Sciencemadness Discussion Board - Stabilization of organic peroxides

Stabilization of organic peroxides

BASF - 11-12-2002 at 02:53

I want to start a little project on stabilization of organic peroxides like acetone peroxide or hmtd.

I want to try several additives (not more than 5-10 weight percent) for stabilization.
It would also be an objective to try slowing down sublimation.

Any thoughts?

-It would be very useful to know the decomposition products and/or the pathway of decay.

HLR

BASF - 11-12-2002 at 09:08

Once i stored hmtd in an iron container.
The iron got corroded and contaminated the hmtd with lots of Fe2O3.
After half a year or so, i opened the container and noticed the intense smell of amines, if my nose was right.

madscientist - 12-12-2002 at 11:34

Perhaps mononitrotoluene could be used to desensitize organic peroxides.

friction

Syanide - 12-12-2002 at 21:17

If you want to make AP less succeptible to detonation becuase of friction, and prevent sublimation, a good way to do this is to turn it into a putty.

Mix AP with some PVC cement so that it makes a putty. Mix them carefully (don't apply too much pressure) and it will eventually harden.

Anarchist - 19-12-2002 at 16:40

you can also make AP putty with double base smokless powder as well, I have heard that this is a fairly stable substance. I don't really know about the sublimation factor though.

DeusExMachina - 20-12-2002 at 05:16

I've heard of AP being put in melted straws by pouring acetone over the straws andthe letting them melt, put in PVC cement and in smokeless powder.

BASF - 14-1-2003 at 05:25

PVC-cement......what is this used for?

DeusExMachina: Do you have more specific info on what you said, maybe a link or sth?

Melting AP...i can hardly believe this...

BASF - 14-1-2003 at 09:53

Not to be misunderstood....i want to experiment with stabilizers for stabilizing HMTD or DPPP(assuming it can be made somewhere in the future...) and AP is under the most volatile and most simple manufactured peroxides, so it should be ideal.

I already had some access with phorone as coating substance reducing the rate of sublimation by 10% over a 14 day- period(approximately 15% phorone).

But phorone is still very expensive...
I want to put emphazis on surface coating, i rather want to have a powder than a block of glued peroxide.

Another way to go could eventually be the addition of several acids/acidic buffering agents, assuming that peroxides are more stable in acidic milieu.

BASF - 14-1-2003 at 16:22

Quote:

First know this:
H2O2 is a peroxyde and is sold when 30% or 50% at a pH (logarithmic acidity
scale) between 2 and 0....the use of oxydiser resistant strong acids is done;
it is not unusual to find H2SO4, CCl3-CO2H, H3PO4 in commercial H2O2!

Secondly:
Peroxydes are less stable in neutral and mild basic conditions because acidity
helps to prevent autocatalytic decomposition of H2O2! In strongly alkaline
media like NaOH when cooled strongly, you can get Na2O2 salt formation (since
H2O2 is slightly more acidic than water)!

Hmm seems that acidity would be the right way to go..

DeusExMachina - 14-1-2003 at 19:50

BASF, I meant melting straws (the type of straws that have nitrocellulose in them) in acetone and then mixing the viscous paste with the acetone peroxide. You can do that or mix it with double base smokeless powder which increases it's power.

DeusExMachina - 14-1-2003 at 19:53

hey BASF, I may have misunderstood what you were gettign at with what you said about phorone but you can make it easily and it is cheap too. HCl and acetone is all you need right?

BASF - 15-1-2003 at 09:39

Quote:

1)TCAP was impregnated with 16% phorone (from Sigma-Aldrich,p.a. 97%, 10$/10g); the weight loss was now only 15% as opposed to 26% uncoated.

2)TCAP was impregnated with less than 45% of an ethanol-soluble grease(non-volatile) obtained by cooking acetone with concentrated sulfuric acid.

The unexpected result was a weight loss of 38%, even more than of pure TCAP.

And that´s the problem.....although we have a vague idea phorone can be made somehow via acetone+hcl, we did not manage to get pure phorone.

As my comparative tests with pure bought phorone and the product from the acetone+hcl experiment show, it is very unlikely that phorone can be made using such method.

Also see "Reactions of HCl with acetone" in the DPPP-thread

http://www.sciencemadness.org/talk/viewthread.php?tid=179&pa...

PHILOU Zrealone - 19-3-2003 at 03:29

BASF:
If you look closer to the link, you will see the PH Z sign under louis texts...it was me!

I not only expressed that acids doesn't destabilise peroxyde and should be better than neutral or basic media!

