a huge unknown, but it seems possible that something like a crackling microstar (dragons eggs) type
of mixture
is a definite possibility here.....resulting in an increased output from what is a fulminating mixture undergoing a rapid DDT in small quantities
unconfined.
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hissingnoise
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| Quote: | The next step is to make sure the detonation does not occur between ETN and Al when stored for a while....
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If prolonged contact with the common metals could cause detonation of ETN wouldn't we have known about it long ago?
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-=HeX=-
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I have cast ETN a fair bit. I have found I can add spherical Al to the Molten ETN, without reaction. It is a rather fun mix 
I have had such a mix, in a small charge, for well over a year now. It was 50:50 ETN:Al, the idea was to try make 'thermobaric mix'.
However, with Al flake... ETN can make the DDT, Perhaps the Al particles cause local heating at the points, have a reaction with the ETN causing heat,
then DDT?
I know a fuse through ETN, loose, in Al foil can go DDT. Not reliable though.
I much prefer the Azo Clathrate, Nitrotetrazoles, or DPNA primaries
My DPNA dets PETN... With ~3mg... There is 2mg Lead Styphinate used to 'Fire' it.
If you give a man a match he will be warm for a moment. Set him alight and he will be warm for the rest of his life.
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quicksilver
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I have read whatever I could find on ETN, which were not only the original patents but some background studies from the USBoM & European material
printed close to the time of the patents, encluding studies of ETN from DuPont and Nobel (who apparently struggled for the patent rights). Some of the
material were comparisons of the various nitrated solid alcohols & their stability. I have never heard of a acid-free nitrated polyol or for that
matter nitric ester in general having a sensitivity to a metal [in that there would be a formation of higher sensitivities].
Did you employ a stabilizer when recrystallizing your ETN? Did you check with more than one means, the ph of the product to satisfy yourself that the
material is truly acid free? There are similarities between MHN and ETN in that they demand a ph neutral synthesis to stay stable. They both are quite
stable when neutral and can be exposed to many environmental variables but heat is not one of them.
In the course of reading a particular comparison of impact & heat sensitivity, both nitrated polyols are similar to NG. This can be raised
dramatically with a sample that is not acid free (USBoM 1913). A "rolling boil" can vary in temp due to container but comes close to the level of
heat necessary for detonation. TTBoMK ETN has no sensitivity to aluminum. However if your sample is not acid free you could be playing with fire
especially if you have not employed a stabilizer. ETN was not employed commercially due to the raw material (at the time) being much too expensive to
be practical for profit. MHN was used to a limited degree but the demands for a powdered nitric ester was outweighed by the production cost of #1 Gehr
dynamite.
From a standpoint of concern for safety, I suggest that you check the ph in a manner that satisfies you totally that the product is neutral. The power
of ETN is very close to NG - as is it's demands for an acid-free condition. I have not heard of a common energetic material except Hg Fulminate that
has a sensitivity to Al. However an acidic batch of most nitric esters eventually become "hyper sensitive" to most stimuli (heat, friction, impact,
static discharge). Generally solid alcohols benefit from re-crystallization in that there is an opportunity to remove acid levels from within the
particulate. Employing a stabilizer is generally a standard (Naoum -- US Railway Commission) in that they can deal with extra Nx should that be
necessary (product may be neutral upon synthesis but contaminated in storage, etc.) Nitric esters were frequently re-washed due to the havoc acidic
conditions can render.
Stabilizers do not HAVE to be diphenyalamine. You may use Urea, Betain ( a vitamin B), or the physical presence of an antacid (not truly a stabilizer
but serves).
Be safe. If you notice higher levels of sensitivity than in the past - check until you are satisfied! However, if you are not very familiar with
nitrated solids, ETN (or MHN in particular) note that they are VERY sensitive & should be treated with the same caution one would NG, Flash, or
any material that demands elimination of ignition stimuli.
[Edited on 13-3-2010 by quicksilver]
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Melgar
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Another thought is that ETN is an oxidizer of sorts, in that when it decomposes, oxygen is one of the decomposition products. Now, if enough heat was
generated from the reaction of this oxygen with aluminum, isn't it feasible that the reaction rate could increase fast enough to cause detonation?
This would be especially true for ETN that was already near its decomposition temperature, as much of it would be.
