Sciencemadness Discussion Board - cheddite

cheddite

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Vikascoder - 11-4-2012 at 23:07

hello friends
on searching net i found a pdf file which stated that generally we make cheddite explosive bu potassium chlorate and petroleum jelly but in this pdf file i read that it can be substituted by potassium permanganate also. is it true?

Attachment: Blasting Explosives 1883 English Patent 5624.pdf (99kB)
This file has been downloaded 1716 times

[Edited on 12-4-2012 by Vikascoder]

Fossil - 12-4-2012 at 06:21

In theory it should work since potassium permanganate is a very powerful oxidizer. I would suggest you first try it first in a small quantity, using the same ratio as cheddite type O, which i believe is 9:1, and see how that goes. I have never tried making cheddite using potassium permanganate, but i have made cheddite type O with potassium chlorate.

Vikascoder - 12-4-2012 at 06:37

ya i used the same ratio 9:1 potassium permangante to petroleum jelly i tried to burn . it burned pretty nice with a crackin sound . i making hmtd to detonate it

PHILOU Zrealone - 12-4-2012 at 11:41

KMnO4 or MnO2 are catalyst for a faster realeasing of O2 out of KClO3 (or NaClO3)...at lower temperatures...this is how O2 was produced in the past for lab demos without risks.

So you may even think to a mix of traces of KMnO4 or MnO2 within your chlorate mix in a way to improve sensitivity.

Note that usually they use nitrobenzene or nitrated hydrocarbons...aside the fuel.
I personnaly used nitrated naphtaline in my KClO3 mixes.

caterpillar - 12-4-2012 at 12:28

Mixtures with KClO3 are much more powerful than their analogues with KMnO4. The last compound contents less active oxygen. I think, mixtures of KClO3 with reducing agents are sensitive enough, therefore one has to think how decrease their sensitivity, but not increase.

Bot0nist - 12-4-2012 at 15:41

Many cheddite mixes, like ones employing wax or petroleum jelly are not very sensitive at all, and it takes a well made, hefty cap or a booster to get them moving, IIRC.

497 - 12-4-2012 at 16:26

Sorry for being a little OT.

A well mixed combination frozen N2O4 crystals in cold gelled kerosene should be extremely insensitive if kept frozen. When ready to use, place it in position, let it thaw and it should become a cap sensitive homogeneous liquid with properties between PGDN and NG. N2O4 isn't too hard to make from OTC materials. If frozen immediately after production the toxicity is not a major problem with normal precautions (being outside!)

PHILOU Zrealone - 13-4-2012 at 01:13

Quote: Originally posted by Bot0nist

Many cheddite mixes, like ones employing wax or petroleum jelly are not very sensitive at all, and it takes a well made, hefty cap or a booster to get them moving, IIRC.

You got it

that is why I proposed an alternative mix of KClO3 and little KMnO4 to ensure better sensitivity to det-caps.

PHILOU Zrealone - 13-4-2012 at 01:17

Quote: Originally posted by 497

Sorry for being a little OT.

A well mixed combination frozen N2O4 crystals in cold gelled kerosene should be extremely insensitive if kept frozen. When ready to use, place it in position, let it thaw and it should become a cap sensitive homogeneous liquid with properties between PGDN and NG. N2O4 isn't too hard to make from OTC materials. If frozen immediately after production the toxicity is not a major problem with normal precautions (being outside!)

More than an little Of Topic

... you speak about panclastites...here the subject is cheddites.
But anyway what you wrote is true

and valuable info. Sole problem is the dangerousity of panclastites vs cheddites towards shock or heat.

Sounds scary as hell, but very interesting. Pretty fast for a non-molecular energetic. (oxidizer/fuel composition).

Quote:

Panclastites are a class of Sprengel explosives...

"During World War I, due to shortages of other explosives, French used some panclastite-class mixtures, which they called anilites, in small aircraft bombs. The mixing of the chemicals was triggered by airflow spinning a propeller on the nose of the bomb after it was dropped, mixing the previously separated chemicals inside. The resulting mixture was so sensitive the bombs did not need a fuze to explode on impact.

In the 1880s, Germans were testing torpedoes with panclastite warhead. Carbon disulfide and nitrogen tetroxide were stored in separate glass compartments, which were broken when the torpedo was launched and the chemicals mixed, and later were detonated by a contact fuse." ~ Wikipedia

[Edited on 14-4-2012 by Bot0nist]

Vikascoder - 13-4-2012 at 21:32

Bot0inst , these days i am little busy with some other project but for sure till 20th of april i will do this experiment and i will post my result . So please wait a little .

caterpillar - 13-4-2012 at 21:58

One thing about sd. just came to my mind. These explosives hardly could be detected- they may content no nitrogen at all and have no smell.

Vikascoder - 14-4-2012 at 05:41

Quote: Originally posted by caterpillar

One thing about sd. just came to my mind. These explosives hardly could be detected- they may content no nitrogen at all and have no smell.

though cheddite cant be detected but a person will need a detonator for detonating it .in my opinion the person will be caught because his detonating primary explosive would be containing nitrogen .he may use other detonators also but generally detonator which do not contain nitrogen are unstable and very sensitive like acetone peroxide, cuprous acetyalide.

Bot0nist - 14-4-2012 at 10:18

Who's worried about smuggling it? Damn guys.

I wonder if compositions employing nitro aromatics and similar fuels would compare to the sensitivity of the types that use more inert, but still energy rich fuels like paraffin and such. I imagine that the latter would be less sensitive. Pure speculation though. Going to try some literature searches when back at me computer. On my phone.

caterpillar - 14-4-2012 at 20:14

Mixtures with KClO4 are much safer than their analogues with KClO3, but preparation of KClO4 is more problematic.

Vikascoder - 14-4-2012 at 23:18

Potassium perchlorate mixtures are even more difficult to detonate then chlorate and also it is very difficult to make as compared to potassium chlorate.

Fossil - 15-4-2012 at 07:56

Quote: Originally posted by Vikascoder

Potassium perchlorate mixtures are even more difficult to detonate then chlorate and also it is very difficult to make as compared to potassium chlorate.

Perchlorate mixes are not hard to set off at all. Take a look at 7:3 flash powder or even 2:1 flash powder.

Edit: quote messed up

[Edited on 2012-4-15 by Fossil]

Bot0nist - 15-4-2012 at 08:12

I believe they mean detonate with explosive shock, not ignite flash powder. While having more available oxygen, perchlorate is less reactive than chlorate. This would likely result in a composition that is much less sensitive, maybe even not cap sensitive at all.

Vikascoder - 15-4-2012 at 08:31

Quote: Originally posted by Fossil

Quote: Originally posted by Vikascoder

Potassium perchlorate mixtures are even more difficult to detonate then chlorate and also it is very difficult to make as compared to potassium chlorate.

Perchlorate mixes are not hard to set off at all. Take a look at 7:3 flash powder or even 2:1 flash powder.

Edit: quote messed up

[Edited on 2012-4-15 by Fossil]

here we are talking to detonate the cheddites not deflagrate the flash powder . Do you know that perchlorate is preferred because it is less sensitive than chlorate and here we are working on the sensitivity not just simply burning. Setting off means detonating not simply burning.

Fossil - 15-4-2012 at 09:28

Sorry, i thought you guys stopped talking about cheddite, and yes, i do know the difference between a deflagration and a detonation.

And yes, perchlorate is used in flash powder compositions because it is much more stable than compositions made with a chlorate mixture.

caterpillar - 15-4-2012 at 11:53

Quote: Originally posted by Fossil

Sorry, i thought you guys stopped talking about cheddite, and yes, i do know the difference between a deflagration and a detonation.

