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Author: Subject: Please do not "play" with Organic Peroxides.
shadowwinter
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[*] posted on 19-10-2015 at 21:47
additives in our chemicals


Just want to throw a couple of ideas out there.
First it might not be your inconsistencys that cause mishaps.
Think, your chems all come from somewere and if you buy them it might becase of inconsistent methods of manufacture something which is out of our control.

The other thing that I think contributes to the danger of peroxides is how easy it is to make them. I would bet big money if you could make lead azide out of readily available chemicals from the dollar store tomorrow that azide would get as bad or worse of a rep.

Its just like guns some are more common than others and so contribute to more deaths doesn't make them any more lethal.
If you get two idiots and give one Hg fulminate and one TATP who is more of a danger to them selves? Exactly its not the compounds but who gets the compounds and right now its easier for someone who has no clue about explosives to make peroxides therefore its common sense that they would cause more injury's to clueless individuals hence the bad rep.

Hmmm my HMTD from what you guys say is unusually safe it is very difficult to detonate with hard blows from a hammer but is quite sensitive to flame.
Could this be from additives in my H202?
It says that it contains phosphoric acid and phenacetin and is 6% home essentials brand are these normal additives?
Am I just lucky?
Also beware peroxides are very touchy on a full moon. Jk.
This is all just my opinion.


[Edited on 20-10-2015 by shadowwinter]

[Edited on 20-10-2015 by shadowwinter]
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[*] posted on 19-10-2015 at 21:59


Quote: Originally posted by shadowwinter  


The other thing that I think contributes to the danger of peroxides is how easy it is to make them. I would bet big money if you could make lead azide out of readily available chemicals from the dollar store tomorrow that azide would get as bad or worse of a rep.

[Edited on 20-10-2015 by shadowwinter]


But you like... Can make lead azide from dollar store chemicals? Sure, it's not as easy as mixing three liquids to make TATP but I think you just lost your big money.

I get your point, and that certainly makes the reputation worse but I still feel they are very dangerous materials without the reputation.
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shadowwinter
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[*] posted on 19-10-2015 at 23:17


Damn I always lose bets.
I see your point even though you might have to go through a long painful and frustrating process of making all the precursors it could be done.
But then again not quite shure how.



[Edited on 20-10-2015 by shadowwinter]
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[*] posted on 20-10-2015 at 00:04


Ok let's see. Bleach, sodium hydroxide, alkali nitrate, sulphuric acid, lead, isopropanol and urea are all that is needed for lead azide. You probably can't get lead at the dollar store but I found mine on the ground so I think it still counts :P

Also I'm pretty sure you meant 'long and joyous process'

[Edited on 20-10-2015 by Tdep]
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[*] posted on 20-10-2015 at 00:13


Oh Tdep. You almost inspire me to make some. Almost.
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[*] posted on 20-10-2015 at 00:26


You could get lead from solder if your lucky.
Build challenge see who can make the best primary and secondary from either the dollar store or super market .
Post your results here.
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shadowwinter
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[*] posted on 20-10-2015 at 00:29


Quote: Originally posted by Tdep  
Ok let's see. Bleach, sodium hydroxide, alkali nitrate, sulphuric acid, lead, isopropanol and urea are all that is needed for lead azide. You probably can't get lead at the dollar store but I found mine on the ground so I think it still counts :P

Also I'm pretty sure you meant 'long and joyous process'

[Edited on 20-10-2015 by Tdep]
joyous hmm depends on my mood sometimes its therapeutic sometimes frustrating.
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[*] posted on 20-10-2015 at 00:45


Shadow, from what i have heard HMTD is more sensitive to heat/friction/shock initiation because of the weak double oxygen bonds in it's molecular structure.

If you gave one idiot mercury fulminate or lead azide and another acetone peroxide, it would probably depend on the amount of knowledge each idiot had on handling the compounds, the slightly more educated idiot in handling primaries would probably be less likely to have an accident. If they both had the same knowledge though, the idiot without the HMTD would probably feel safer.
I used to use AP as the primary charge in detonators and have since moved to Lead azide.
In my eyes, properly prepared lead azide is far superior to use than organic peroxides if you can obtain the precursors.

With HMTD, you have an explosive that needs to be used straight away to avoid decomposition, has a low ignition point and heat stability (130 degrees C I think) and is quite a high sensitivity to shock and friction.

Compare this with lead azide which is storage stable when properly manufactured, has a high heat stability (300 Degrees+ causes detonation) and is less sensitive to friction and shock from my experience as long as you watch the crystal size. I suppose it loses points because of the toxic precursors though.







