Sciencemadness Discussion Board - HMTD safety

HMTD safety

mewrox99 - 28-9-2010 at 20:49

I'm thinking of making some HMTD sometime. Simply because it seems like an interesting substance.

I have no intentions of detonating it. I just think that deflagrating <100mg amounts with my 200mW laser would make for a cool youtube video.

I have some questions though.

Is spontaneous detonation likely? If taking precautions against shock and static electricity. I have made organic peroxides before and my limbs are intact.

Am I following a safe synthesis.

25mL of 6% H2O2 is chilled
In an ice bath 1.4g of Hexamine is added slowly and dissolved
2.1g of Citric Acid is added with stirring in small portions
It is stirred slowly.
It is left in a ice bath for three hours.

The crystals are collected and left to dry in a dark place.

I have played with organic peroxides before. But I've heard HMTD is really really dangerous.

Which synthesis is safer, citric acid or HCl

I also did research on legality and where I live HMTD is not listed as a controlled explosive. Neither is TATP.

[Edited on 29-9-2010 by mewrox99]

hissingnoise - 29-9-2010 at 01:58

FLchem10 had a disquieting experience with HMTD.
You might want to scroll down and read his thread.
IMO, the safest synthesis for HMTD is the one in COPAE.

mewrox99 - 29-9-2010 at 02:09

I read that before posting scary stuff.

I'll be using a lot less. Whats COPAE

hissingnoise - 29-9-2010 at 02:14

It's "The Chemistry of Powder and Explosives" by Tenney L Davis and it can be downloaded from the site library. . .

franklyn - 29-9-2010 at 15:37

http://www.sciencemadness.org/talk/viewthread.php?tid=14514#...

.

Engager - 4-10-2010 at 00:02

HMTD is a mess. Personally i think that acetone peroxide is much safer to handle. One exotic manner about HMTD is that it can produce spontaneous explosions on storage and during crystallization. I heard many stories about it, some people on forums here in Russia propose even to store it in numerous small batches scattered in different places since in this way it is less likely that the whole mass go boom spontaneously. I personally heard a story then carefully deacidified and phosphate stabilized HMTD exploded then guy was doing vacuum cleaning of carpet at his room, one another story was that stored HMTD exploded from shock of closing room door.
One of the main disadvantages of HMTD is that it is slowly decomposes at storage, rendering it's behavior unpredictable. Acetone peroxide is volatile and looses mass on storage due to vaporization, but it is not decomposed at common temperature (then carefully deacidified and stabilized of course). So i advise to handle HMTD with great care and dispose of it as soon as possible.

1. This ref describes spontaneous explosions of HMTD (on Russian language):

Attachment: Spontaneous Explosions Of HMTD (Fogelzang).djvu (1.3MB)
This file has been downloaded 1664 times

2. Decomposition of a Multi-Peroxidic Compound: Triacetone Triperoxide (TATP), Propellants, Explosives, Pyrotechnics 27, 209 ± 216 (2002).

Attachment: Propellants, Explosives, Pyrotechnics, Volume 27, Issue 4 (p 209-216).pdf (212kB)
This file has been downloaded 1729 times

3. Decomposition of a Multi-Peroxidic Compounds. Part II. Hexamethylene triperoxide diamine (HMTD). Thermochimica acta 388 (2002) 215-225.

Attachment: HMTD.pdf (162kB)
This file has been downloaded 1810 times

4. Some insights on spontaneous explosion problems on crystallization can be found in this book: Fast reactions in solids / F.P. Bowden and A.D. Yoffe. In chapter 8. I can attach this book here, but i have only Russian version. Details on original English book: http://catalogue.nla.gov.au/Record/769453

[Edited on 4-10-2010 by Engager]

mewrox99 - 4-10-2010 at 03:18

I have made TATP before. Is it safer than HMTD.

Engager - 4-10-2010 at 03:50

Yes it is. It is also far more stable if properly purified from acid. It can be stored in frost camera of freezer for many years without any change. Some long time ago i personally stored it for at least 5 years in form frozen with some water, after defrost i recovered completely unchanged material.

DDTea - 4-10-2010 at 04:09

If you only want to set off ~100 mg batches of HMTD with a laser, why are you trying to make >1 g quantities? Prepare as much as you're going to use so you don't have to worry about storage, which will create an added headache for you.

madscientist - 4-10-2010 at 07:00

Acetone peroxide sublimes when stored, forming crystals that you won't want to break.

Nothing with "peroxide" in the name is safe. Period. It's only a matter of time and chance before something goes off semi-randomly. If you must make organic peroxides, keep the amounts small enough that you could live with them going off at any point during handling.

The WiZard is In - 4-10-2010 at 07:56

Quote: Originally posted by Engager

HMTD is a mess. [snip]

4. Some insights on spontaneous explosion problems on crystallization can be found in this book: Fast reactions in solids / F.P. Bowden and A.D. Yoffe. In chapter 8. I can attach this book here, but i have only Russian version. Details on original English book: http://catalogue.nla.gov.au/Record/769453

I can.