And yes, perchlorate is used in flash powder compositions because it is much more stable than compositions made with a chlorate mixture.

Perchlorates have better oxygen balance too. One way to prepare KClO4 is to melt KClO3. I suspect that this op is potentially dangerous one.

Vikascoder - 16-4-2012 at 05:22

most easy way of making potassium perchlorate from potassium chlorate is to just add hydrogen peroxide. this will give one mmore oxygen atom to potassium chlorate molecule forming potassium perchlorate

Bot0nist - 16-4-2012 at 05:52

Quote: Originally posted by Vikascoder

most easy way of making potassium perchlorate from potassium chlorate is to just add hydrogen peroxide. this will give one mmore oxygen atom to potassium chlorate molecule forming potassium perchlorate

Says who? They lied to you. That is a silly assumption that a non chemist would make.

With all due respect Vik, that is total BS. If that was so, people wouldn't bother with thermal dissappropriation or electrolysis. This lie has been shot down on SciMad many times. Please do not regurgitate misconceptions.

Also, if the production of perchlorates is your interest, please continue in the many perchlorate threads. Don't further derail this one, which has nothing to do with perchlorate manufacturing.

Thanks.

Quote: Originally posted by woelen

That video is crap. Chlorate does NOT react with peroxide to make perchlorate!

Making perchlorte from chlorate cannot be done with MMO anodes, but it can be done with PbO2 anodes or platinum anodes. Another (more dangerous) option is to carefully heat perfectly pure KClO3 in a perfectly clean heat resistant glass apparatus until it just melts and then keep the temperature constant. Slowly the chlorate is converted to perchlorate and chloride. This latter procedure was used in the past as the main method for making perchlorate, but nowadays it is replaced by electrolysis with PbO2 or platinum anodes, because of safety concerns.

[Edited on 16-4-2012 by Bot0nist]

weiming1998 - 16-4-2012 at 06:14

Quote: Originally posted by Vikascoder

There has been discussions about the oxidation of KClO3 to KClO4 on this very forum. Example: http://www.sciencemadness.org/talk/viewthread.php?tid=16931

On that thread, it says that H2O2 will not work in oxidizing KClO3 to KClO4. It is not a strong enough oxidant. But elemental fluorine, ozone and ferrates will work though, with the last option being the least dangerous.

[Edited on 16-4-2012 by weiming1998]

Vikascoder - 16-4-2012 at 07:12

thanks Bot0nist and weiming 1998 for correcting me . i was also thinking that this process doesnt seem to work but according to this video i got the information
http://www.youtube.com/watch?v=9YVsEX-ikUQ
and i told you what it was told in this video .thanks once again for correcting me .i havent tried it myself i hope i have not irritated you. and i am not interested in making potassium perchlorate.
please forgive me for my wrong information

Hennig Brand - 22-4-2012 at 12:45

I have never detonated a cheddite, but I plan to do some experimenting soon. I have read that MNT and DNT will both work well. I have some pdfs of some old books with procedures for preparing some cheddites. IIRC, from reading the cheddites that use nitroaromatics are much easier to initiate than the cheddites that just use fuels/hydrocarbons. They are also more powerful of course.

I am going to try MNT and DNT with KClO3. Should I try nitro-naphthalene next, or a different nitroaromatic?

This was from an old book (early 1900's). I kept this section as a word document, sorry I don't seem to have the reference.

"Chlorate and Perchlorate Explosives.
The developments of electro-chemistry having resulted in the production of
chlorates in large quantity, an outlet for these was sought in the sphere of
explosives and ultimately found. Chlorates have long been forbidden lor
explosives manufacture on account of the sensitiveness of mixtures containing them
to shock and friction. Street found, however, that by using castor oil in the mixture
this danger was obviated (D.R. Patent 100,522, 1897; 100,532, 1897; 117,051,
1898; 118,102, 1898). Cheddites, so-called from their place of manufacture,
Chedde, in Haute-Savoie, are composed as follows (Dr Escales' article on
" Explosivstoffe," Dammer's "Chemische Technologie der Neuzeit"): (1) KC1O3
79 per cent., nitro-naphthalene 15 per cent., castor oil 6 per cent. ; (2) KO08
79 per cent, dinitro-toluene 15 per cent, nitro-naphthalene 1 per cent, castor oil
5 per cent; (3) NaC10s 75 per cent., dinitro-toluene 19 per cent, nitro-naphthalene
1 per cent, castor oil 5 per cent.; (4) KC103 80 per cent., dinitro-toiuene 2 per
cent., nitro-naphthalene 10 per cent., castor oil 8 per cent.

Manufacture
The dinitro-toluene and nitro-naphthalene are dissolved in warm (6o°-7o°) castor
oil contained in a double-walled enamelled iron vessel, and the finely pulverised,
dried and sieved potassium chlorate is added with constant stirring or kneading by
means of a large wooden paddle. After further working the explosive is corned
and on standing for some time is made into cartridges which are waterproofed."

I have more material on cheddites too, if I can find it.

[Edited on 22-4-2012 by Hennig Brand]

quicksilver - 23-4-2012 at 11:02

CHEDDITE is still a commercial company. They may be publicly traded in Europe's various sock exchanges. They make a great deal of firearm's related energetics.

Hennig Brand - 23-4-2012 at 18:12

Yes, if you search for cheddite now you are more often than not going to get hits for shot gun primers and things, very annoying if you want the old fashioned main explosive charge type.

Here is a little more specific information on Cheddites:

Taken from the chapter on Potassium Chlorate, in the text Military Pyrotechnics Vol 1 by Faber, Henry Burnell

The following jpg is of the table which preceeds the text below.

"In making cheddite mixtures, the nitro compounds are
first dissolved in the castor oil at 80° C, and the finely pow-
dered, dry, warm chlorate is then added gradually, while the
mass is stirred with a wooden rod. The incorporation of a
charge of 25 kilograms lasts about 10 minutes. The mate-
rial is then carried to another building where it is further
mixed on a wooden board while half -cold for another 10 min-
utes, so as to get it in a suitable granular condition. Each
particle of chlorate should be entirely coated with the oily
mixture. The material is next sifted and what is too fine is
added to a later charge. That which is of the corect size is
made into cartridges by ramming it into wooden molds, from
which it is transferred to paper cases. If the explosive con-
tains sodium chlorate, the cases should be then dipped in
molten parafiin to prevent the absorption of water : If the
per cent, of moisture rises above 1 per cent, the explosive is
impaired.

Cheddite is a soft yellowish material of fine grain, but is
sometimes artificially colored. In consequence of its plastici-
ty, it can easily be compressed. It is generally put up into
cartridges 22 cm. long and 2.5 cm. diameter. Cheddite
(41) is a slow, mild explosive, which splits rocks rather than
shatters them. Cheddite (60) is more violent, and the so-
dium-chlorate cheddite (05), still more so. The velocity of
detonation of cheddite (60) was measured by Llieure
and found to be 3,175 meters per second, about half that of
picric acid, and blasting gelatine and other very high explo-
sives, and that of (02), 2,750 meters per second."

[Edited on 24-4-2012 by Hennig Brand]

Farnsworth - 18-5-2012 at 18:41

Point of curiosity related to this thread.