Now, for both batches of ETN, the crystals were made basic with ammonia, then allowed to evaporate, then rinsed, then allowed to evaporate for a
really long time (like a week). Now, I doubt there would be a significant amount of acid remaining because of the excess of ammonia, and any extra
ammonia would have evaporated a long time ago, plus it tested neutral with test strips, so I really don't think acid is what's doing it, unless it's
formed in-situ from the decomposition of the ETN.
I don't suppose anyone has a small amount of ETN to verify this reaction with? It would be at most an easier way to detonate ETN and at least a huge
warning to anyone who plans to use the stuff.
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quicksilver
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While the molecule does carry oxygen ETN is not an oxidizer; it's actions when heated would most likely yield nitrogen first prior to anything. It's
good to hear that you washed the yield with a basic material and did a test. However, there are exposure phenomenon such as placement in a container
wherein an acid existed, etc, etc. I am only re-iterating this for surety's sake and the description of what may have been "a reaction". Principally
because the last damn thing I want is for anyone to get hurt. One thing that would certainly help is a re-crystallization. ETN is interesting in that
acetone is actually a bit too strong a solvent and ethanol or methanol is generally used (or a mix ). The re-crystallization opens the material to
antacids and is a solid way to make sure a bit isn't creeping around in there & is the most opportune time to test for acidity.
Decomposition in nitric esters is accompanied by the release of Nx and the smell generally alerts one to that issue. Smokeless powder has been known
to decompose to the point of seeing the "brown fumes" when a container is opened. Nitric esters have some similarities in that respect. Getting in the
habit of using a stabilizer is always a good move. And the best opportunity to use it is during a re-crystallization. One of the difficulties when
reading written descriptions is that the reader does not see the phenomenon. The material IS seriously sensitive & packs a punch: that's a fact!
Likelihood is that as long as you check on it periodically & respect it like you would NG everything will be fine.
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The_Davster
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Quote: Originally posted by Melgar  |
I made two batches, one which was crystallized from ethanol, and one that wasn't. Both had the same reaction with aluminum. The uncrystallized ones
are very pale yellow chunks and the the crystallized ones are white crystals.
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This is what I was wanting to know. While in solution during recrystalization did you do any neutralization?
As quicksilver says, base rinsing while solid can leave small traces of acid trapped within the crystal.
I am trying to eliminate the possibility of acid traces having a reaction with the metal. This would release nitrous gasses greatly accelerating
decomposition.
When you said it turned orange, was it just a small layer at the bottom where it was in contact with Al, or was the pile completely orange?
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Melgar
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| Quote: Originally posted by The_Davster | This is what I was wanting to know. While in solution during recrystalization did you do any neutralization?
As quicksilver says, base rinsing while solid can leave small traces of acid trapped within the crystal.
I am trying to eliminate the possibility of acid traces having a reaction with the metal. This would release nitrous gasses greatly accelerating
decomposition.
When you said it turned orange, was it just a small layer at the bottom where it was in contact with Al, or was the pile completely orange?
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I checked the pH of the dissolved ETN, and it was neutral. When I put it over the flame, it first melted to a clear liquid, then the orange color
started to appear from the bottom once it started to boil. But the amount was very small and the detonation followed this phase almost immediately,
so I wasn't able to observe it that closely. However, I can state for certain that I didn't see the orange color when I did the same thing on steel
and glass. Although, thinking about it, the steel was really dark and the glass didn't provide any contrast, so I'll have to try that again with
closer observation.
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quicksilver
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What you're seeing is decomposition....This is pretty common nitric ester phenomenon. Imagine what happens with a so-called "run-a-way"......What do
you see? Those red-brown fumes, right? So when you expose the material to decomposition stimuli like heat, you get a change in color. The
decomposition continues....to a point; & then the material breaks down. And when it breaks down, you have an energetic reaction.
.....Sounds like all is cool & and well. The original phrasing of the 2nd post made it seem like the stuff was "going orange on you" for no
apparent reason. - Thus the concern. Think of color changes that occur as a rattle from a snake; unless there is voluntary input on your part (heat,
etc).
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chief
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Anyhow there was a thread on roguesci where they detonated stuff with exploding wires,
==> i.a. capacitor-discharges through thin wires ...
A larger Capacitor will have at 1 kV an amout of energy expressable in terms of "grams of TNT", and the release is just as quick as the circuit
permits ...
==> So it's no big deal to create a shockwave around a thin wire ...
Has anyone tried that ? Probably much safer than handling primary-explosives ...
[Edited on 14-3-2010 by chief]
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hissingnoise
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Nitromannite is close to being a primary as it can detonate from the heat of the flame of a match.