[Edited on 20-10-2015 by greenlight]




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[*] posted on 20-10-2015 at 01:03


Yes though I am still very new to this I have to agree with you.
I just find it unusual my last batch of HMTD refused to detonate after multiple strikes with a hammer on a piece of wood.
The varying degrees of sensitivity must be caused by something and if it can be figured out what I believe accidents would decline.

Side note I am looking for a new primary because of the horror stories surrounding HMTD.
Must be non toxic storable and easy to synth any suggestions?
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[*] posted on 20-10-2015 at 01:07


Doesn't LA create toxic dust/fumes upon detonation?
If so is it enough of a problem to worry about?
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[*] posted on 20-10-2015 at 01:41


I used to have AP batches that were considerably less sensitive than others and could sustain a fairly good wack with a hammer without initiation. I think one factor that helps is temperature, the best batches were done with the temperature never rising above 5 Degrees to promote formation of the safer trimer form.

That is the problem, all the less sensitive primaries are more complicated to synth and require more advanced or toxic chemicals. You would be hard pressed to find a safer primary that is easier or as easy to produce as organic peroxides hence why everyone uses them to start.

I believe you are right, the lead azide is toxic itself and does create toxic fumes when detonated, just don't test small amounts in an enclosed space or close to you.

[Edited on 20-10-2015 by greenlight]




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[*] posted on 20-10-2015 at 02:17


For my next primary I might try to make ETN for thermal shock detonators.
They are a lot safer though less reliable or maybe DDNP.
I'm going to try my first secondary this weekend which will be ANWAX initiatiated with a 4 gram cap of HMTD in a tightly rolled paper tube these things are loud.
You really don't have an appreciation for how powerful these are until you've seen and felt them.
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[*] posted on 20-10-2015 at 03:13


ETN is not really a primary explosive, it is much more stable and can be rolled into a plastic explosive which you would never attempt with primaries.
If you stick a detonator in your ETN that would be your first secondary.
It acts like a primary if heated very rapidly like in a thermal shock detonator like you mentioned but other than that a detonator is needed.
Nitro-genes and Roscoe bodine have done an enormous amount of work on a DDNP synth from common paracetamol tablets which I haven't tried the updated final step yet but Nitro-genes has gotten product from it.




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[*] posted on 20-10-2015 at 05:14


AP can be less sensitive if small quantity of water or oil is added to it. I mentioned the reference paper in this post.
I like AP coz it is very easy to synthesis , cheap , non-toxic , fast to make , powerful , ...

ETN/PETN are perfect as secondary EM. They are widely used for NG to achieve the high velocity.
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[*] posted on 20-10-2015 at 06:40


p-DDNP almost rivals AP in terms of cost, in return you get something that isn't as INSANELY friction sensitive and prone to sublimation as AP. It's synthesis is listed here:
https://www.sciencemadness.org/whisper/viewthread.php?tid=63...

To put the difference in friction sensitivity between the two in perspective; DDNP is considered to be still somewhat sensitive to friction as a primary, having a friction sensitivity of between 40 and 5 N. For AP it is listed as 0.01 N, this means DDNP is between 4000 and 500 times less sensitive to friction as AP...just to give you an idea...

To give a couple of real-life examples of how these properties of AP have lead to severe injury or even death:

1. AP was pressed in a drinking straw as a detonator for an ammonium nitrate based explosive. Ammonium nitrate as a tendency to cake, turning the secondary into a rock hard stuff over time. On site though, you are filled with adrenalin and when the detonator doesn't get in immediately you decide to push harder, the straw bends generating enough friction to set off the AP...end of story

2. A detonator using AP was made some time ago, but since it still looks OK you decide to use it anyway. You insert the detonator and light the fuse...end of story. Sublimation of the AP has filled the spaces in between the blackpowder grains within the fuse, basically turning it into detcord instead of a slow burning fuse.

3. AP was stored in a screwlid type container, since making it everytime is of course a lot of work. The sublimed AP immediately detonates when the lid is unscrewed...end of story

4. A small amount of AP was poured into a detonator, halfway pouring, the detonator explodes prematurely....fingers flying..jerking off and wiping your ass will never be the same. Yes...AP has been know to explode while simply pouring it from a paper. Maybe static electricity, friction or perhaps a combination of both, but there a several stories where this has happened. Make no mistake, the fact it hasn't happened yet doesn't mean it can't happen.