I proposed a simple test to be sure of possible stabilisating or destabilisating effect of acids or base!
1)Make CTAP filtrate it and wash it with cold distillated water; then cut it in 4 parts while stil wet!
Part 1: allow to dry and get pure CTAP
Part 2: add 10% solid citric acid (grinded) and allow to dry the same way as part 1
Part 3: add 10% solid Na2CO3 (grinded) and allow to dry as part 1 and 2
Part 4: add 10% solid NaCl (grinded) and allow to dry as P1,2,3!
Better make the drying of all together in the same place to be sure the cristal size is the same and the time of drying too!

Then simply compare the Temperature of decomposition of each towards each other!
If T explosion/fire/detonation are expressed as T1,T2,T3 and T4 for each group:

Then if: T1=T4>T3=T2
Pure neutral CTAP and with inert ingredient is stabler than acid or neutral one!

If: T3>T1=T4>T2 acid destabilises while base stabilises!

If: T2>T1=T4>T3 acid stabilises while base destabilises!

If: T4>T1 inert ingredient stabilise

If: T4=T2=T3>T1 all ingredients stabilise by simple dillution effect

There are other possibilities but with a little logic they are combinatation of the above conclusions!

This simple experience would close all debate about the subject and prove what is right and what is wrong!!!!

BASF - 19-3-2003 at 06:53

Sorry Philou, forgot to add your initials...

Interesting info.....
The idea of surface coating was from a patent on stabilization of methylene dinitramine where they used picric acid as coating substance...

HLR

Nu-ANFO - 13-5-2011 at 12:00

I've read a lot about TATP and I really need it too to make a AP/ETN compound cap.I do some test mixing 50:50 AP/ETN
and ignite by Rcandy fuse.The result is fail det.It just burn.I have an idea to stabilize AP with ETN.Dissolve both with acitone and evaporate.For fuse sensitive,use more AP.For more stable less sensitive use more ETN.Also this mixer will give more power .Important: Both AP ane ETN must be neutrallize by recrystalization with alcohol or acitone by adding some Naco3. AP must be synthesis below 10c. with HCl.

Bot0nist - 13-5-2011 at 12:08

TATP is a really shitty choice in a compound initiator for a multitude of reasons. If you have the means to make ETN you out to be able to make some more suitable primaries that are more reliably and a hell of a lot safer than that suicide dust. Also, I know your trying to stabilize the AP, but mixing it with the ETN may not be the most effective way to 'get the train rolling' in the cap.

hissingnoise - 13-5-2011 at 12:45

A Lazarus thread . . .
Anyway, AP has this unfortunate habit of stabilising its handlers - sometimes permanently!
HMTD is unpredictable but AP is just plain treacherous!
http://www.sciencemadness.org/talk/viewthread.php?tid=8038#p...

Nu-ANFO - 14-5-2011 at 02:45

I just give an idea to stabilize AP with ETN. Actually I use AP in AP/ETN compound cap in 2 train.I add Rcandy in 0.5cm vinyl tube and follow by small amound of AP about 100mg or less and press it very sofly with cotton stick. Then add 500mg ETN next to it.This is more than relieable blasting cap.I use this cap with very care form heat,static,pressure during insert to the main charge.AP will be safe if use very small amount as posible and do it with care(I 've even made 2g AP blasting cap for several times).And people must do several test and learn a lot before making it. HMTD can not be safer than AP.Some time it is more dangerous than AP to reacth with some metal container. Never use organic peroxcide as a main charge. Hold it with very care,use it as less as posible ,synthesis at cool as posible(under 10c.) and also becarful about static.So, you will sure be safe i garantee.

vulture - 14-5-2011 at 03:50

Quote:

Never use organic peroxcide as a main charge

That doesn't guarantee your safety! You seem to assume that your AP is only dangerous in larger quantities. What if your 100mg of AP goes off when you're inserting the det into the main charge?

Nu-ANFO - 14-5-2011 at 06:44

All primary are not safe.TATP is one of the most sensitive so that we get advantage of it.It is so sensitive does not mean it sustains self detonation.I mean we have to use this AP all proper way like using it as fresh,a little bit moister.I have an i dea to add a little % AN to AP and let it sit for a round 5 or 10 minute so that AN obserbs some moister from the air.Maybe 10% of AN has been add to it.This should still can be use as a primer and can be ignited by heat,fuse.I am goint to do some friction and impact test with this compound too. I also working with heating ETN in foil cap.So that no primary is needed.See this forum also.
http://highexplosivesforum.forumotion.com/

Bot0nist - 14-5-2011 at 07:25

While moist TATP is much less sensitive to premature detonation, it is also less effective at shooting a secondary. Your are right about the synthesis of TATP needing to be cold. The dimer is more unstable and less effective. You are also right to minimize any stimuli that you can when handling the compound, as it will happily maim you. I think you should try and see if the hygroscopy of NH4NO3 will effectively keep the TATP moist enough to desensitize it, while still allowing detonation in a small scale, controlled experiment.