In the older text cited above concerning the substitution of KMNO4 for chlorates in a cheddite mixture brought to mind an older topic concerning sodium chlorate combined with liquid fuels and water for achieving unusually high detonation velocities. See:

http://www.sciencemadness.org/talk/viewthread.php?tid=4076

I know KMNO4 is bad news when combined with most of the common fuels discussed in that thread. Everyone knows what happens with glycerine and according to the MSDS it becomes a dangerously spontaneous explosive when combined with diethylene glycol. Are there any suitable liquid fuels with which it can be combined without becoming dangerously unstable / self decomposing? Ethyl alcohols seem to be out due to reactivity which would have been a very convenient package. MSDS pegs it as highly soluable in methanol but also notes that it's incompatible with alcohols in general. Can someone with a better understanding of its full spectrum of reactivity chime in?

Edited for details.

[Edited on 19-5-2012 by Farnsworth]

Vikascoder - 3-6-2012 at 07:46

One more cheddite compositon i found . As i failed in making picric acid yesterday by mistake i made dinitrophenol instead of trinitrophenol. I mixed 2 grams of dinitrophenol with 3 grams of potassium chlorate and detonated it with HMTD and a no 8 blasting cap it was really very loud bang.

Hennig Brand - 3-6-2012 at 09:33

There is a good section in the COPAE on Cheddites. I have included a snip-it from the text.

niertap - 29-6-2012 at 08:52

Potassium Dichromate supposedly catalyzes perchlorate decomposition. I've seen multiple references to it in pyrotechnic star primes, though never a scientific source.

However i'm unsure if it would also apply to the reaction conditions of detonation. Also cancer.

I've only had luck with chlorate cheddite when it's bound with some nitrocellulose and has a little MnO2 in it. Though this was without a booster and just a little AgN3.

al93535 - 1-7-2012 at 11:09

Dichromate absolutely does catalyze the decomposition of KClo4. While trying to make stars at work safer to manufacture, I removed the 5% dichromate. In a mine those stars burned so much slower, they almost came back to the ground. So there is a significant effect that the dichromate has upon the stars burning speed.

You do bring up a good point about if the dichromate will assist in a KClo4 detonation.

I would like to try making a cheddite but replace the KClo3 with KClo4. Now i am considering adding 3% milled Potassium Dichromate to the mix.

I am considering this:

KClo4 70
DNT 17
Dichromate 3
Vaseline 10

However there is not very much information on perchlorate explosives, I have found my only reference in COPAE.

I have made regular cheddite with 90% KCl03 and 10% vaseline. It was easily detonated with a commercial No. 8 cap. I have a video of it, If I can put a link here to it??

Hennig Brand - 26-12-2013 at 13:28

I finally got away from the city for a little bit and took a break from eating Christmas cookies and turkey to do a little experimenting. Had some impure KClO3, with a little graphite mixed in from carbon electrode errosion, and some TNT heavily contaminated with DNT (~76% TNT / 24% DNT). I have always put off making a Cheddite, but decided that today was the day. A nifty little pull igniter was used, which was activated from 100 feet away or so by the pull of a string, in order to initiate the firing train.

In general the instructions from COPAE were used for preparing the Cheddite. Water was boiled in a kettle and then put into a saucepan which was used as a hot water bath. A 600 mL beaker was used to mix the components together and was held in the hot water bath to keep the mixture at around 80 C. The TNT-DNT mixture was dissolved in the castor oil first then the powdered KClO3 was added, by the spoonful, and the mixture stirred well with a piece of small diameter wooden dowel. Once the mixture was considered homogeneous it was dumped out onto a table, on a big piece of waxed paper, where it was flattened out with the back of a plastic spoon and allowed to cool before being broken up with the same spoon.

Quantities used:
84 g KClO3
16 g TNT/DNT
5.5 g Castor Oil

I pressed half of what was made (~ 53 g) into a plastic pill bottle of about 40 mL in volume, which gave an overall charge density of about 1.32 g/mL. I was not, however, nearly careful enough to get the density uniform throughout the charge. The blasting cap was made with about 0.6 g PETN as base charge, 0.3 g lead azide as primary and a little basic lead picrate as flash igniter. Visco fuse (1/8") was used. The end of the fuse which was to be placed directly beside the percussion cap was dipped in NC lacquer and covered in black powder (fast burning powder/dust from the ball mill) before being allowed to dry several hours before use. A little gun cotton was also stuffed in around the base of the primer, but was probably not needed.

About 100 feet of thin nylon cord was used to pull the pin. The firing train worked perfectly, even where the fuse had been cut and 4 matches put in place where it had been taped back together. The charge however was only a partial success. There was a definite detonation, but the ground below the charge was littered with undetonated material. It seems from looking at the aftermath that the material next to the detonator went off, but the material much below did not.

A few pictures:

[Edited on 27-12-2013 by Hennig Brand]

Hennig Brand - 26-12-2013 at 13:38

A little KMnO4, or a couple percent of NG, might make a big difference in the ease with which this mixture is initiated.

The charge and initiating system where not put together for aesthetic appeal, but more to test some concepts, as can be seen by the clumsy looking system. BTW, the KClO3 was powdered using ~ 100 mesh SS screen (from a fuel screen) epoxied into a small kitchen strainer and a wooden rod with a rounded end. If doing large quantities a ball mill or some other automated milling machine would be very advantageous.

As you can see the little piece of maple that the charge was attached to was blown to splinters. even though there was only a partial detonation. The biggest piece of the maple stick found was located 6-8 feet away after detonation, and can be seen in the pictures below.

The partial detonation could have been prevented. A strong detonator was used, but charge density was not carefully controlled (even though overall charge density was in the correct range) and there was very weak confinement.

A few more pictures:

[Edited on 27-12-2013 by Hennig Brand]

Turner - 26-12-2013 at 14:53

Cool why such a way to light the fuse?

Hennig Brand - 26-12-2013 at 16:05

Thanks, it was just a test, but really it is a much safer way to light the fuse. Even with good fuse, bending over a charge lighting a fuse with a lighter or match is taking a risk. Pulling the cord from 100 feet away is very low risk in comparison. The simple design above uses a compression spring, but most grenades etc use a torsion spring which makes them much more compact. I saw a few youtube videos, and then made a few modifications of my own.

[Edited on 27-12-2013 by Hennig Brand]

Pard - 28-12-2013 at 17:23

Is that a cap gun cap there? I take it that it sets of your detonators charge.

Hennig Brand - 29-12-2013 at 07:05

Yes, with a suitable firing train they can reliably light visco or cannon fuse (or whatever).

Zyklon-A - 29-12-2013 at 19:21

Here, I found something that says you can make a 'cheddite' with KNO3, I don't trust this site at all, but I tried it anyway, it says ''When wet it is harmless... but when it dries it is
highly explosive and shock sensitive. ****store in oil''.
''Well this is stupid'', I thought, petroleum jelly never will dry, anyway, it didn't work at all, I followed the instructions exactly, and just for fun I set it out to 'dry', now 2 months later it looks the same, not going to work at all, ever.
I suggest that you don't try anything from this site, about half of the things they say are false, and the other half can get you killed.

[Edited on 30-12-2013 by Zyklonb]

Turner - 29-12-2013 at 20:27

I hate those kind of websites, books, manuals like you linked there.

Hennig Brand - 30-12-2013 at 13:35

There are lots of good books on explosives, which are readily available for download, some of which right from this forum's library. Why bother with those foolish cookbooks?

Anyway, I used the other ca. 53 g of Cheddite for another test. The previous partial detonation indicated that poor propagation through the charge was an issue. In an attempt to improve performance about 1.4 mL of nitroglycerine was added, producing a charge of about 4% NG by weight. A blasting cap nearly identical to that used in the previous trial was used. A couple pictures, and 4 stills from a video, are included below.