Attachment: Fast Reactions in Solids Ch 8.pdf (1.1MB)
This file has been downloaded 1323 times

Rosco Bodine - 4-10-2010 at 09:31

The meaning of the word "safe" is highly relative, qualified, and subjective.

Is the electricity which powers our modern world safe ?

Is the fire under the teakettle safe ?

A little knowledge, too little knowledge, is often a very dangerous thing.

We do all live in a universe where the laws of probability generally apply.

Great safety is enjoyed in the presumption that everyone will do their
own "risk assessments" with regards to their own conduct and choices.
That safe presumption extends to include that some who would assert
their fitness to govern others will then seek to impose upon others the effect
of their own risk assessments, whether those assessments be "reasonable"
or right or wrong.

It is also of significant doubt that the "safest" world is a thing desirable.

Where is challenge met and any real accomplishment found for risk free enterprise, where all is done in "safety" ? Do not misunderstand that I
mean by the question to advocate recklessness.

HMTD TATP 1st Use

The WiZard is In - 4-10-2010 at 10:21

First terrorist use ca. 1983.

Attachment: HMTD TATP.pdf (781kB)
This file has been downloaded 1750 times

mewrox99 - 4-10-2010 at 15:34

I think I might just steer clear of organic peroxides.

Why take the risk? I'll just make some NC to light with my laser.

There is just so many things that could go wrong with TATP or HMTD.

Nitrocellulose will give the effect I'm trying to achieve (fireball) and is safer on every level. Annoyingly I don't have any HNO3. So will have to make do with KNO3/H2SO4

[Edited on 5-10-2010 by mewrox99]

the Z man - 5-10-2010 at 04:07

surely NC is the best choice. Actually NC was my first "good" HE (made tiny amounts of AP before but I was too scared even to let it dry completely). With NC I learned the basics of nitration and I spent a lot of time to optimise the ratios and temperature of reaction. Finally I managed to make NC with NH4NO3/H2SO4 that burned almost as fast as the one made with nitric acid

While researching on NC I started to use roguesci and this forum as my first reference.
Sorry for the OT but nitrocellulose always reminds me the good old times and a lot of entertainment

mewrox99 - 5-10-2010 at 04:10

Should I use KNO3 or NH4NO3.

My KNO3 is a dry powder, while my NH4NO3 is prills

the Z man - 5-10-2010 at 04:39

I haven't tried with KNO3 but I have the feeling that using AN will make the nitrating solution less thick, and since the good quality is given by the complete absorbtion of the nitating mix I think AN is the best choice.

mewrox99 - 6-10-2010 at 02:16

Ok will try tomorrow! Time to calculate the stoichiometry.

0.5mol NH4NO3 = 20.00g
0.25mol H2SO4 = 24.52g *1.84 = 45.1mL

Can anyone tell me if i did it wrong

Also do I have to grind the NH4NO3 or can I use prills

[Edited on 6-10-2010 by mewrox99]

DDTea - 6-10-2010 at 03:42

Quote: Originally posted by mewrox99

Ok will try tomorrow! Time to calculate the stoichiometry.

0.5mol NH4NO3 = 20.00g
0.25mol H2SO4 = 24.52g *1.84 = 45.1mL

Can anyone tell me if i did it wrong

[Edited on 6-10-2010 by mewrox99]

Check your calculation. 1.84 is your density, correct? Density has units of 1.84 g/mL.

[Edited on 10-6-10 by DDTea]

the Z man - 6-10-2010 at 04:26

errr... excuse me for the question but have you ever performed a nitration before? Stoichiometry is almost useless with nitrations (especially synthesis of nitroesters and using nitrate salts instead of nitric ) as you always have to use large excess of acids and different ratios for every synthesis. Nitrations are more like an "empirical" type of reaction.

mewrox99 - 6-10-2010 at 18:15

Damm your right. DDTea

That's why you shouldn't calculate things when you haven't had enough sleep.

I tried the 20g AN in 50mL H2SO4. Seem to work fine. Let it nitrate for about 20mins.

The cotton is now a slight yellow color. I'll test it tomorrow when it's dry

mewrox99 - 7-10-2010 at 01:04

I took some of the not so dry stuff and put it on my hot plate at max heat. It took a lot longer then expected to ignite and still left ash.

Anyway I'll get some HNO3 someday in the near future. Also this thread has gone of topic as it's initially about HMTD

I think I used to much cotton and under nitrated. I used enough to completely absorb the nitration solution

KNO3me - 14-10-2010 at 19:07

Quote: Originally posted by Rosco Bodine

The meaning of the word "safe" is highly relative, qualified, and subjective.

Is the electricity which powers our modern world safe ?

Is the fire under the teakettle safe ?

A little knowledge, too little knowledge, is often a very dangerous thing.

We do all live in a universe where the laws of probability generally apply.

Great safety is enjoyed in the presumption that everyone will do their
own "risk assessments" with regards to their own conduct and choices.
That safe presumption extends to include that some who would assert
their fitness to govern others will then seek to impose upon others the effect
of their own risk assessments, whether those assessments be "reasonable"
or right or wrong.

It is also of significant doubt that the "safest" world is a thing desirable.