Mixing AN and TATP is nothing new though, and I must again reiterate that I advise against using TATP in an initiator of a larger secondary charge. It is SUICIDALLY sensitive to stimuli and even if you have never had a premature detonation or a near miss with it yet, it can happen for no real apparent reason. The worst thing is that it seems pretty tame most of the time. Also, it isn't a very good primary. It is powerful, sure, but the physics of its explosion make it a poor initiator. There is a reason it has never been considered for commercial use, even in war time. Only ever attractive to teens and jihadist, probably do to its retardedly simple synthesis.

Many primaries are easy to synth, much better at initiation, and perfectly sensitive to flame. Check 'em out.

Nu-ANFO - 14-5-2011 at 12:05

People make me more afraid of AP everyday.More and more. Yes i should belife that.Actually I am using ETN -heat-in -foil cap that worke for me everytime blasting both underwater and underground.
Then i just lose my 600g ANFO in the water because fail det.So,i am thinkking to start syn and using TATP again.When i read more and more about TATP,it make me more worry to handle it. Now I start to do some more improve ETN cap again to make it relieable 120% No primary needed so mean safe. Hope people to stick to this too. Don't pay attention to much about weak chem bond HE

AndersHoveland - 14-5-2011 at 12:48

Acetone peroxide is dangerous!

Because it is easy to make, acetone peroxide is popular among those with little knowledge of chemistry, which is very unfortunate.

ETN and nitroglycerin are not really primaries. Although they can be dangerously sensitive to friction or mechanical impact, such compounds do not reliably detonate from flame or electrical ignition.

There do exist several other good primaries, which are both much safer than acetone peroxide, and are better at initiating the booster charge. However, these other primaries can be somewhat more complicated to make.

Please do not prepare more than a few grams of any organic peroxide (such as AP) ! The ammount of AP required to directly detonate ANFO is a very unsafe quantity. If you insist on "experimenting" with ANFO, please do some research about other safer primaries. Especially if you are under 21 years old, it is a very bad idea to prepare or store more than a few grams of any explosive substance.
Younger people with an interest in explosives almost always have poor judgement about all types of risk- and the dangerous thing is that they do not realize it.

hissingnoise - 14-5-2011 at 13:29

Nitromannite, according to Davis, is a near-primary and will detonate from the flame of a match!
KClO4/AL flash should reliably initiate MHN with strong confinement . . .

textex - 14-5-2011 at 17:02

Quote: Originally posted by Bot0nist

It is powerful, sure, but the physics of its explosion make it a poor initiator. There is a reason it has never been considered for commercial use, even in war time. Only ever attractive to teens and jihadist, probably do to its retardedly simple synthesis.

I dunno, but i would belive that one of the worst things about AP is that it sublimes so fast. Making it really bad for commercial stuff. One thing is making a cap and then setting it off 3 hours later, but making 1000 caps that will be used the next 6 months? Or using it in shells which is gonna be shipped to the far east and then used in a war there.

Just my 3cents though, i just ocasionally use it in 10mg quantitys in caps.

Any of you tested how AP-putty reacts? that being ap dissolved in nc-laquer if im not wrong.

[Edited on 15-5-2011 by textex]

VladimirLem - 14-5-2011 at 21:32

Hi guys

I have seen, that HMTD is pretty much unsensible against shock etc when it was only a bit wet of ethanol...

1-3% of ethanol should "stabilize" it enough...

But careful, if it is too wet it doesnt detonate...

hissingnoise - 15-5-2011 at 05:02

Quote:

I have seen, that HMTD is pretty much unsensible against shock etc when it was only a bit wet of ethanol...
1-3% of ethanol should "stabilize" it enough...

That is a pretty unsafe assumption to make, considering ethanol's volatility . . .

VladimirLem - 15-5-2011 at 06:06

Quote: Originally posted by hissingnoise

Quote:

I have seen, that HMTD is pretty much unsensible against shock etc when it was only a bit wet of ethanol...
1-3% of ethanol should "stabilize" it enough...