5. AP exploded while drying outside. Yes, these peroxide bonds are so unstable that UV light is enough to break them pretty fast.

The isopicramic acid takes only 1 day to synthesize, and can be stored and handled safely. Despite the suspected toxicity of picramic acid, it is still used in certain types of hairdyes, everything is relative I guess. Same goes for the synthesis of AP: ever got stinging eyes from the drying AP? It is because of the chloroacetone formed during synthesis using HCl as catalyst. Did you know it is extremely mutagenic and has been used as a war gas? --> https://en.wikipedia.org/wiki/Chloroacetone

If you would have isopicramic acid, if a primary is needed, all you would need to do is basically dump 1 gram of isopicramic in any mineral acid available, dump in 0.4 grams of any nitrite solution, stir a few minutes and presto...an on demand, exceptional primary in quantitative yield, in under 5 minutes. Since you need only 100 mg, you could store the other 900 mg in a plastic tube under demineralized water. No problem, DDNP can be stored for long periods of time and even safely transported that way...

Silver acetylide nitrate double salts are also a good choice, 50-100 mg suffices for ETN or PETN.

[Edited on 20-10-2015 by nitro-genes]
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[*] posted on 20-10-2015 at 12:45


Thanks for all the advice I think I might try That DDNP synth and see how it gos.
Wow I had no idea there was that much of a difference in sensitivity. Out Of curiosity why are the military detcaps so safe? Have they had many accidents involving them.

Thank you all for your time it is highly appreciated
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[*] posted on 20-10-2015 at 14:39


Quote: Originally posted by nitro-genes  
p-DDNP almost rivals AP in terms of cost, in return you get something that isn't as INSANELY friction sensitive and prone to sublimation as AP. It's synthesis is listed here:
https://www.sciencemadness.org/whisper/viewthread.php?tid=63...

To put the difference in friction sensitivity between the two in perspective; DDNP is considered to be still somewhat sensitive to friction as a primary, having a friction sensitivity of between 40 and 5 N. For AP it is listed as 0.01 N, this means DDNP is between 4000 and 500 times less sensitive to friction as AP...just to give you an idea...

To give a couple of real-life examples of how these properties of AP have lead to severe injury or even death:

1. AP was pressed in a drinking straw as a detonator for an ammonium nitrate based explosive. Ammonium nitrate as a tendency to cake, turning the secondary into a rock hard stuff over time. On site though, you are filled with adrenalin and when the detonator doesn't get in immediately you decide to push harder, the straw bends generating enough friction to set off the AP...end of story

2. A detonator using AP was made some time ago, but since it still looks OK you decide to use it anyway. You insert the detonator and light the fuse...end of story. Sublimation of the AP has filled the spaces in between the blackpowder grains within the fuse, basically turning it into detcord instead of a slow burning fuse.

3. AP was stored in a screwlid type container, since making it everytime is of course a lot of work. The sublimed AP immediately detonates when the lid is unscrewed...end of story

4. A small amount of AP was poured into a detonator, halfway pouring, the detonator explodes prematurely....fingers flying..jerking off and wiping your ass will never be the same. Yes...AP has been know to explode while simply pouring it from a paper. Maybe static electricity, friction or perhaps a combination of both, but there a several stories where this has happened. Make no mistake, the fact it hasn't happened yet doesn't mean it can't happen.

5. AP exploded while drying outside. Yes, these peroxide bonds are so unstable that UV light is enough to break them pretty fast.

The isopicramic acid takes only 1 day to synthesize, and can be stored and handled safely. Despite the suspected toxicity of picramic acid, it is still used in certain types of hairdyes, everything is relative I guess. Same goes for the synthesis of AP: ever got stinging eyes from the drying AP? It is because of the chloroacetone formed during synthesis using HCl as catalyst. Did you know it is extremely mutagenic and has been used as a war gas? --> https://en.wikipedia.org/wiki/Chloroacetone

If you would have isopicramic acid, if a primary is needed, all you would need to do is basically dump 1 gram of isopicramic in any mineral acid available, dump in 0.4 grams of any nitrite solution, stir a few minutes and presto...an on demand, exceptional primary in quantitative yield, in under 5 minutes. Since you need only 100 mg, you could store the other 900 mg in a plastic tube under demineralized water. No problem, DDNP can be stored for long periods of time and even safely transported that way...

Silver acetylide nitrate double salts are also a good choice, 50-100 mg suffices for ETN or PETN.