It's a good candidate for this kind of experimentation. . .
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Microtek
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If this turns out to be a real and reliable way to induce detonation, I think you just missed out on a possible business opportunity. I can certainly
think of quite a large number of uses for such a phenomenon.
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User
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| Quote: |
Anyhow there was a thread on roguesci where they detonated stuff with exploding wires,
==> i.a. capacitor-discharges through thin wires ...
A larger Capacitor will have at 1 kV an amout of energy expressable in terms of "grams of TNT", and the release is just as quick as the circuit
permits ...
==> So it's no big deal to create a shockwave around a thin wire ...
Has anyone tried that ? Probably much safer than handling primary-explosives ...
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I assume you are familiar with the term "EBW" and its complications for assembling a decent system, not saying it is impossible.
Or do you mean incorporating such a system into the Al+ETN idea, e.g. pumping a lot of power into a Al wire so that it super heats(burning or
evaporating) very sudden thus detonating the ETN?
The last case I described would seem plausible.
It would be a very controllable method.
[Edited on 15-3-2010 by User]
What a fine day for chemistry this is.
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Microtek
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I tried a setup like that a few years ago. It wasn't a true EBW, but a piece of cardboard with a strip of Al foil glued on. The foil covered both
sides, crossing a single edge. I then cut out triangular sections of the foil where it crossed the edge so only a ca. 1 mm bridge connected the two
sides. Leads were then connected to the sides and two capacitors from disposable cameras were discharged through the setup.
The narrow bridge of Al foil exploded with a very sharp crack, so I tested an identical setup in a 3 mm ID brass tube with loosely packed MHN.
This produced an explosion that ruptured the brass tube, but didn't produce a large number of fragments.
So I just concluded that either it was a low order detonation or a deflagration.
Either way, with sufficient tweaking it could definately be employed in a detonating train, but the question is how much reliability you would
sacrifice for a little safety.
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chief
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Of course I talk about detonating the Al-wire ...; not sure what you mean with EBW, probably "exploding bridge wire" ?
The circuit has to be quick enough, that means: Thick enough wires to conduct the energy to the point, resistivity only in the detonating wire, high
enough voltage ...
==> Double the voltage at the same capacitance gives 4 times the energy, double the speed and 8 times the peak-wattage ... (linear assumptions
...), so much more meaningful to use 5 kV than 500 V ... ;
I would first try thin copper-wires: Standard-quality obtainable; can be very thin: The discharge will go through the plasma as well ...
Maybe another way is possible: Discharge through a thin layer of insulating explosive ... ; maybe with some graphite-content ...
==> Could be much quicker superheated ... (shocked ...)
==> A good insulator will need anything between 5 and 50 kV per mm, so use 5 kV at 0.1 mm ; the plasma will have pressure and extremely high
temperatures, beyond that of any combustion ...
[Edited on 15-3-2010 by chief]
[Edited on 15-3-2010 by chief]
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PHILOU Zrealone
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To my feeling there are two factors that might explain the ease of D2DT of ETN in contact with heated Al foil.
Aluminium and Iron belongs to a class of metals that react weird upon exposure to concentrated HNO3...they get passivated...Aluminium displays a
stonger passivation hability than Iron because it forms a protective unsoluble oxyd layer so HNO3 doesn't need to be as concentrated to lead to
passivation.
The passivity is weird in that it can be deactivated for Iron by a simple contact with a metallic copper piece. The passivity of Aluminium is
dependant on the nature of other dissolved components like ammonium cation, chloride anion...
1°)So it can be that during your neutralisation process with ammonia you make some NH4NO3 and that this allows the Al to be unpassived and
unprotected by an oxyd layer and therefore very much more reactive (strong reducer).
Upon contact with NH4NO3, Al foil is rapidly chewed through and this oxydation process evolves heat!
I find strange that you use strong ammonia base to affect neutralisation while mild neutralisation by carbonate/bicarbonate is the favoured way to
conserve the polyesterification level; strong base inducing the reverse reaction to the esterfification (nitratation); thus the hydrolysis.
2°)It can be that during the heating some ETN decomposes leading to HNO3, HNO2, NOx and carboxylic acid moeties (from the oxydation of the alcoholic
functions)...then HNO2 and carboxylic acids corrodes the Al leading to unpassivation and naked unprotected Al. Aluminium salts are very prone to
hydrolyse and so their pH in water is very acidic! I suppose that during the unpassivation process locally you have high acidity spots.
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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