The detonation was very loud (much louder than before), and with a large cloud of smoke (as in the first trial). It was obvious from examining the post detonation scene that there was a much more complete detonation. A small amount of undetonated material was found, but it was estimated that it amounted to less than 10% of the total charge, whereas before an estimated 30% was seen scattered on the ground.

From reading, it was found that the Chedittes were made to be used in larger charge sizes and/or with significant confinement. My 50-60 g charges were very small, and had very weak confinement, which was not ideal. Also, the castor oil components main purpose, in a Cheddite, is to reduce sensitivity. I believe if the castor oil was eliminated, or its quantity at least reduced, initiation would be easier and propagation better in smaller, less well confined charges. A solid fuel could be used in place of the castor oil which should increase sensitivity and improve propagation. The added NG definitely improved propagation, which was no surprise.

[Edited on 31-12-2013 by Hennig Brand]

roXefeller - 30-12-2013 at 19:02

A lovely and tranquil scene. It must add to the pleasure of loud noises and the smell of smoke plumes wafting by. Is it your plan to plow that 2-track this winter with more charges?

BTW, great idea for remote ignition, I've been trying to conceive of something like that but I was only imagining pistol primers. Do you use a sufficient length of visco to give visual indication at a distance that the firing train is lit?

[Edited on 31-12-2013 by roXefeller]

Hennig Brand - 31-12-2013 at 06:49

Thanks, depending on atmospheric conditions there are sometimes really nice echoes over the country side following a detonation. Warm humid days, or rainy days, in the summer seem to produce the best audible effects. Dry cold days in the winter don't produce as nice an effect. This is my perception anyway. In the last few weeks we have had probably about 6 little storms, so it is hard to keep ahead of the snow. The visual effect of the fuse burning down does add a lot to the whole experience, yes. I normally use 6-10 seconds of fuse probably, but I am sure the experts would say to use much more for safety.

Zyklon-A - 31-12-2013 at 19:15

Quote: Originally posted by Turner

I hate those kind of websites, books, manuals like you linked there.

Yes, I hate them to, but I have to admit, as far as I remember that is what got me interested in chemistry, I saw something there, tried it, and miracle of miracles, it worked, almost nothing else there works though.

Pard - 31-12-2013 at 22:46

Quote: Originally posted by Zyklonb

Here, I found something that says you can make a 'cheddite' with KNO3, I don't trust this site at all, but I tried it anyway, it says ''When wet it is harmless... but when it dries it is
highly explosive and shock sensitive. ****store in oil''.
''Well this is stupid'', I thought, petroleum jelly never will dry, anyway, it didn't work at all, I followed the instructions exactly, and just for fun I set it out to 'dry', now 2 months later it looks the same, not going to work at all, ever.
I suggest that you don't try anything from this site, about half of the things they say are false, and the other half can get you killed.

[Edited on 30-12-2013 by Zyklonb]

Wow wee, this must be writ by comedians. Listen to this one tells you to tape nails to a can of vaseline and then stick a fuse in and it will blow up? What nonsense.

Currently I have some NH4ClO4 and will obtain some vaseline soon in order to try the cheddite as proposed with it. I cannot recall which thread it was exactly, perhaps this one.

Zyklon-A - 31-12-2013 at 23:50

It seems like they think a 1 to1 raito will work all the time, or some times, nothing at all."Just mix I2 with NH3 (aq), and you'll get some black stuff, just filter it off and then leave it to dry in you're room (or some other very safe place like your closit or behind the toilite").

markx - 1-1-2014 at 04:19

Quite the energetics these chloratites....made a small test on the simplest formulation with 9 kclo3/1 kerosene (30g):

The yellowish coloration is due to iron oxides from the milling media, but nonetheless it left a nice mark on the witness body

Hennig Brand - 1-1-2014 at 07:11

If you used a ball mill, you would have easily been able to get the chlorate down to smaller particle size than I did, which should improved sensitivity and propagation. What I produced with the homemade sieve was about 100 mesh, but a ball mill could do much better. What did you use for an initiator?

Is the piece of material (witness plate) in the second picture supposed to be the same as the piece of material in the third and fourth? Not really sure what the charge is supposed to have done to the target exactly. What is the target?

[Edited on 1-1-2014 by Hennig Brand]

roXefeller - 1-1-2014 at 07:42

It looks like a C-channel steel, or a rectangular extrusion. With a difference in lighting conditions, they seem to be the same, same hole placement and black splatter on the left.

[Edited on 1-1-2014 by roXefeller]

markx - 1-1-2014 at 08:43

Test body is rectangular steel tube with 1,6mm wall thickness. There was no pinpoint objective on what the charge should have done to the test body in that experiment...I guess what you see in the last pictures is about exactly that what could have been expected

(And yes, the pictures are of the same test piece)
ETN/SADS (600/60mg) compund cap was used for stirring things up. Like this one:

[Edited on 1-1-2014 by markx]

Dany - 1-1-2014 at 08:53

Quote: Originally posted by markx

Test body is rectangular steel tube with 1,6mm wall thickness. There was no pinpoint objective on what the charge should have done to the test body in that experiment...I guess what you see in the last pictures is about exactly that what could have been expected

(And yes, the pictures are of the same test piece)
ETN/SADS (600/60mg) compund cap was used for stirring things up. Like this one:

[Edited on 1-1-2014 by markx]

What about the loading density of each of each explosive tested? this is important so you can compare between the 3 explosives. having the same mass (0.6 g) is not enough for comparison if you don't know the loading density. Have you tried to check up the loading density?

Dany.

markx - 1-1-2014 at 09:24

Yes, I'm well aware of the importance of loading density and no, I have not tried to measure or match it so far. But when referring to the series in my last post, I owe an explanation: the three compounds were used not to compare their effect, but to test the primary's ability to initiate them

Therefore I did not spend any effort on exacty matching their density, they were just lightly compacted to fit the casing snugly and uniformly.

Dany - 1-1-2014 at 09:41

Quote: Originally posted by markx

I did not spend any effort on exacty matching their density, they were just lightly compacted to fit the casing snugly and uniformly.

As you know the initiating ability of a substance depend also on the density of the main charge. with increasing density charge the initiation become harder (because of the lack of enough voids and inhomogeneities for hot spot formation). Some explosive become dead pressed when confined to high density (which is not a problem in your case). So density should be checked as far as possible so as to get good results with logical conclusions

Dany.

roXefeller - 1-1-2014 at 10:04

Quote: Originally posted by markx

Therefore I did not spend any effort on exacty matching their density

By matching do you mean identical densities? Is having identical densities necessary? I suppose that propagating waves would have less reflection and more transmission at the boundary if there wasn't a density discontinuity, but this seems like a minor effect.

markx - 1-1-2014 at 10:40

All true...the tighter it sits, the harder it is to wake up (thanks for pointing that out), but I worked towards a specific case this time : these 3 compounds, "hand compressed" with same mass of primary/secondary through the series. The question: go or no go?

Got my answer

No further conclusions were drawn from the results this time.

Of course having identical densities is not neccesary, but it may make comparison easier (depending of course on what the initial goal of the experiment is)

[Edited on 1-1-2014 by markx]

Hennig Brand - 1-1-2014 at 12:12

The following table, showing more modern French Cheddite formulations, is from "Military Explosives TM 9-1300-214" (1984). Average density for these charges was stated as being 1.3 g/mL. Notice that there is more DNT and less chlorate used than in the older formulations previously posted. Notice also that no castor oil is used.

Hennig Brand - 1-1-2014 at 12:27

The following is a copy/paste from an archived copy of some of the rec.pyrotechnics newsgroup posts. These guys know a lot about the subject matter, and I thought it would be good to post this very concise and informative description of how these types of explosives behave.