Where is challenge met and any real accomplishment found for risk free enterprise, where all is done in "safety" ? Do not misunderstand that I
mean by the question to advocate recklessness.

I couldn’t have said it better Rosco Bodine, that’s what the nanny states around the world just don’t seem to understand for some reason.

Anyway, back on topic, I have synthesized HMTD only once and it didn’t turn out right. The deflagrations were very slow and I think it may have been because I rinsed with plenty of sodium bicarbonate and didn’t rinse the explosive of sodium bicarbonate.
I plan on synthesizing HMTD again later on and I’m wondering if it’s okay to rinse with denatured alcohol rather than methanol, after I wash with distilled water?
This time I’ll be using Tenney L. Davis’ Hexamethylenetriperoxidediamine synthesis. He say’s to rinse with alcohol after thoroughly washing with water but Davis doesn’t specify on which alcohol.

FLchem10 - 12-2-2011 at 14:07

Yes I was the one who labeled my post "HELP ME" but I have made energetic materials for years.....I work in a college lab I should of asked for an opinion not said help.....Yea HMTD is very dangerous but that being said it has alt of history of being made and HELL ALL OF THIS STUFF PEOPLE MAKE IS DANGEROUS!!

I had a fluke mishap which happend but thats science with Energetics and I had it all in a very safe place.....If you were to go ahead and make it HCL and Citric are both tricky to add without using proper procedures.....

My thread got bash by someone who believes I didnt know what I was doing as he should because I look on here alot and see KIDS, 13 year olds, doing things that they should NEVER BE DOING... If your going to do any of this type of chem. you have to be aware that things go wrong and you should be prepared.

Anyways if you make your own HMTD make a small amount at a time....keep it in a container that is not glass....much like a specimen jar that are usually plastic and put it in a plastic bag like the one's people use for pot dime bags and leave it in, if you have one a safety cabinet if you plan to store it but even a high watt light bulb will heat it to combustion and all the other FLUKE things that might happen but you can be safe making such things...

If you ask me half of the things people make here are MUCH worse that that!!

quicksilver - 12-2-2011 at 17:10

There is no "worse". The term has very little relevance to the subject.

Energetic materials are subject to stimuli. Education as to the threshold of stimuli basis for initiation is an issue that reflects the inherent danger. Without it anything can be dangerous (don't run with scissors).

......"Pot dime bags"? Static and plastic bags have a unique relationship.

Frankly the amount of actual synthesis is low compared to the level of reading and discussion of the subject matter. I have no idea how many people synthesize [what level] of materials within the Forum. I suspect that it's relatively minor. Yet have no idea; nor would I suggest that 13 year old children do so. The educational level of an individual is fairly obvious when they post.

Somniferrous - 15-2-2011 at 23:01

Quote: Originally posted by hissingnoise

FLchem10 had a disquieting experience with HMTD.
You might want to scroll down and read his thread.
IMO, the safest synthesis for HMTD is the one in COPAE.

There is a potential problem with the COPAE synth in that during the warming phase (just after the 3 hour 0c mixing phase) one can get frothing and/or a minor eruption as it comes to room temp that makes a mess and deposits acidic hmtd where you probably don't want it.

I have been able to prevent it by adding more H2O to the initial solution. This suggests that the frothing/eruption problem is likely due to use of more concentrated H2O2 solutions and that the reaction continues long after the 3 hour 0c mixing period.

I have also found that allowing the solution to stand for a while ("a while" = 6 to 24 hours) after warming to room temp increases yield somewhat.

Good luck and stay safe. Make only as much as you need so that you won't have to store it and worry about that.

James

FLchem10 - 16-2-2011 at 11:53

To all thinking of making HMTD You must be careful when you use citric because it seems to have a tendency to not completely dissolve when making it the amateur way ( Which I dont recommend at all ) I did have a very bad experience with ONE of my HMTD experiences BUT things happen when you mess with EM's not using the right processes and equipment so for all the people making this in a home lab that is very poor NOT to be down on home labs some home labs are better than real labs Ive been in!! but if your making this stuff in you kitchen with materials bought from wal-mart dont make HMTD there are so many other things to make and please spend your money getting the right equipment before you rush into making chemicals!!

But good luck to all I have made HMTD a good amount of time that turned out just fine bu make a small amount and when drying it be very careful where you store it because it might just.....well you know

odin14 - 30-11-2014 at 10:33

I need some help detonating my HTMD caps, I packed some HMTD into some 5.56 casings and lit the fuse and it did not explode. Can someone help me please, I made a thread about it but it got deleted...

Bert - 30-11-2014 at 11:01

Quote: Originally posted by odin14

I need some help detonating my HTMD caps, I packed some HMTD into some 5.56 casings and lit the fuse and it did not explode. Can someone help me please, I made a thread about it but it got deleted...

It is not deleted. It is in "Detritus"

Read the forum FAQ.

odin14 - 30-11-2014 at 11:06

Quote: Originally posted by Bert

Quote: Originally posted by odin14

I need some help detonating my HTMD caps, I packed some HMTD into some 5.56 casings and lit the fuse and it did not explode. Can someone help me please, I made a thread about it but it got deleted...