That is a pretty unsafe assumption to make, considering ethanol's volatility . . .

thats right...maybe you could take oil instead ethanol...i dont know

hm...i'm going to try this^^

hissingnoise - 15-5-2011 at 06:15

If you have to use HMTD, it's essential that it be washed well several times with cold water and it's kind of worth noting that aluminium is the only common metal it won't react with.

Lord Emrone - 15-5-2011 at 08:10

If you, for whatever reason have to use peroxides, use drop-caps. Make a paper tube with ETN at the bottom, drop-cap attached to the top with fuse. When fuse burns, cap drops and dets the ETN.

quicksilver - 15-5-2011 at 08:20

When this thread was started the term "stability" was used as a root (via "stabilization"). I believe that stability is much less difficult to achieve than a lowering of sensitivity. It is sensitivity that has made HMTD a "non-candidate" for industrial usage.
As a rhetorical question I have occasionally wondered why many folks insist on using a description of some materials as"unstable" when in fact they are highly sensitive. Stability can be achieved through proper synthesis, appropriate storage conditions, yet it's sensitivity that has been the contributor to problematic employment (or lack thereof).

Nu-ANFO - 16-5-2011 at 05:10

I think add 10-20% AP to ANFO or ANNM will make AP more stable and make ANFO and ANNM cap sensitive. It's more safe than use very dry APAN alone. AP some seem to disolve in nitromethane,i think add 5-10% NM to APAN is also more safe than use APAN alone and this will make APAN little more slurry and more VOD .I have done some test with this. AP is not that bad if you handle it properly and do diferent test of it. The most i worry about AP is electric static sensitive. We can't see static by our eyes so becarful with static. Making AP more slury or look wet with fuel oil or NM will make AP less static sensitive.

VladimirLem - 16-5-2011 at 07:25

Quote: Originally posted by Nu-ANFO

I think add 10-20% AP to ANFO or ANNM

i dont know which many ANFO you make, but 10 up too 20 percent of the secondary explosive is waaay too many.......4 up to 5 -...should work...but 20? That crap is expensive and at up to 20% it will be fuckin dangerous, i think...

The WiZard is In - 16-5-2011 at 07:32

Quote: Originally posted by Bot0nist

Also, it isn't a very good primary. It is powerful, sure, but the physics of its explosion make it a poor initiator. There is a reason it has never been considered for commercial use, even in war time. Only ever attractive to teens and jihadist, probably do to its retardedly simple synthesis.

Amen La Jihadist use another peroxide as a primary.

Decrease TATP's sensitivity? I would file this under —
The tiger does not change its stripes.

And by da — Dem pest'y Jihadist make TATP with the mindset
that — if it blows up — they will be met by Seven Virgins in
Heaven. What's in the back of your mind?!?

djh
----
Appeasers beleive that if you keep
throwing steaks to a tiger, the tiger
will become a vegetrarian.

Heywood Broun

Nu-ANFO - 16-5-2011 at 10:12

20% AP to ANFO actually too much.Just 5-10% to increase sinsitivity ANFO cap sensitive and small diameter charge. APAN is not powerful powder-powder binary explosive unless u make AN very fine powder. If add some 10% nitromethane to APAN it become very powerfull because it link AP to mix with AN nicely(Add 1 or 2 % water too to desensitizing AP). I 've tried this before.It is considered to power of 75:25 ANNM. Nitromethane is fucking expensive so i use APAN/NM for 100g charge or to boost ANFO

12:88:5:1 AP:AN:NM:water try this ha ha ha fucking powerful and can save a dollar of NM VOD is something 5000-6000m/s

vulture - 16-5-2011 at 14:10

Erm, adding ammonium nitrate to AP to stabilize it?? You do realize that AN is acidic, right?

AndersHoveland - 17-5-2011 at 16:07

Actually, one would think that acidity, in one way, may help to chemically stabilize organic peroxides, because hydrogen peroxide is more stable against decomposition (it slowly breaks down into H2O and oxygen gas) under acidic conditions. In another way, however, acidity may promote hydrolysis of the acetone peroxide with moisture, back into acetone and hydrogen peroxide.

Dangerously sensitive explosives can seem safe

Often compounds that seem not to be very sensitive, can nevertheless blow up for seemingly little reason. Even if you have experience that suggests that something is not sensitive at all, that does not mean extreme caution should not still be used. For example, many experimenters have thrown bottles of organic peroxide hard against pavement without any detonation. Even little static sparks directly on the compound have failed to detonate it. Despite the seeming insensitivity, organic peroxides can still spontaneously explode when being handled.