Newsgroups: rec.pyrotechnics
From: arno@utu.fi (Arno Hahma)
Subject: Re: Na/KClO3 w/ Vaseline??
Organization: University of Turku
Date: Wed, 5 Jul 1995 10:16:03 GMT

In article <3tavr6$rh1@geraldo.cc.utexas.edu>,
Gerald L. Hurst <glhurst@onr.com> wrote:

>not both. My question relates to whether the
>material truly supports a classic detonation head
>or if, instead, it reacts only at the deflagrating
>surface like a propellant, only much faster than

Yes and no. The (per)chlorate/vaseline mixture detonates at about 3000 m/s
at a density of 1.3 g/ccm and about 4000 m/s at a density of 1.5. [J.
Wuorinen, "Räjähdysaineoppi", Otava (1928), Helsinki, Finland, pp.
162-165, in Finnish; T. Urbanski, "Chemistry and Technology of
Explosives", Pergamon Press (1986 reprint), Exeter, Great Britain,
Vol. 3, pp. 277-279].

If you calculate the theoretical detonation velocity assuming 100 %
reactivity, you'll get something like 5000..6000 m/s. With the mere
3000 m/s there is still a detonation, but only about 30 % of the
material is reacting based on calculations. Thus, the detonation is
highly unideal (i.e. not a classic one) and sensitive to the particle
size of the chlorate (more surface, more contact to the fuel, more fuel
reacting, higher detonation velocity) and to the way the material is
packed and initiated. Also, the nature of the fuel is going to make a
big change - use something like nitrobenzene or dinitrobenzene and
you'll get a considerably higher velocity because shocking the fuel is
not eating so much energy as shocking vaseline.

Potassium chlorate is pretty "neutral" towards shock, it releases some
energy when decomposed, but not enough to sustain detonation. As a
result, you only need to add a little energy to get the detonation
going. But, you need a continous phase of some kind to transmit the
shockwave through the mass without too much attenuation. This
is one of the reasons, why powdered mixtures (like perchlorate/Al or
chlorate/sugar) are so hard to detonate.

KClO4/Al at least does not detonate at all (not even deflagrates
reliably, unless the Al is extremely fine powder), which doesn't mean
it wouldn't be hazardous or wouldn't explode. I have an article
in print about this in Propellants, Explosives, Pyrotechnics and I'm
also going to present information about it in the next ADPA conference
in September.

>Many people might say "who cares," but it is of
>very great interest to me and probably others
>in this forum.

Yep! The same applies to ANFO as well. ANFO also detonates
very unideally with only about 50 % of the material contributing
to the shock energy unless extremely well confined. Again, the amount
of material reacting at the reaction zone (as far as classical
detonation is concerned) is highly dependent on variables like charge
diameter, confinement, particle size, degree of mixing, fuel
composition etc. Good references are C. Mader, "Numerical Modeling of
Detonations", UCLA Press, Berkeley and LA (1984), p. 99 and A. C. van
der Steen et al., "Detonation Velocities of the Non-Ideal Explosive
Ammonium Nitrate" in Propellants, Explosives, Pyrotechnics 15 pp. 58-61
(1990).

testimento - 2-1-2014 at 23:42

So, packing up 90 parts of powdered chlorate and 10 parts of fuel oil with a good detonator will do the job?

markx - 2-1-2014 at 23:54

Quote: Originally posted by testimento

So, packing up 90 parts of powdered chlorate and 10 parts of fuel oil with a good detonator will do the job?

That is ratio by mass, as always (just to avoid confusion). And yes, it packs quite a punch....is loud as hell too.

testimento - 3-1-2014 at 01:43

Excellent. Gotta wake up my 3kW electrolysis cell.

Could this composition be initiated with ball mill powdered ammonium perchlorate aluminium mixture, maybe 10-50g charge?

markx - 3-1-2014 at 02:44

I do not know if flash will wake it up....I would not count on it though. I'd rather try a smaller sharper slap to get it going (nitric esters, nitramines etc.). Besides if only your booster is already going to weigh 50g, man, better not to work with such quantities. Keep it safe, friend!

Hennig Brand - 4-1-2014 at 04:22

Quote: Originally posted by markx

Quote: Originally posted by testimento

So, packing up 90 parts of powdered chlorate and 10 parts of fuel oil with a good detonator will do the job?

That is ratio by mass, as always (just to avoid confusion). And yes, it packs quite a punch....is loud as hell too.

Potassium chlorate and fuels, liquid and/or solid, can be made to detonate, but they are not Cheddites AFAIK. I have seen a couple of different definitions, that differ slightly, but I think a Cheddite always has nitroaromatic(s) in it.

markx - 4-1-2014 at 06:12

Urbanski also states mixtures without nitroaromatics as members of the cheddite family:

So I guess the definitions are a bit vague...

Hennig Brand - 4-1-2014 at 07:13

The common link in that table seems to be the moderant (castor oil or petroleum wax). Ok, potassium or sodium chlorate with wax or Vaseline are often classified as Cheddites, but I don't think Chlorate with liquid hydrocarbons alone are (I could be wrong). Anyway, interesting that it works especially since it is a very simple explosive with easily obtained/made components.

Zyklon-A - 6-1-2014 at 08:21

How well do cheddites work with no kerosene (only petroleum jelly), are they more difficult to detonate. I don't have any kerosene an the moment.

testimento - 6-1-2014 at 09:07

Do you have any idea what would be the RE Factor and detonation velocity of ball milled Na/KClO3+FO 90:10 mixture initiated with good booster like ETN?

And btw, why everyone outright prefer potassium chlorate instead of sodium? The latter has more oxygen in weight(6%), it comes straight out of chlorate cell and it's only drawback is that it absorbs water - but hey, everyone still uses AN with FO and everyone's fine with that? I suppose that NaClO3 can be dried ground dry when heated up to 150-200C.

[Edited on 6-1-2014 by testimento]

Gargamel - 6-1-2014 at 10:38

Thank you for posting your experiences and blast reports.

I'm very interested in this kind of mixtures because my chlorate cell provides me with an endless supply of raw material.

The old commercial mixtures with nitroaromatics in them aren't much of value for the hobbyist, especially with nitrates and acids becoming more regulated for us in the EU.

I'd prefer to produce something like ETN over wasting precious nitric ect. for DNT, only to get stuff that is barely faster than 3000m/s and has obviously trouble to fully detonate without confinement.

Quote:

And btw, why everyone outright prefer potassium chlorate instead of sodium? The latter has more oxygen in weight(6%)

I wonder if one can actually use this oxygen with oil. Most Chlorate mixtures do not seem to detonate very well with more than 9% oil. Therfore I wonder if the common ratios have necessarely something to do with OB?

[Edited on 6-1-2014 by Gargamel]

Turner - 6-1-2014 at 16:53

TNT can be very nitric acid efficient depending on the operator and reaction circumstances.

RDX is by far the worst and most frustrating explosive if you value the costly nitric acid, 50ml gave me 6 grams of RDX and that isn't far off from theoretical yield.

Hennig Brand - 6-1-2014 at 18:46

DNT can be made much more easily than TNT, and with just nitrates and without the most highly concentrated sulfuric acid.

DNT in a Cheddite should actually increase sensitivity and propagation. It provides a continuous phase of high explosive material throughout the charge covering every particle of chlorate. The last table I posted was from a US military text published in 1984 and the text associated with that table described the mixtures as modern Cheddite formulations I believe. Nitroaromatics are generally considered to make Cheddites perform better, from what I understand.