It is not deleted. It is in "Detritus"

Read the forum FAQ.

Thank you Bert, and thank you for the concern, I am sorry to worry you like that I should have mentioned that I had already insulated the HMTD from the metal. I use wax and straws. Because it not only insulates from the metal but helps prevent accidental detonation due to an electric shock.

tube for HMTD

Laboratory of Liptakov - 30-11-2014 at 11:34

Plast tube for HMTD iniciator konstruction about 200mg content. Hand pressed. Rezistor 1,5 ohm/ 0,6W metalic. LL

[Edited on 30-11-2014 by Laboratory of Liptakov]

Hey Buddy - 3-1-2023 at 20:32

The detriments of HMTD are:
1) crystal morphology dependent sensitivity
2) slow decomposition >40 C in open moist conditions
3) highly sensitive relative to some other primary explosives
4) corrodes metals under moisture, acids / metal ions decomp HMTD
5) low decomposition temp 75 C

Accolades of HMTD may be:
1) simple preparation scheme, relative to other primary explosives
2) storable long term, in dry air, or under dry, select conditions
3) high performance primary explosive character
4) high flame sensitivity, suitable for thermal initiation
5) compatible with many organic materials
6) non hygroscopic
7) practically insoluble in water / organic solvents
8) compatible with basic aq. solutions (NH3, CO3/HCO3)

PTFE doped primaries typically decrease in mechanical sensitivity by a factor of twenty, doped by around 2-5%. Something like that could easily take care of mechanical sensitivity. Decomposition issues wouldnt be solved entirely by PTFE but a polymer binder could solve mechanical sensitivities and decomposition issues other than perhaps direct UV exposure (which is a non issue in detonators. A binded pellet could prevent reaction with materials. For instance a homogenous HMTD polymer bound pellet inside a length of straw with NC seal on both ends.
Has anyone attempted to pelletize HMTD using nitrocellulose or chlorinated rubber or VAAR binder? Parlon can be worked with acetone as solvent and in pyrotechnics it makes hard, near water-proof loads. Surely this has been tried with HMTD by someone before?

MineMan - 4-1-2023 at 02:15

Hey buddy, how do coat something with 2-5 percent PTFE… don’t you need a fluro
solvent?

Hey Buddy - 4-1-2023 at 08:13

As far as I know, PTFE powder is so small and sticks to everything that it only requires handmixing, 2-5% by weight. It's not soluble so you can mix it with a volitile solvent by hand and it coats pretty well. --There is a paper I was thinking back to of a sensitive nitrate ester from NM + Glyoxal
doi: 10.1002/prep.201000133

"For safety reasons, the impact and friction sensitivity was
tested according to BAM methods. Compound 3 is sensitive
to both of the stimuli (approx. 2 J and 50 N, respectively),
but the values are within the normal range of sensitivity of nitrate esters.
Because of high sensitivity to friction and impact, the explosive
must be tranquilized before pressing into pellets. Therefore, a composition containing 95% of compound 3 and 5% of Teflon was prepared using a slurry method. Afterwards, the sensitivity to impact and friction was reduced
to approx. 15 J and 160 N, respectively. The composition was pressed into mechanically durable pellets with density of ca. 1.82 gcm"

In this example case 2 J to 15 J and 50-150 N isnt 20x reduction but it is significantly reduced sensitivity. Other compounds are reduced in impact and friction with PTFE even more than this. I assume some differences arise from the crystal shape/volume vs the PTFE shape/volume. But it seems to pretty universally tame mechanical sensitivity. I bought PTFE powder on ebay for around $20 per kilo IIRC a few years ago. I got it for PTFE thermites, but found out it works better than anything else for phlegmatizing.
I could try it after I finish some other stuff Im already working on. I figured someone must have tried HMTD with binder or something. It seems like a logical extension.

[Edited on 4-1-2023 by Hey Buddy]

Laboratory of Liptakov - 4-1-2023 at 12:01

Flegmatisation of sensitive primary is further manipulation with sensitive primary. Of course, is it possible. If someone used HMTD, used him with minimal manipulation steps. And usually with low density.

Hey Buddy - 4-1-2023 at 19:04

Quote: Originally posted by Laboratory of Liptakov

Flegmatisation of sensitive primary is further manipulation with sensitive primary. Of course, is it possible. If someone used HMTD, used him with minimal manipulation steps. And usually with low density.

okay, twst my arm. I'll try it.

MineMan - 4-1-2023 at 20:46

I have found 5 percent PTFE increases the sensitivity in some mixes like flash powder. An actual spherical coating would be better. It is possible, I wanted to do a patent on it…. So I haven’t mentioned it. But I think there was already a paper published on it last year.

You will find the particle size of the PTFE to be crucial. I tried moly disulfide several years ago and it added a red phosphorus like sensitivity to detonating flash powder mixes. If the PTFE is nano I predict it will increase sensitivity.