This reasoning should extend to nitroglycerin. Even though it is fairly difficult to detonate, and can take impacts or burn without incident, does not mean that it will not later explode for no reason when it is being gently handled.
The reasons for the great variability in initiating these compounds are subtle, but likely have to do with impurities, crystal formation, envirormental humidity, and age of the compound. Extreme caution should always be used, as there is always the chance that unknown causes can result in seemingly safe primaries exploding without warning. NG is fairly difficult to RELIABLY initiate, but it is NOT "reliably" resistant against detonation. One tube of NG might not go off if thrown hard onto pavement, while another tube with a different batch, or the same batch that has sat around for a year, may go off just by accidently tipping over and being jarred against the top of the table.

One should never assume that any primary is safe, whatever prior experience with the compound would suggest. One example is TrinitroAnaline. This is a very insensitive explosive, and yet it has a seemingly unanticipated danger of spontaneous detonation in storage. This is caused by trace impurities that act as reducing agents, initiating a chain reaction that eventually results in explosion.

One of the reasons for variable sensitivity in nitroglycerin, for example, is formation of tiny air bubbles that act to sensitize the liquid. Impact as low as 20g/cm can detonate NG.
http://www.jstor.org/stable/97914

Be sure you know the proper precautions that need to be taken, and the things not to do, before working with any primary explosive. While an accident might be unlikely, many younger people have suffered severe injuries (losing fingers, suffering permanent ear damage, or losing sight in an eye, and even death).

One particular note, while acetone peroxide is very simple to prepare, it is one of the most dangerous primary explosives to handle, being far more sensitive than nitroglycerine. A teenager in Sweden killed himself when handling a over a kilogram of this dangerous substance. Please never prepare or store more than 2 grams of this substance (about the size of a large spoon full)!! Sometimes this substance can be thrown against a hard surface without incident, while other times it can detonate when being cautiously divided with a thin plastic playing card.

[Edited on 18-5-2011 by AndersHoveland]

holmes1880 - 17-5-2011 at 17:03

I don't understand how these threads are tolerated. While at it, let's also purify mercury fulminate. Meh.

Acetone Peroxide

The WiZard is In - 17-5-2011 at 17:07

Me The Analogue Guy again. I have a serious need to
find something in my files, while looking came across these
two and another that will have to wait.

Byda no doubt you will A- Astounded and B- Amazed —
too know who owns a copy of both the Davis and Hawkins
books mentioned. Time permitting on the morrow I'll see
whats worth scanning.

PHILOU Zrealone - 18-5-2011 at 00:11

Peroxydes can also be stabilised by sodium stannate salt...We used this (in a hair cosmetic fabric where I have worked) as a stabiliser for peroxyde hair decolourizing cremes made from H2O2 33% and a stiffening wax... to get a final product of 10% H2O2 content.

The gain of stability against heat and storage was very strong...

It is funny that stannous and stannic chlorides are used in the process of cyclotetraaceton peroxyde (CTeAP) what is reputed to be slightly more stable than the cyclotriaceton peroxyde (CTAP) brother.
Maybe does the stabilisation come from the same effect as the stannate salt?

Stangely Na stannate is quite basic and holds a transition metal in it I had thought it would make the H2O2 less stable...but it seems to make a complexation or a radical scavenging of the peroxyde...

It is something on my to do list to test.

[Edited on 18-5-2011 by PHILOU Zrealone]

The WiZard is In - 18-5-2011 at 06:01

Quote: Originally posted by The WiZard is In

Me The Analogue Guy again. I have a serious need to
find something in my files, while looking came across these
two and another that will have to wait.

Byda no doubt you will A- Astounded and B- Amazed —
too know who owns a copy of both the Davis and Hawkins
books mentioned. Time permitting on the morrow I'll see
whats worth scanning.

Well .... Hawkins is just a bunch of chemistry and all I ever get
is complaints that I post toooo much... so I won't take the
time to scan it.

Organic-Peroxides-Davies-196.jpg - 500kB

Organic-Peroxides-Davies-197.jpg - 541kB

Organic-Peroxides-Davies-198.jpg - 397kB

Organic-Peroxides-Davies-199.jpg - 406kB

Organic-Peroxides-Davies-200.jpg - 166kB

Criegee has collated the data on typical organic peroxides. [74]

[74] Criegee, Methoden der Organischen Chemie
(Houben-Weyl). Tbhieme, Stuttgart, 1952, 8, 844

Reproduced by Tobolsky and Mersobian, Organic Peroxides,
Interscience, New York, 1954, pp. 177-180.

Once again no doubt you will be A&A'd to know who shelves this
book. I have things of use upon me to be a doing, it is on my
do it latter list.