Here are the 2 big reasons my charges had issues with propagation (I think).

1. The chlorate was not ball milled, but passed through a 100 mesh screen. Ball milling would have produced much finer material resulting in much better contact between the chlorate and the nitroaromatic(s) and fuel, resulting in better propagation, sensitivity, power, etc.

2. The chlorate was homemade and contained at least a small amount of chloride contaminant. The KCLO3 was made several years ago by electrolysis. I believe it was recrystallized once, but honestly I can't remember. The amount of chloride in any commercial sample, I would imagine would be far less than in mine. Sodium and potassium chloride are diluents, but they also cool the explosion, and also are hygroscopic which usually results in chlorate with higher amounts of moisture. Even small increases in moisture content greatly reduce sensitivity, etc, etc.

Honestly, I think the biggest difference between my test and Markx's test would be chlorate particle size. Small charges with weak confinement require other variables to be improved, and that means particle size, degree of mixing, density, strength of initiation, possibly added sensitizer, etc.

BTW, a couple or a few percent of aluminum powder is supposedly excellent for increasing sensitivity of Cheddites. I have never tried it with Cheddites, but I know it greatly increases the sensitivity of dynamites.

[Edited on 7-1-2014 by Hennig Brand]

testimento - 6-1-2014 at 21:05

Quote: Originally posted by Turner

TNT can be very nitric acid efficient depending on the operator and reaction circumstances.

RDX is by far the worst and most frustrating explosive if you value the costly nitric acid, 50ml gave me 6 grams of RDX and that isn't far off from theoretical yield.

Funny thing that HNO3 is more available to me than sulfuric acid, which why I prefer nitrations that do not need SA.

According to my calculations, one will need a total of 533ml sulfuric acid, including oleum, and a total of 231ml HNO3 100% to get about 200 grams of TNT. The sulfuric acid is mostly recoverable through concentration, but it cannot be boiled up to oleum back anymore, so one will need to regenerate it somehow.

Turner - 6-1-2014 at 21:09

Of course if I had stockpiles of pure Nitric Acid I would do a lot with RDX, but for me it's distilling it from already expensive sulfuric acid and nitrate. I once made around 20 grams and detonated that, cool material because it is very different sound than say an explosive like ETN, almost muffled and not as loud, but just as damaging.

markx - 7-1-2014 at 00:30

Quote: Originally posted by Hennig Brand

DNT can be made much more easily than TNT, and with just nitrates and without the most highly concentrated sulfuric acid.

DNT in a Cheddite should actually increase sensitivity and propagation. It provides a continuous phase of high explosive material throughout the charge covering every particle of chlorate. The last table I posted was from a US military text published in 1984 and the text associated with that table described the mixtures as modern Cheddite formulations I believe. Nitroaromatics are generally considered to make Cheddites perform better, from what I understand.

Here are the 2 big reasons my charges had issues with propagation (I think).

1. The chlorate was not ball milled, but passed through a 100 mesh screen. Ball milling would have produced much finer material resulting in much better contact between the chlorate and the nitroaromatic(s) and fuel, resulting in better propagation, sensitivity, power, etc.

2. The chlorate was homemade and contained at least a small amount of chloride contaminant. The KCLO3 was made several years ago by electrolysis. I believe it was recrystallized once, but honestly I can't remember. The amount of chloride in any commercial sample, I would imagine would be far less than in mine. Sodium and potassium chloride are diluents, but they also cool the explosion, and also are hygroscopic which usually results in chlorate with higher amounts of moisture. Even small increases in moisture content greatly reduce sensitivity, etc, etc.

Honestly, I think the biggest difference between my test and Markx's test would be chlorate particle size. Small charges with weak confinement require other variables to be improved, and that means particle size, degree of mixing, strength of initiation, possibly added sensitizer, etc.

BTW, a couple or a few percent of aluminum powder is supposedly excellent for increasing sensitivity of Cheddites. I have never tried it with Cheddites, but I know it greatly increases the sensitivity of dynamites.

[Edited on 7-1-2014 by Hennig Brand]

Probably the difference was in particle size, but I did not really measure the sieve curve of the oxydiser so I can not comment if it was much below 100mesh or not. Judging by eye is pure speculation. And I did not make an effort to get it as fine as possible, just a more or less uniform powder (around 30min in the ball mill for about 500g batch). The fuel was mixed in by just shortly shaking around in a plastic container. Actually I've been amazed how well this simple mix propagated in sub 50g qunatities...as a matter of fact I also expected a partial reaction, but I've not been able to find any unreacted material after any test. Just a fine coating of KCl on the surroundings.
Maybe the iron oxide contamination from the milling media also had a fertilizing influence? It's not impossible as many metal oxides act as catalyst for chlorate breakdown reactions....although at these reaction rates it may be less probable. Guess more testing is needed to clarify the situation

papaya - 7-1-2014 at 03:39

Are chlorates compatible with more powerful nitric esters? Because instead of having problems with DNT (any aromatic nitro) one could easily synthesize liquid esters (EGDN?) and try it in chlorate/fuel/ester dynamite mixtures for example. As I understand the highest yield of all different nitrations is expected from O-nitrations (alcohols) - compare troubles and yields for TNT, RDX vs EGDN, ETN, etc. However what I said is purely speculative, check literature for compatibility, stability before ever considering to try. Btw, chlorate mixtures are inferior to AN ones, isn't it?

Hennig Brand - 7-1-2014 at 09:21

Markx, in order to try and get much meaning out of your test a lot of assumptions are required. I have seen Youtube videos from several years back with people detonating liquid hydrocarbon and chlorate, and of course it works. Its power is less than the ones with nitroaromatics of course, and I bet it doesn't store well (but I could be wrong). If it was really better to use only liquid hydrocarbons and chlorate then why bother making more complicated mixtures for the last hundred years? I guess what is better may depend on your position (whether hobbyist or industry or military etc)

Quote: Originally posted by papaya

Are chlorates compatible with more powerful nitric esters? Because instead of having problems with DNT (any aromatic nitro) one could easily synthesize liquid esters (EGDN?) and try it in chlorate/fuel/ester dynamite mixtures for example. As I understand the highest yield of all different nitrations is expected from O-nitrations (alcohols) - compare troubles and yields for TNT, RDX vs EGDN, ETN, etc. However what I said is purely speculative, check literature for compatibility, stability before ever considering to try. Btw, chlorate mixtures are inferior to AN ones, isn't it?

When you say highest yield, what are you basing that on? Is it based on nitric acid/nitrate or on the organic backbone used? I have noticed that it takes very concentrated acids, industry uses oleum actually, to get good use of acids (or glycerine) when making NG for instance. A DNT synthesis on the other hand allows me to get yields based on nitrate (and toluene) used in the high 90% range.

Ammonium nitrate is of course a better gas producer, since it produces all gaseous products and KClO3 has a lot of potassium and chloride taking up valuable space in the explosive. Ammonium nitrate is probably closer to an actual detonating explosive in its pure form than the chlorates are also. I think the Cheddites hold their own though, especially the nitroaromatic and nitric ester Cheddites. They also have another wonderful feature, chlorate makes up the largest proportion of these explosives (usually around 80%) and it is very easily made and in large quantities from salt and electricity.

Nitric esters can be used in Cheddite type explosives, there is quite a bit written about it in "Nitroglycerine and Nitroglycerine Explosives" and several other sources I have seen.