Hey Buddy - 4-1-2023 at 21:15

PTFE is a strange bird because the fluorine and carbon can either act as an oxidizer or a fuel depending on what it's added to. For metal containing comps it is usually oxidizing to gaseous fluorinated species. The main advantage of PTFE is its low reactivity and high melting point which tends to thermally stabilize pyrotechnic mixes. Ive tried to use it as a stabilizer in NPED mixes like NQ+ClO3 but it actually stabilizes it to the point of being non-explosive, whether calculated as oxidizer or fuel. With metal compositions I believe fluorine from PTFE is faster than oxygen derived oxidation so it is usually pretty intense, but the activation energy in terms of temp is usually floating around mp of PTFE >320 C, unless using a really low melting point ingredient, (which HMTD is). I have no clue what it would do with HMTD. I suspect it would tranquilize mechanical sensitivity a bit. Without experimenting, and just guessing out of my buttocks, I think parlon binder matrix via acetone would be better suited to HMTD than simple PTFE mix. Assuming it doesnt dilute the HMTD to becoming non explosive. Ambient HMTD decomposition could be theoretically stopped by appropriate binder, and it would eliminate moisture which seems to catalyze decomp of HMTD in practically all instances, from what I have read. If parlon worked the same manor as other comps with HMTD, it would be like putting it in an airtight container. For HMTD that promotes stability. It could be that because HMTD isso simple to produce, the effort of a binder isnt even sought after, perhaps its notorious sensitivity and unpredictability is related to its low effort, open air low density use.

Raid - 6-1-2023 at 06:31

when you're making any organic peroxides make sure to clean them VERY well. the more you wash them the more stable they are.

Hey Buddy - 6-1-2023 at 08:53

I'm assuming you mean washing the crystals free of surface acid using an insoluble wash, like water or alcohol? --That reminds me to ask, I'm seeing no recrystallization in references to HMTD. Is that accurate? Are people making HMTD and not attempting recrystallizing at all generally?

Laboratory of Liptakov - 6-1-2023 at 16:40

Recrystallizing and neutralisation HMTD is interesting idea. But how type of solvent should be use...?

Hey Buddy - 6-1-2023 at 23:49

Quote: Originally posted by Laboratory of Liptakov

Recrystallizing and neutralisation HMTD is interesting idea. But how type of solvent should be use...?

I take that as a "no".--I have no idea what HMTD would be soluble in. I've never made it so I have no familiarity with it. Ive watched darian ballards videos. It's been a while but IIRC he's not doing any purification or washing in his HMTD videos. I havent read about recrystallization in any of the literature Ive read. Perhaps the question is silly because its a peroxide, and no one does that, but it does use an acid. Citric acid is the most interesting method because it is so OTC. I supposed that acid could be trapped in the crystals. Probably very likely if no recrystallization. Acid contact is known to catalyze decomposition in HMTD according to lit, so perhaps the instances of random high sensitivity are related to moisture and acid? I dont know, just taking a guess.

I think if something like HMTD could be controlled predictably it would be really neato.

[Edited on 7-1-2023 by Hey Buddy]

ManyInterests - 8-1-2023 at 18:34

Quote: Originally posted by Hey Buddy

Quote: Originally posted by Laboratory of Liptakov

Recrystallizing and neutralisation HMTD is interesting idea. But how type of solvent should be use...?

I also watched Darian Ballard's video on it, and his one on TATP and MEKP even though I have no interest in making any peroxide based explosive. They're far too unstable and sensitive for me to even dream of making any.

HMTD and TATP aren't recent discoveries. They've been around since 1885 and 1895 respectively. They actually did make blasting caps with HTMD originally, but its well known stability issues quickly made it an unsuitable replacement for mercury fulminate.

I think that if it had any potential it would have been discovered by now, but testing has been done historically. I mean the recipe that is on the wiki and so many other places all come from the 1943 book Chemistry of Explosives and Powders that we all know They made more tests for it there.

Hey Buddy - 8-1-2023 at 20:03

That's true. I was thinking of the relatively recent emergence of HMTD in terrorist incidents and subsequent studies since then. I also have been reading up on it more and I do find it interesting but I just dont like what I'm reading. I think I will have to reconsider and pass. Perhaps I will just undertake a small familiarization synthesis to make a few parlon/hmtd 4mm pellets. store one test others. Just for the interest.

ManyInterests - 8-1-2023 at 20:52

Quote: Originally posted by Hey Buddy

That's true. I was thinking of the relatively recent emergence of HMTD in terrorist incidents and subsequent studies since then. I also have been reading up on it more and I do find it interesting but I just dont like what I'm reading. I think I will have to reconsider and pass. Perhaps I will just undertake a small familiarization synthesis to make a few parlon/hmtd 4mm pellets. store one test others. Just for the interest.

The relatively recent use of peroxide based explosives in terrorism is a result of several factors.

Firstly, explosives control around the world has gotten a lot tighter. Once upon a time people stealing a whole bunch of TNT or dynamite and boxes full of detonators wasn't uncommon. I think in the 1990s several tons of the stuff were stolen in the US alone.