The WiZard is In - 18-5-2011 at 16:03

Quote: Originally posted by PHILOU Zrealone

Peroxydes can also be stabilised by sodium stannate salt...We used this (in a hair cosmetic fabric where I have worked) as a stabiliser for peroxyde hair decolourizing cremes made from H2O2 33% and a stiffening wax... to get a final product of 10% H2O2 content.

The gain of stability against heat and storage was very strong...

It is funny that stannous and stannic chlorides are used in the process of cyclotetraaceton peroxyde (CTeAP) what is reputed to be slightly more stable than the cyclotriaceton peroxyde (CTAP) brother.
Maybe does the stabilisation come from the same effect as the stannate salt?

Stangely Na stannate is quite basic and holds a transition metal in it I had thought it would make the H2O2 less stable...but it seems to make a complexation or a radical scavenging of the peroxyde...

It is something on my to do list to test.

[Edited on 18-5-2011 by PHILOU Zrealone]

Stannous chloride.

This from Hawkins.

The WiZard is In - 25-5-2011 at 13:17

Quote: Originally posted by PHILOU Zrealone

PHILOU Zrealone - 25-5-2011 at 23:58

Thanks "The WiZard is In" it is nice to have you here...Don J Haarmann (djh)

I suppose you did left Alt.engr.explosive forum because it was not popular anymore?

BTW why did you change your pseudo during the transition?

Anyway, we must be a few of the old chaps from AEE.
Your information is as usual very valuable.

I think the documents you have provided about Na stannate stabilisation of H2O2 are very good...too bad they didn't investigate further...
We used much more than 70ppm (between 500 and 1000 ppm (0.5-1g/kg)) and the pH was lower than 5 (6.5-8)

About the cyclotetraaceton peroxyde (CTeAP), it is made via catalysis with some SnCl2 (or better SnCl4) with HCl. It is logical that being a higher multimer than cyclotriaceton peroxyde (CTAP) it must be of equaly or higher thermal (shock/friction) stability (this rule is observed for a variety of explosive stuffs)...probably because longer molecules have much more heat dissipating modes on a molecular level).
The finders of CTeAP (it is mixed with a little CTAP), mentionned it is significantly more stable towards heat and shock... but I wonder if the stability doesn't come from the presence of traces of Tin/Stannum into the mix.

[Edited on 26-5-2011 by PHILOU Zrealone]

The WiZard is In - 26-5-2011 at 05:50

Quote: Originally posted by PHILOU Zrealone

Thanks "The WiZard is In" it is nice to have you here...Don J Haarmann (djh)

I suppose you did left Alt.engr.explosive forum because it was not popular anymore?

BTW why did you change your pseudo during the transition?

Anyway, we must be a few of the old chaps from AEE.
Your information is as usual very valuable.

Some years back I retired and move out here in the country
with the cows. My fastest dial up speed was 24K, the RBOC
told me I was lucky to get dial tone so I switched
to Hughes Net satellite service, which I am happy to report has
gotten a lot more reliable/faster. H. Net does not support
newsgroups, leaving Deja.com as only free access. It is more
bother then worth.

Don't be remembering why I dropped donald j haarmann
for The WiZard is In. Occasionally — Mr. Emous - Emous, Anon -
Anon Emous.

Then there was a time when someone had the bright idea that
if they loaded tons of junk posts to rec.pyrotechnics,
alt.engr.explosive, sci.chem &c., someone would pay them to
stop.

Rosco Bodine - 26-5-2011 at 06:34

The tetrameric acetone peroxide gotten by use of the stannous or stannous chloride catalyst was done in absence of any added free HCl although surely
some low amount of HCl would be present due to hydrolysis. EDTA could also be reportedly used as a catalyst.

The WiZard is In - 26-5-2011 at 08:29

Quote: Originally posted by PHILOU Zrealone

Thanks "The WiZard is In" it is nice to have you here...Don J Haarmann (djh)

I suppose you did left Alt.engr.explosive forum because it was not popular anymore?

I have used The WiZ off/on since my first column in American
Fireworks News #15 October, 1982. NB - Note capitalization.

djh
----

The WiZard is In - 26-5-2011 at 09:00

Quote: Originally posted by BASF

I want to start a little project on stabilization of organic peroxides like acetone peroxide or hmtd.

Will this work for acetone peroxide.....?

Byda benzol peroxide was once used by the really brave for
movie Special F/X. Leaving it sitting out in the sun on a hot
day was considered a really bad idea.