[Edited on 7-1-2014 by Hennig Brand]

papaya - 7-1-2014 at 11:47

I meant overall simplicity of production, and back in the time when once I prepared some quantity of EGDN(actually it was a test of synth) using concentrated H2SO4 (not oleum, not even more than 92% based on density) + AN mixture as nitration agent and pure EG. If I remember correctly I got nearly quantitative yield based on EG, and maybe the nitration mixture was taken with only a little excess. It was a smooth synth, no troubles, and low temps (from 0 to 10 C) cause less oxidation thus I say higher yields compared with nitroaromatics (high temp).
Unfortunately a good anode for chlorate remains a dream for me, do you use TiO2-RuO2 as usually people use? (I managed to produce 50g of chlorate with DIY Ti-Co2O3 anode, and when it finally passivated I gave up).

Hennig Brand - 7-1-2014 at 13:52

I think the nitroaromatics, like DNT or MNN, make the best use of acids though. Getting to DNT is pretty simple. It does take a bit of time though and temperature control and monitoring, this is true. I have a really unpleasant allergic reaction (or some sort of physiological response) to MNT and even toluene itself a little bit, so I don't like working with it unless I have very good ventilation.

I just use graphite rods for making chlorate. If you start with sodium chloride and make sodium chlorate before conversion to potassium chlorate, it is easy to vacuum filter the solution through a layer of diatomaceous earth. Filtering through diatomaceous earth can remove practically all graphite particles, leaving you with nice snow white chlorate. I do have a pretty good size MMO anode that I used to make sodium chlorate in the past, and a platinum anode and titanium cathode I have used in the past to prepare sodium perchlorate. The sodium perchlorate was immediately converted to potassium perchlorate once all the chlorate contaminant was destroyed. Wish I had made some ammonium perchlorate. Ammonium perchlorate was used a lot in explosive formulations as well.

papaya - 7-1-2014 at 16:09

MNT is toxic so no wonders on its bad effects. When I tried to use welding rods as anode for chlorate process they were degrading way too fast even at low currents, I guess these rods are not made of true graphite, rather from pressed carbon.

Hennig Brand - 7-1-2014 at 16:18

The following relates to storage stability issues with these type of explosives.

Here is a couple of old posts from an archived copy of the old Rogue Science forum, which seemed interesting. The thread was called "Degradation of Chlorate-Vaseline Mixtures Over Time".

"Faeriedragon

July 8th, 2005, 09:59 PM

What is the chemical reaction that renders the chlorate & vaseline explosive mixture useless over time? I've seen this degradation happen before. When the mixture is freshly made, a speck of it works properly even with the drop of a hammer. A week later, the same mixture will not generate any reaction, even when smacked quite viciously. I've read that similar cheddite formulas were once used in wars half a century ago and now we've moved to better things but...how was the explosive stablized to prevent it from degrading?

Diabolique

July 15th, 2005, 06:19 PM

Many explosives that are plasticized (incl. Cheddites, Comp. A, Comp. C-series, etc), suffer from recrystalization. The result is that the plastic mixture solidifies and becomes insensitive to initiation. Something similar happens in blasting gelatin.

In Chlorate-Vaseline, the vaseline slowly disolves a tiny proportion of the chlorate (doesn't need to dissolve much), and the solution-deposition differential between the small and large particles (due to the mass:surface area differential) causes the large particles to grow and eventually merge. The result is like concrete, and about as explosive.

This is used to allow Comp A to be press-loadable into munitions, then solidify into a stable charge in the munition.

To reduce this, and prolong the plastic life of the explosive, ~0.5% of lecthin (food additive) is used. I believe I learned this from T. Urbanski's 'Chemistry and Technology of Explosives' - which cost ~$50 per volume when I was a teenager. Today $1500 for the set. My background - I taught this stuff in the Army. :eek:"

And the same member posts again in another thread the following year. This thread was called "Guhr Dynamite + KClO3 nitrobenzene cheddite".

"Diabolique

August 3rd, 2006, 04:07 PM

The finer the ingrediants, the faster the detonation. Some become easier to detonate, but others became very difficult to initiate into detonation.

Using (90%) KClO3 with (10%) vaseoline, the velocity increases with density, which is related to particle size and loading pressure, until it reaches a critical density, where it becomes insenitive even to PETN or RDX boosters. I understand that this, and uniformity of the mixture, are the problems with most Cheddites and related explosives. In WW1, the Germans added sulfur to Carbonit (bombs & grenades) to make it more cap sensitive. You may try this to sensitize some mixtures.

You may want to add 0.5% lecithin (find in health food stores) to slow down the recrystralization of the chlorate. Semtex today eliminates lecithin from its formulation to reduce diversion to terrorists - it hardens like concrete after a year or two. KClO3 & vaseoline will harden in about two weeks without lecithin."

Hennig Brand - 7-1-2014 at 16:34

Regarding carbon anode erosion. Current density is a big factor, but it may also be that your carbon rod is lower density than some resulting in accelerated erosion. The rods can be soaked (days) in linseed oil or safflower oil I have read, and then lightly sanded before using them. Apparently this treatment does slow down erosion. I bought a box of 50, either 1/2" or 5/8" diameter and about 1 foot in length carbon rods a couple years back, and IIRC I only paid 40-50 cents for each individual rod. I think I was getting 1/2 lb or more of chlorate before the anode was useless, so I figured it wasn't worth bothering with the treatment (always meant to try it anyway though).

It seems to me that the anode always eroded far worse at or just below the surface of the electrolyte. If this portion of the carbon anode was well covered or sealed, the anode would last quite a bit longer most likely.

[Edited on 8-1-2014 by Hennig Brand]

markx - 8-1-2014 at 05:26

In the early days of my electrosynthesis experiments I also used graphite as anode material for chlorate production(sawn off section of a huge industrial graphite anode). Aside from current density another big factor for anode wear was cell temperature. With graphite and a cell temp over 40C the anode wear became really pronounced. The anode worked for a long time, but getting the graphite particles out of final product was really frustrating. I used KCl based electrolyte and hot filtering was the only option for purification. The bottleneck was filter material...it had to be permeable to allow for a fast filtration without the solution cooling too much and product precipitating in the material, yet it had to catch the graphite dust. The best I found was actually coarse glass wool (laminar thermal insulation board type), it caught the graphite particles exceptionally well even in a rather loosely packed form.

Hennig Brand - 8-1-2014 at 06:06

I have done the hot filtering with KClO3 too, but it is so much easier and more effective to start with sodium chloride. Best to produce sodium chlorate with your cell, filter out the graphite particles, then perform the metathesis reaction with potassium chloride and obtain nice clean potassium chlorate. Yeah, higher temperatures probably do increase erosion, but higher temperatures, to a point, are beneficial for the process in general. I usually ran my cell in a very cool basement, at a moderate amount of current for the size of the cell, and the cell got warm but not really hot. Also, the cell was sealed and a vent line was attached which lead outdoors. Doing this outside or in an outbuilding of some sort would be preferable, but I was doing this when there was a lot of snow and it was 20C below much of the time.

I found that bit about carbon electrode treatment from Yarchive. The author was Bill Nelson I think (was a lot of names in some of those posts), back in 1994.

"Carbon electrodes don't corrode, but they _erode_, because
of the action of singlet oxygen produced in the electrolyte. They can be
stabilized by impregnation with high molecular weight binders, but this
just slows down erosion, it doesn't prevent it. However,
since carbon electrodes are readily available (from #6 dry cells, for
example), they are often the choice of DIY chemists. They can be used
successfully if they are properly prepared. First, all of the zinc salts
must be entirely removed. This requires boiling in hot water for a few
hours, which also removes most of the manganese dioxide. They must then
be dried thoroughly in an oven and allowed to cool. The carbon should
then be impregnated with a binder. The two easily obtained binders are
safflower oil or better, linseed oil. The carbon should be soaked in the
oil for two or three days, removed and wiped off, and allowed to dry
(harden) for at least a week. Then, and this is quite important, the
surface must be lightly sanded with find sandpaper to make the carbon
adequately conductive."