Legal restrictions on things like detonators also went up. I think that blasting caps aren't weren't as control as the secondaries that need them. And even if you stole a whole pile of dynamite, it's useless unless you have proper detonators for them. Making reliable detonators is hard, and peroxide based stuff is the easiest to manufacture and the ingredients aren't restricted in many parts of the world. Until the 2020 European chemical controls getting most of the stuff was a sinch.

The other thing is that the terrorist organizations that use them, especially Islamist groups in Europe, don't have the networks to get actual high explosives needed. The IRA did far more bombings than Islamists ever did (and probably ever will do) but they didn't resort to dangerous to make and use peroxides. They were able to get tons of Semtex that many IRA cells that still exist probably have well hidden in case some political chaos starts to happen again.

Finally... explosives detection equipment wasn't able to detect peroxide based energetics until around 2015 or so. This is because most explosives sniffers and detection equipment were originally made for nitrogen based stuff, which is almost all explosives, but stuff like TATP has no nitrogen in its structure, that makes it undetectable. This has been rectified, thankfully.

Hey Buddy - 8-1-2023 at 21:45

Well, I mean that Im convinced peroxides and HMTD specifically are under-investigated, and not well understood. They have quite a stigma of being AD-prone. Most of the recent investigation is well, recent interest.-- As for explosive detection, that's a whole separate tangent, I really shouldnt get started on, but most of that stuff is contract-award non-sense. I dont want to get into specifics but I'm aware that explosives are not detected by conventional explosive detection systems. I would have to guess that perhaps there have been actual situations where explosives have been detected, (only because I cant imagine how they would remain in use if they never functioned), but a majority of the time, explosives are very difficult to detect and explosives go through things like airports and postal service etc. quite often and are not detected. They are definitely more often not detected than detected by a lot. I have no confidence whatsoever in digital explosive detection, chemical detection works, imaging detection of conspicuous devices works if someone is paying attention, explosive detection dogs can* work, if trained on actual explosives. Most of the real time digital detection stuff is just a company filling a governments need to check a box and show they spent money on it. Nothing more. Ive seen government employees forget explosives in their cargo and not realize it until they are in unloading their stuff. The idea that explosives can be detected en masse of the worlds populations is a "feel good" non-reality.

[Edited on 9-1-2023 by Hey Buddy]

ManyInterests - 8-1-2023 at 22:35

That story about people 'forgetting' explosives is just... terrifying. I know complacency can set in on anything. But this is stupid. Stupider than police who forget their guns somewhere, like in Canada in 2006 when some cop took off his gun belt to use the toilet and 'forgot' it. It was recovered several years later at the site of a shooting that resulted in several deaths...

But wouldn't the digital explosive detection use some kind of chemical detection? How does it work?

Early forms of explosives detectors until 2000 couldn't detect semtex. I heard that it is only because of the taggants that the manufacturer added to their newer batches, but earlier batches made prior to 1990 (of which there are probably quite a few tons of around the world, not just in the IRA's inventory) might still be difficult to detect.

Hey Buddy - 9-1-2023 at 00:30

Quote: Originally posted by ManyInterests

But wouldn't the digital explosive detection use some kind of chemical detection? How does it work?

Yes they use digital sensors, and most of the IP is "protected" or "sensitive technology" meaning that it cant legally be independently validated. Or you will often see "tests" regularly scheduled to validate a certain detection device, and the test will have "standards" but the standards arent applicable to the real world, they are only applicable to controlled tests, merely so a contractor can check a box saying "yes we tested this and it works correctly." In war time, I once witnessed fly-by-night international contracting companies selling boxes to the local national military as "Explosive detection devices". Simple box devices used to search for explosives at checkpoints. The USA in this case, provided funding to the host government, and they buy these things from large companies that pop up. The host military would have problems with the technology on the ground, errors, problems understanding the use of the equipment etc. Then theyd bring it to US military to troubleshoot. Well the problem was the devices were basically non-sense LED microprocessor driven randomly flashing whiz-bangs and they didnt detect anything at all, nor could it be determined what they actually were designed to do. Im not saying it's *that* egregious at the TSA, but it's basically the same principle on a more subtle, large scale.

The taggants are sometimes reported to be added for the purpose of detection, but the ultimate purpose is simply to trace explosives after they are found like in cases of stolen explosives. Explosives are stolen or misplaced everywhere, all over the world, all the time. Everything from people maliciously stealing all the way to forgetting explosives or administrative peculiarity stuff. For example, in the US military, the record standards are stringent with explosive drawing. Explosives have to be drawn based on a need of use, they cant really be returned once drawn, they all have to be detonated or destroyed. Munitions turned back in can be damaged or unserviceable and could cause detonation of bulk storage, so it is common practice, the explosives only go one way, out. It becomes an issue of balancing demolition draw by the real world need versus the paperwork "need", which is usually predrafted, standardized, then signed, by the ammo supply point and receiving command etc. Sometimes you dont draw enough and cant complete the actual mission and dont have the option to draw again (if its a weekend or holiday or middle of the night or something). That can lead to big problems for soldiers getting disciplined for some failure. So what happens? It is standard practice to over-draw by ~5-10% then stash the extra and cycle it out each new draw cycle. This practice in the military dates back to I dont know when, but at least vietnam if not WW2 or WW1. So pretty much at every military base I know of, and Ive seen it in multiple continents, you randomly find equipment sheds, janitor closets, connexes or vehicles with unaccounted explosives. It probably occurs in every country with a military --Im not saying it's necessarily wrong for them to do that, Im just saying you would never read about it in a military manual but it is standard practice.