From :—

Tobolsky & Mesrobian
Organic Peroxides
Interscience 1954

Rosco Bodine - 26-5-2011 at 09:20

There is no need to stabilize trimeric or tetrameric acetone peroxide, they are already stable. They are sensitive explosives yes indeed, and so are many other explosve materials which are also quite chemically stable absent the requisite stimuli which will cause their explosive decomposition. However, instability has the property of a gradual decomposition at ordinary temperature which must
be counteracted by some sort of stabilizer which interferes with and slows the
gradual decomposition. Such is not the case for trimeric or tetrameric acetone peroxide. Explosive is not at all equal to "unstable". For example silver fulminate
is quite dangerously sensitive and quite explosive, yet is also quite stable in the absence of those stimuli as would cause its explosion.

AndersHoveland - 26-5-2011 at 13:18

While Rosxo Bodine is making an excellent point that the proprty of stability is different from sensitivity, I would like to share some observations dealing specifically with acetone peroxide.

If the wet precipitate that forms on the surface is carefully scooped off, and the solid placed in a container for six months, the solid appears to separate out, leaving mostly liquid, with a portion of solid remaining on the bottom which occupies a volume which is only a small fraction of the original solid. I suspect that the compound is actually not chemically stable in long term storage. There will inevitably be some hydrolysis to acetone and hydrogen peroxide, the latter of which will very slowly attack the acetone through a spontaneous radical cascade mechanism.
For example, although H2O2 generally does not oxidize sugar, solutions of the two are not stable in storage and there is inevitably some oxidation, the rate of which rapidly increases with traces of iron ions or exposure to light.

Also, hexamethylene triperoxide diamine (HMTD) is not chemically stable, in addition to being very sensitive. It degrades after several months in storage to the point that it becomes impossible to detonate. Although supposedly, if the compound is free from traces of acid there is no degredation.

[Edited on 26-5-2011 by AndersHoveland]

Rosco Bodine - 26-5-2011 at 13:39

Correct HMTD is unstable at ordinary temperature, it gradually and steadily decomposes. If you have a pure dry sample of acetone peroxide, perhaps gotten by sublimation or by recrystallization from cooling of warm toluene in which AP is extremely soluble, my experience is it is stable at ordinary temperatures.
However AP has significant vapor pressure as a solid so it sublimes steadily,
which makes the containered material phase mobile. AP continually resublimes in any container using the container as a heat pipe for accomplishing its phase change loop, continuously recrystallizing itself like frost in a cycling freezer compartment.

detonator - 30-6-2011 at 02:41

I have tried using polyvinyl acetate emulsion mixing HMTD,then drying, be a mixture of more stable.

Adas - 23-11-2011 at 09:57

Some weeks ago I was trying to make TATP using direct dry ice cooling (putting dry ice into the reaction mixture), but it had no effect! No increase in stability, maybe even decrease. One time I have made very stable TATP, but I don't remember exact conditions. Shame. Now I am experimenting with how to remove lower/opened acetone peroxides. I will post the results soon.

AndersHoveland - 29-11-2011 at 11:35

If you are asking how to make organic peroxide explosives less sensitive, my answer would be that there essentially is no way to do this. To reduce sensitivity, there are only two possible routes:

Prevent formation of crystals. The best ways to do this would be to either dissolve the solid organic peroxide into an explosive liquid of lower sensitivity, simply use a liquid organic peroxide such as MEKP, or fully absorb the organic peroxide into a compatible polymer. Unfortunately, acetone peroxide partially sublimes at room temperature and can recondense in an enclosed container into crystals.

Dilute the organic peroxide. The problem with this is that mixing an inert subtance with the explosive will not proportionally reduce the sensitivity as much as it reduces the power. Alternatively, the diluting substance could be a less sensitive explosive. If the explosive used to dilute the organic peroxide is a solid, the organic peroxide will have to be so diluted that the initiation of a few localized grains would be unable to propagate. Essentially, one would think that no more than 20% organic peroxide could be used. Although a 1 to 1 ratio mix of acetone peroxide and ammonium nitrate seems to show decent resistence to flame initiation, such a mixture likely is much more sensitive to friction [although this has not been tested]. Any reduction in sensitivity caused by addition of ammonium nitrate is more likely due to the hygroscopic nature of ammonium nitrate, which helps to wet and keep the acetone peroxide moist. But besides from a "cushion" effect from the moisture, this is merely a form a dilution with liquid, since the water helps keep the residual acetone absorbed into the acetone peroxide. If this type of sensitivity reducing effect is desired, it would be much more effective to just moisturize acetone peroxide with some 1-butanol. If the explosive used to dilute acetone peroxide is a liquid, there are not any commonly available options that are ideal.