BTW, in my first post of this thread, back on page two, I included a copy/paste from a text regarding Cheddites and didn't include a reference. The text it was taken from was, "Industrial Nitrogen Compounds and Explosives" by Geoffrey Martin and William Barbour, published in 1915.

Regarding storage stability, having all the chlorate particles coated in solid nitroaromatic(s) should prevent or at least slow down the recrystallization and hardening process, which eventually leaves the explosive completely insensitive to initiation (I think).

[Edited on 8-1-2014 by Hennig Brand]

Gargamel - 8-1-2014 at 12:16

Quote:

Sodium and potassium chloride are diluents, but they also cool the explosion, and also are hygroscopic which usually results in chlorate with higher amounts of moisture. Even small increases in moisture content greatly reduce sensitivity, etc, etc.

I dont't have the values ready right now, but are the chlorides really more hygroscopic than the chlorates?
At least for sodium i'm pretty sure that that's not true.

Have you guys ever thought about using catalysts like iron oxide?
They speed up deflagration a lot, but I've never seen them in detonating mixtures with KClO₃ or NH4NO₃

Quote:

a couple or a few percent of aluminum powder is supposedly excellent for increasing sensitivity of Cheddites

The effect on AN mixtures is very distinct, even 1% of dark al make a big difference. But I wonder how unsafe this gets. One could add the oil first an than the Al...
But it's still some kind of chlorate flashpowder.

Quote:

In Chlorate-Vaseline, the vaseline slowly disolves a tiny proportion of the chlorate (doesn't need to dissolve much), and the solution-deposition differential between the small and large particles (due to the mass:surface area differential) causes the large particles to grow and eventually merge. The result is like concrete, and about as explosive.

Any Idea if this will this happen with liquid paraffine oil too?

papaya - 8-1-2014 at 12:42

I've read that in some old cheddites MnO2 additive was usually present, anybody knows what for?

Hennig Brand - 8-1-2014 at 13:24

I guess I was a little unclear there. Never used sodium chlorate due to its water loving tendency. Potassium chlorate when pure is very non-hygroscopic, and potassium chloride and sodium chloride are both much more hygroscopic. Sodium chlorate is in some of the old Cheddite formulations, but I doubt most people would be interested in using it, if they had a choice, probably for most of the same reasons people into fireworks would usually prefer to use the potassium salt.

Explosives in general are dangerous, and chlorate explosives are probably more dangerous than most. I don't know how to quantify it exactly, but I know there is a big difference between a pile of loose chlorate-aluminum powder and a Cheddite where the chlorate particles are well coated in nitroaromatic and/or wax and/or oil. If the aluminum particles are well coated, as well as the chlorate particles, I would imagine this type of mixture would be much safer than chlorate-aluminum flash powder. Not really 100% sure on this one.

Yes, I would imagine that chlorate recrystallization and charge hardening would be a problem with liquid hydrocarbons. I am assuming they mean petroleum wax when they specify paraffin in Cheddites, but I guess in other parts of the world paraffin can mean a liquid hydrocarbon like diesel fuel or kerosene. Just assumed if its role was as a moderant that it would probably be solid at room temperature and coat the chlorate particles like the solid nitroaromatics do, but I could be wrong. The only Cheddite I can think of right at the moment without a solid coating material is the Vaseline Cheddite, and most of the time I have seen that Cheddite referenced paraffin (petroleum wax?) was included in its composition.

MnO2 is a catalyst commonly used to lower the activation energy of chlorate mixtures (increase sensitivity). I don't know if I have seen a Cheddite formulation with it, but it is used (or used to be maybe) in small impact sensitive type fireworks and in some oxygen generator applications. Do you have any references? Would like to read about that.

[Edited on 9-1-2014 by Hennig Brand]

papaya - 8-1-2014 at 14:23

Not much I have to say, I looked in my refs to find where I read that, but only little information is found (russian book "chlorate and perchlorate explosives", Blinov ) : mixtures containing MnO2 were used by french and called "Prometheus", oxidizer is composed of 90-95% KClO3 and 5-10% MnO2, fuel: nitrobenzene (50%) + turpentine (20%) + oil(30%, crude?), oxidizer/fuel ratio is 87:13.
Surprisingly the web search gave nothing related, maybe I search wrong? But I remember I've seen it more detailed somewhere..

[Edited on 8-1-2014 by papaya]

Hennig Brand - 8-1-2014 at 18:38

That’s interesting, there are so many ways to sensitize these mixtures. We have actually bumped on a half a dozen or more in the last while in this thread.

Industrial prices for potassium chlorate are about 2 to 3 times, per ton, what they are for ammonium nitrate right now. Industrially this would make chlorate explosives unattractive. However, for the hobbyist, if there was no access to nitrates it would be much easier to produce chlorates than nitrates on a reasonable/usable scale. Cheddites, and chlorate explosives in general, don't have the performance of the powerful molecular explosives, but they are very well suited to the hobbyist in some ways.

markx - 9-1-2014 at 00:55

For those who are familiar with the russian language:

Attachment: Blinov_I_F_Hloratnye_i_perhloratnye_vzryvchaty.djvu (1.4MB)
This file has been downloaded 676 times

This is a rather nice compendium of information on the kind of mixtures that are being discussed here.

Hennig Brand - 9-1-2014 at 04:45

Wow, wish I could read that. Is there much new information, or is it a lot of repetition of what we have discussed already in this thread? If there are some things that stand out as being new and interesting, please, feel free to share in English. If you didn't mind you could write a brief summary of some of the things that seem new.

markx - 9-1-2014 at 06:29

Well, the main functional topics rely on same principles as already discussed on this thread....understandably the laws of nature have a broad jurisdiction

There are some interesting facts about history of chlorate based energetics and their use though. For example potassium perchlorate based "cheddites" predate chlorate based ones as their development was independent from the development of (electro)synthesis. Potassium perchlorate occurred naturally in chilean salpetre deposits (4%) and was extracted from there. And there is a huge plethora of different compositions discussed (or mentioned at least)....to give some as example: manlianites, cratites, coronites, chloratites, cremonites, carlssonites, albites, almetrites, permonites....the list goes on

I'm not sure I translated all of them correctly into english as the russians have a habit of translating (sort of) names and doing the reverse engineering on that is like solving a differential equation- you end up with a multitude of solutions.
There is also a lot of practical technical information on the precursor materials properties (chemical, thermal stability vs. different contaminants, hygroscopicity vs contaminants, brisance aptitude to detonation vs additives fuels etc).
I really do not know which picks to take for translation..........best would be of course to fully translate the book, but I honestly can't find the time or strenght in me to do that. Even the thought of it drives me to drink

Hennig Brand - 9-1-2014 at 09:55

It sounds really good, is there any way of feeding that into a translator?
Just drink some Vodka, the Russian will be just flowing out of you then.

papaya - 9-1-2014 at 10:22

Russians don't like vodka jokes btw., it's something like democracy jokes for americans

Hennig Brand - 9-1-2014 at 10:59

I'm Canadian and there was no disrespect intended really. Just trying to increase his activity/energy level through agitation.

Well, ok, I might of been having a little bit of fun at his expense.

I am trying to do the translation using various free software, but so far no luck.

papaya - 9-1-2014 at 11:09

First you must do OCR, then automatic translation, I guess you already knew..

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