Things happen, people forget about the stash, people draw a stash one draw but not the next, then forget, people get reassigned bases or deployed in wartime. Explosives get abandoned, or people in the unit know about where the stash is and steal it. Point is, there are exposives out there everywhere. In war zones, the situation is an order of magnitude worse, ie. missing cargo trucks. They put taggants in explosives so they can track the dissemination of undocumented explosives and isolate trouble areas. Because the largest manufacturers and customers of explosives also have the largest losses.

EDIT: also I should point out while Im on a rant: it is a plain and simple fact that legally authorized manufacturers and transporters of explosives are responsible for the overwhelming numbers of civilian deaths that have been caused by explosives. The number of civilians killed by accidental detonation of explosives by "authorized" authorities vastly and grossly outweighs any and all instances combined, to a massive degree, of all historical malicious terrorist-killings of civilians.

Im not apologizing for terrorists, Im just saying the loss of a life is a loss of a life, whether a terrorist killed them or a government.

[Edited on 9-1-2023 by Hey Buddy]

[Edited on 9-1-2023 by Hey Buddy]

Herr Haber - 9-1-2023 at 12:36

I think the taggant was added by a Czech manufacturer to distinguish it from other manufacturers (Lybia!) that didnt care much where their product ended.
PETN seems to be otherwise quite easy to detect nowadays anyway.

Hey Buddy - 9-1-2023 at 14:02

Quote: Originally posted by Herr Haber

PETN seems to be otherwise quite easy to detect nowadays anyway.

If you say so.

Raid - 14-2-2023 at 06:24

any easy way to destroy peroxides?

Destruction of peroxides

Baiuvarian - 23-4-2023 at 10:31

This paper is all about the destruction of peroxide compounds, specifically HMTD, TATP and DADP:
http://energetics.chm.uri.edu/system/files/Peroxide%20Explos...

For solid peroxide compounds, 5 mol of either (NaBr, KMNO4, CuCl2, ZnCl2, ZnSO4, SnSO4, sulfuric acid only) were put on top of 1 mol of the peroxide and a few drops of sulfuric acid in different concentrations (37 %, 50 %, 100 %) were added, destroying the peroxide within 14 hours. For faster destruction, concentrated mineral acids like sulfuric acid (98%), nitric acid (70%), and hydrochloric acid (36%) can be used, but will likely cause even small samples to detonate.

In my experience, when placing about 1 g of loose HMTD powder on a flat surface it can be lit with a torch and will just burn with a fireball and won't detonate. There is no excuse for handling larger amounts than 1 - 1.5 grams of peroxides, so in practice, burning the unconfined compound (maybe in smaller batches, depending on the surroundings) seems to be the best way to effectively destroy peroxides in my opinion.

HMTD: Synthesis, properties and my thoughts on safety

Baiuvarian - 17-5-2023 at 11:46

Factors like the purity and morphology of a substance can have a great influence on its properties. So when discussing the properties, these parameters should be considered. Since it is pretty hard in a home lab to exactly characterize the material, especially impurities, I suggest at least describing the synthesis in as much detail as possible. That way, others have the chance to reproduce it. Also, when comparing syntheses and corresponding material properties, correlations may be found.

Synthesis
This synthesis is based on [1]. The main difference is that I use more hydrogen peroxide but I don't recall where I got that from. Finishing washing with isopropyl alcohol is done to get rid of contaminants that are not water soluble and to help with drying.

Chemicals:
- 20 ml H2O2 30 % (stabilized, typ. with 1-2 % phosphoric acid)
- 3.5 g Hexamine (ground Esbit tablet)
- 5 g Citric acid (food grade)
- distilled water
- isopropyl alcohol

Materials:
- small beaker (I use 50 ml)
- ice bath
- magnetic stirrer
- filtration setup (I use a coffee filter)

Procedure
- Put the H2O2 in the beaker, set in the ice bath and start stirring.
- With the H2O2 below 0 °C, add the Hexamine while stirring continuously.
- When everything is dissolved as good as possible (the wax binder in the Esbit and I think even some Hexamine won't dissolve, the solution is cloudy) add the citric acid in small batches, making sure the temperature stays below 0 °C.
- Keep stirring for about 1.5 hours while the ice bath and the solution warm up to about 10 °C.
- Set beaker in a place at room temperature for about 3 hours. Don't set the beaker on anything well insulating like a paper towel to make sure the solution doesn't get warmer than necessary.
- Filter off the solids and wash thoroughly, first with distilled water (5 times) and then with isopropyl alcohol (3 times). Make sure to start each individual wash from the very top of the filter. Otherwise, contaminants like acid will stay there and will get into the product later.
- Split filtrate into 2 - 3 portions and let them air dry

For this timing I got a yield of 2.4 g HMTD, with longer times (3 h stirring, 20 h at room temperature) I get 3 - 3.2 g.