[Edited on 20-10-2015 by nitro-genes]


I totally agree that AP is not the best primary but it has a lot of advantages as stated in this post.
Primaries should be handled only by experts.
I always store AP under water to avoid point 3.
point 1 is a mistake because he didn't use a metal casing !

DDNP seems not that easy to be made compared to AP but I would give it a try.

If you want to be more safe you can use chlorates as primary. I found some patents on google (Primary detonating explosive US 2127106 A) that use KClO3 with other additives to form a primary which has better sensitivity and thermal characteristics
I am not sure if Armstrong mixture can be used as primary !

[Edited on 20-10-2015 by ecos]

[Edited on 20-10-2015 by ecos]
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[*] posted on 20-10-2015 at 18:25


Nice writeup on the AP sensitivity and accidents Nitro, really puts it into perspective.

Shadowwinter, the military detonators are made in a factory remotely not up close by hand I believe. They use aluminium casings and lead azide as the primary which would be pressed remotely.
The military caps have the contents pressed and are also completely sealed up as well so nothing can move inside.
They are mostly electrical initiated making them even safer than fused caps as well.

So a combination of good grade safer explosives, remote pressing and manufacture, sealed design and electrical ignition all make them safer to handle and use.


[Edited on 21-10-2015 by greenlight]




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[*] posted on 21-10-2015 at 02:50


Remote pressing ? I like this idea. I never thought of it.

I found a video for pressing blasting cap using special tool :) : https://www.youtube.com/watch?v=zkfiKlYDxno
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[*] posted on 21-10-2015 at 04:40


"I totally agree that AP is not the best primary but it has a lot of advantages as stated in this post".

Apart from the fact it is easy to make, name one

"Primaries should be handled only by experts."

After some experts and professionals lost their fingers due to AP, experts consider AP to dangerous to handle.

"I always store AP under water to avoid point 3."

Not sure about this one, but IIRC there was someone on roguesci a long time ago, who actually tested how efficient water was in stopping sublimation and surprisingly...AP still sublimed even when kept under water

"point 1 is a mistake because he didn't use a metal casing !"

What metal casing would you use? Some metals, like copper may be very dangerous in combination with AP. To my knowledge it has never been published, patented or otherwise studied what incompatibilities and best conditions for AP are for use in detonators. Why do you think this is?


"If you want to be more safe you can use chlorates as primary. I found some patents on google (Primary detonating explosive US 2127106 A) that use KClO3 with other additives to form a primary which has better sensitivity and thermal characteristics"

Apart from the fact that sulfur nitride is pretty hard and dangerous to synthesize, chlorates aren't very useful as a primary for a number of reasons. One is their incompatibility with acids, forming chlorine dioxide, which ignites with almost anything organic. Second is that, rarely, oxidizer/fuel mixtures produce enough peak pressure to reliably initiate secondaries. Chlorate mixtures produce maybe few kbars peak pressure, DDNP about 240 kbars for example.

The example with sulfur nitride is different, since the sulfur nitride itself adds a lot of energy itself apart from being a fuel. Maybe you were contemplating to mix chlorates and AP to desensitize the AP, but whatever you do, don't mix organic peroxides with anything! AP with potassium chlorate WILL explode in storage or upon mixing due to trace acids present from the AP synthesis!

"I am not sure if Armstrong mixture can be used as primary!"

Mixtures like armstrongs are among the most sensitive compo's around. Its quite a challenge to dry-mix small amounts of KClO3 and red P without explosion.

[Edited on 21-10-2015 by nitro-genes]
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[*] posted on 21-10-2015 at 15:50


Hi Nitro-genes, Thanks a lot for the info you provided in your last thread. I wasn't aware of many of them.

I think chlorate/perchlorate mixtures would have enough power to initiate ETN ! no need for 240Kbars. this would do the job after that.

I have the aim now to find a better primer rather than AP but I have a real problem to find concentrated Nitric acid/nitrate salts . I can get them in small quantities.
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[*] posted on 22-10-2015 at 06:40


No problem, I've had a close encounter with organic peroxides myself a long time ago. Information on fora like this didn't exist back then. Suffice to say, I'm very lucky to have all fingers and limbs still attached...