Theoretically, a solid 'fusion' between the two solids may also be possible, but actually making this would be problematic. Melting is just not an option, and if the two solids would have to be somehow isolated from a solvent before they had time to crystallize. A simple physical mix would not decrease sensitivity so much if microcrystals were allowed to form. I do not see this option as realistic.

TinkerKABOOM - 21-1-2015 at 16:07

I have never made AP or TATP but I have a few comparatively similar recipes I am going to try. I really hope everything works.
As far as stabilizing it for future use storage and transport I will try placing desired amount of AP in plastic wrap and then dipping that in melted wax. I should be able to make some nice bars or balls that I can stack and whatever.

Zyklon-A - 21-1-2015 at 19:09

Why not dip in molten lead? It'd be even stronger.

ecos - 22-1-2015 at 02:25

I didnt follow the whole thread , but what i know that anything that has peroxide in its name is very dangerous and sensitive.

this patent show some peroxides explosives : US 3047441A

it seems the mixtures there might be a more stable than AP.

[Edited on 22-1-2015 by ecos]

ecos - 22-1-2015 at 02:33

This mixture of "glycerol + H2O + H2O2" seems to be stable as stated by author : US2452074

PHILOU Zrealone - 22-1-2015 at 08:15

@TinkerKABOOM
Beware of overheating during wax melting an dipping. I don't understand what you want to do but it is risky!

@Zyklon-A
You are joking, are you?
Lead melting point = 327-328 °C
CTAP boiling point = 130°C
Also molten lead way over critical temperature for CTAP initiation

@ecos
I wouldn't play with H2O2 in high % mixed with non chemically pure chemicals.
H2O2 decomposition is highly dependant on impurities acting as catalyst (especially metals and organic matter).

Zyklon-A - 22-1-2015 at 19:13

Yeah, I was joking. Even candle wax seems dangerous, and I doubt it would help much anyway.

ecos - 23-1-2015 at 12:58

did u read the patent of glycerin-peroxide ?
you can use H202 with percentage like 50% and get it exploding , check the triangle in the beginning of the patent.
i would like to give it a try ...

btw, the author said it is bulletproof ;D

ecos - 29-1-2015 at 11:48

I think this study paper is excellent ; http://www.wydawnictwa.ipo.waw.pl/cejem/vol-10-2-2013/Matyas...
they decrease the sensitivity with water or oil.
have a look , it may help

VladimirLem - 30-1-2015 at 08:11

Quote: Originally posted by ecos

I think this study paper is excellent ; http://www.wydawnictwa.ipo.waw.pl/cejem/vol-10-2-2013/Matyas...
they decrease the sensitivity with water or oil.
have a look , it may help

YOU should have a look how fucking sensitive and dangerous peroxides are...

I use them too, but only as an ignition cap (smallquanitities), not as a maincharge or propellant

ecos - 30-1-2015 at 10:17

Hi vladimiR
who said that i want to play with peroxides??
I just try to help with articles i read

VladimirLem - 30-1-2015 at 11:02

Quote: Originally posted by ecos

Hi vladimiR
who said that i want to play with peroxides??
I just try to help with articles i read

your previous thread?

ecos - 2-2-2015 at 06:30

you should fix ur english

I don't want to change the topic here, I found some articles that might help others so i share it with them.
thanks

markx - 4-2-2015 at 01:09

Quote: Originally posted by VladimirLem

Quote: Originally posted by ecos

I think this study paper is excellent ; http://www.wydawnictwa.ipo.waw.pl/cejem/vol-10-2-2013/Matyas...
they decrease the sensitivity with water or oil.
have a look , it may help

YOU should have a look how fucking sensitive and dangerous peroxides are...

I use them too, but only as an ignition cap (smallquanitities), not as a maincharge or propellant

Never seizes to amaze how the illusion of safety becomes so pronounciated by the application of small quantities that people choose to handle peroxide based initiators. In my humble opinion this is about the most unsuitable application for these compounds. Small quantities can be viewed as unable to inflict permanent damage due the fact that the amount of energy released by them is quite harmless, but that does not make them safer intrinsically and only holds true for a situation where this energy is not transferred over to other compounds that are able to propagate detonation. In an initiator application this condition is not met...in fact by design the reverse in every aspect is promoted. Hence everything energetic connected to a peroxide "hair trigger" becomes just as unstable and unpredictable. It's a serious matter that deserves rethinking the approach...

ecos - 4-2-2015 at 10:34

I think all primary explosives are unstable !
do you have any stable primary Ex?