Please note that anything I describe below refers to "my" HMTD created this way. Other syntheses (e.g. with different acids, ratios, washing ...) may lead to a product with very different properties.

Physical appearance
Crystal sizes (longest dimension) vary between about 30 µm and 400 µm. There are some longer linear aggregations of connected crystals up to 1 mm long. I was worried about those (because TATP tends to form very sensitive needles) but they are very elastic and bend and break up easily without any reaction.

Recrystallization
Oxley [2] suggests recrystallization with a 70/30 v/v mix of ethyl acetate (EA) / acetonitrile (ACN). However, the solvent can't be fully removed even under high vacuum. That and the availability of the solvents are the main reasons why I don't recrystallize the HMTD, especially considering I never noticed any issues with decomposition (see below).

Sensitivity and Stability
I tested the sensitivity with about 20 mg HMTD on a milled steel block and a hammer. No amount of friction on the face, edge and corner of the hammer could set it off, neither did light taps (light for a hammer, they would still hurt quite badly of it was your head). A slightly harder blow would set it off. About 1 g of loose powder on a steel plate touched with a flame gives a short yellow "fireball" with a deep "oompf", the entire burn with visible flame lasting about 0.3 seconds.

I then stored a sample of about 1 g in a flat glass dish covered with cling wrap in a dark place for two months at about 8 - 12 °C and 40 - 70 RH, repeatedly checking on it. There was no measurable weight loss (considering the measurement uncertainties I can be sure it was less than 3 % over two months). The appearance, sensitivity and burning characteristics did not change subjectively with the tests described above. I realize those tests are quite rudimentary and I'm working on that (see "What I plan next").

Storage: Keeping it as a loose powder in well separated portions of 1 g max. contained
- in a way that doesn't cause mechanical stress including potential pressure build-up
- in a way that doesn't constrain it in case it burns
- far away from metals, metal compounds and acids [2]
- in a cool, dry and dark place
seems reasonably safe to me. If it were to burn it's a quick intense flame. No detonation, no shrapnel.
I would still not recommend storing it for longer periods of time since it is known to slowly decompose, depending on the conditions [3,4].

Usage: My main use for HMTD is in detonators. The the same rules as for storage apply to the detonator, except for the constraining part of course, so appropriate precautions (PPE, shielding, ...) must be taken. Building a detonator with the HMTD contained in a plastic syringe is one simple way to avoid metals (pressing the HMTD is not recommended). Wrapping the detonator it in something non-transparent like electrical tape blocks light. The use of detonators containing HMTD is still limited to environments with at most moderate temperatures. All of that is not a problem in my applications.

Toxicity
Hexamine and citric acid are approved as food additives. Hydrogen peroxide will decompose into water and oxygen. The main decomposition products of HMTD are CO2 and trimethylamine [4], both of which are not very toxic and can just be ventilated away.
Of course "the dose makes the poison". However, many other primaries and required reagents are just highly toxic. The LD50 for lead azide and silver fulminate is about 30 mg / kg, the same as sodium cyanide [5,6]. Keep in mind that some substances (like lead) even in trace amounts will accumulate in your body over long periods of time. Also, doses well below the LD50 can cause serious damage like cancer. With a good lab setup and meticulous operation, contamination can be managed but for many home labs (being part of a home means long exposure to contamination), toxicity is a significant safety concern that needs to be considered in the selection of projects.

Conclusion
The toxicological aspects of other primaries, along with the availability of reagents, are a big part of why I chose to experiment with HMTD. I chose HMTD over TATP due to TATPs tendency form large, fragile crystals by sublimation while also being twice as sensitive to impact [7]. TATP does decompose slower than HMTD [8] but that is in practice mostly relevant at elevated temperatures which are not a concern in my applications.
I don't want to "promote" HMTD here but I do want to share my experiences with what I think is a practical primary for some applications, that can be handled appropriately in many home labs even on a low budget.

What I plan next
The sensitivity tests described above are quite rudimentary. I have since built a friction testing apparatus very similar to the BAM machine as well as other testing capabilities, which I will use to further characterize HMTD and other substances.
I will try to desensitize HMTD using graphite, comparing properties quantitatively and sharing the results here.

References
[1] Tenney L. Davis: "The Chemistry of Powder and Explosives"
[2] Jimmie C. Oxley: "Destruction of Peroxide Explosives"
[3] Jimmie C. Oxley: "Synthesis and Degradation of Hexamethylene Triperoxide Diamine (HMTD)"
[4] Jimmie C. Oxley: "Decomposition of multi-peroxidic compounds Part II. Hexamethylene Triperoxide Diamine (HMTD)"
[5] https://en.wikipedia.org/wiki/Azide
[6] https://en.wikipedia.org/wiki/Silver_fulminate
[7] Rudolf Meyer: "Explosives" 6th Edition
[8] Jimmie C. Oxley: "Determining the Vapor Pressures of Diacetone Diperoxide (DADP), and Hexamethylene Triperoxide Diamine (HMTD)"