I'm actually surprised you are able to find and buy hydrogen peroxide and perchlorates, but no nitrates. Over here >3% hydrogen peroxide is no longer sold in general stores, and asking for a liter of 30% at the pharmacy will raise some eyebrows and they will ask some questions what you need it for. I heard some kid was got a visit from the police because he ordered 30% hydrogen peroxide. :o

Anyway, for example...you could try NPEDs based on ETN, in which case you don't need a primary at all --> (http://www.sciencemadness.org/talk/viewthread.php?tid=24817

Another composition worth mentioning is 60% potassium picrate/40% potassium perchlorate (dont use chlorates insetad!). With strong cap confinement I have no doubt it could set off ETN. This composition is chemically very stable, and almost insensitive towards friction or impact. Picric acid is easy to make, even in small quantities. Just search the forum.
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[*] posted on 22-10-2015 at 09:19


Quote: Originally posted by nitro-genes  


Another composition worth mentioning is 60% potassium picrate/40% potassium perchlorate (dont use chlorates insetad!). With strong cap confinement I have no doubt it could set off ETN. This composition is chemically very stable, and almost insensitive towards friction or impact. Picric acid is easy to make, even in small quantities. Just search the forum.

Why not with KClO3?

This would make it close to KClO3/Na benzoate (or NaClO3/K benzoate detonating wistle mix of Dornier) and to the hypothetically more powerful mixes with nitrobenzoates, dinitrobenzoates or trinitrophenates instead of the benzoates...

K picrate/KClO3 must be stable to a certain impact and heat level since there is no reason for sensitization of the KClO3 by acid traces or NH3 (the two main dangers with chlorates).

By the way, the S4N4 with chlorate patent is a good idea to use the detonability of S4N4 and to boost the energy output by burning down the sulfide as SO2.

--> To make things even more detonating/sensitive; one may go further and use:
-detonating chlorates (Hg(ClO3)2 or AgClO3) or chlorites (Hg(ClO2)2 or AgClO2).
-Maybe some permanganates like Hg(MnO4)2 and AgMnO4...
-Some detonating heavy metal nitroformiates (Hg(C(NO2)3)2, AgC(NO2)3)

Mercury is interesting because it will get more oxydizer per weight being bivalent and because HgO is unstable above a certain temperature and set O2 free!
HgO -heat-> Hg(g) + 1/2 O2(g)
But also gaseous Hg... :(


[Edited on 22-10-2015 by PHILOU Zrealone]




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[*] posted on 22-10-2015 at 15:26


@nitro-genes.
It is a problem in my country to buy any nitrate salt since nitrate=explosives to many
I can buy AN in small amounts (~2 Kg) from fertilizers stores. It always have a lot of impurities and costs more than 1 liter of H2O2 with 50% concentration. I know that sounds wired but this is my country !

H2O2 with 30% will not be a problem if you mention that you use it for hair bleaching !
I know a chemical store where I can buy 50% concentration without a problem. Acetone is hard to find with high concentration.

after reading your post again and again I would say I am convinced to stop using AP and find a better alternative.
I am interested to read more about chlorate since I became fan of propellent more than explosives but anyway I found two patents for chlorate as detonator :
1-Detonator composition US 1462075 A:
70% to 90% of nitrostarch + 10% to of potassium chlorate or ammonium perchlorate + 1% to 10% of Urea
This has same strength as a detonating cap of mercury fulminate of what is calle No. 6 grade
2-Non-primary detonators WO 2000026603 A1 (same as PHILOU Zrealone last post)
5 to 15% potassium picrate, 5 to 15% potassium perchlorate and 70 to 90% PETN
since PETN exists it would be strong detonator.

[Edited on 22-10-2015 by ecos]
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[*] posted on 22-10-2015 at 17:03


Hair bleaching huh... with 50% you'll do more than just bleaching your hair. :) And yes rocketry can be pretty cool as well. https://www.youtube.com/watch?v=CxjSMej7wZg

@Philou:

Agreed, a mix of pure potassium picrate (without traces of free picric acid) and chlorates, pressed on thoroughly bicarb neutralized and recrystallized ETN should be no problem at all. The chlorate mix will probably even accelerate somewhat faster than with perc. Chlorates are avoided in pyrotechnics whenever possible for a reason though and somehow the shelf life of many compositions containing chlorates and sulfur is pretty limited and are considered dangerous to store :)

The sulfur nitride is interesting indeed, it is one of these energetic compounds that has been mentioned many times, but for some reason I've never read any actual hands on experiences about this compound in energetics related fora, perhaps since it requires disulfur dichloride (a rather high profile chemical to have at home) and a good lab setup. Being patented says little about the long term stability of a S4N4/chlorate mix, for instance, is there a chance sulfur oxides/acids can be formed from direct/indirect hydrolysis with moisture? Interesting from an experimental point of view though...
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