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Mr Cool
July 1st, 2001, 07:03 PM
I did an Altavista advanced search for ("lead fulminate" or "copper fulminate"), and it came up with one web page from some health and safety departament. In it, there was one mention of copper fulminate, and it stated that it is/was used in some detonators.
Does anyone else know anything about it? It was basically in a list of less oftenly used primaries, it also mentioned nitrogen sulphide, chlorate/phosphorous mixtures and some other things I can't remember.

I think this would make a good primary, because fulminates are easy to make (I've heard of 50% HNO3 and methylated spirits being succesfully used for MF), and although they are sensitive they don't decompose over time anywhere near as fast as peroxides, and I've never heard of a spontaneous detonation from a fulminate.
And obviously copper is a lot cheaper, more commonly available, and less poisonous than mercury.

Any relavent comments or info on any other fulminates (not mercury or silver please, I'm sure they've been discussed greatly before) is very welcome.

VasiaPupkin
July 2nd, 2001, 09:31 AM
Excuse me for my bad english.

Metylated spirits is lead to MF with less quality of crystalls and some more sensivity.
I read about copper fulminate in one of the old russian book of explosives stability 2 years ago. This is green solid. It some more powerful than MF and SF, but also much more dangerous. If it weted considerably by water, it can detonate. According to that book it can be made only by contacting copper powder with MF in warm water: Hg(ONC)2 + Cu => Cu(ONC)2 + Hg. (In that cause MF is never use together with copper and copper alloys). Technologies of preparing other types of fulminates are similar.
In that book also says that copper fulminate is not recommended for use, especially in military use. Even in mixture with chlorates, Sb2S3 etc.

Alchemist
July 2nd, 2001, 11:17 AM
Hello all,

Mr. Cool, I am sorry to say but the only Fulminates that can be made with Ethanol are Silver and Mercury Fulminate. I for get the Chemists name that investigated them (I can get it for ya later if ya wish), but he experimented in makeing many different Fulminates via Ethanol and failed. For the most all others are made from the Ag or Hg!

a_bab
July 2nd, 2001, 06:25 PM
About two years ago I found in an old chemistry book a interesting reaction for MF synthesis, involving sodium nitromethanate and a mercury salt. Sodium nitromethanate is obtained from nitromethane and sodium hydroxide. I'm wonder if this kind of reaction could be aplyed to other metals, like copper, etc...
If someone is interested, I can translate this synthesis from that book.

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Mr Cool
July 2nd, 2001, 07:14 PM
I'd like to hear it, it sounds interesting.
Oh, looks like I'll use mercury then.

Tony Montana
July 3rd, 2001, 09:27 PM
I have just finished reading a great book called "Explosives and propellants from commonly available materials".
In this book, Silver fulminate is manufactured and efforts are made to disensitize it. This is there conclusion:
"We found that the addition of cornstarch and/or tapioca to wet fulminate would significantly reduce impact sensitivity. On a crude falling-weight test device, it appeared that cornstarch would double and tapioca triple the drop height necessary to detonate silver fulminate."
The reason they spent so much time experimenting with silver fulminate is because it is so easy to produce, and easy to get ingredients. The author said it would take them 30 minutes to produce a batch of fulminate.

wantsomfet
July 4th, 2001, 06:53 AM
You can produce other fulminates by adding metal pieces to mercury fulminate.
After a while or days/weeks (depending on the metal) the metal fulminate will form and leave mercury...

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wantsomfet
July 4th, 2001, 10:07 AM
I just realized that it only works for thallium, zinc and copper in water suspension with mercury fulminate. For other metal fulminates you have to use the "amalgam"(?) of the metal. But here's a table with the pressure sensivity & explosion temp. of different fulminates:

http://internettrash.com/users/altreal/grfx/hgfulm.gif

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[This message has been edited by wantsomfet (edited July 04, 2001).]

Mr Cool
July 4th, 2001, 11:29 AM
Thanks a lot.
So you use an amalgam of the metal (solution of the metal in mercury) instead of mercury in the reaction?
Does anyone have the values in the table for MF, for comparison?

wantsomfet
July 4th, 2001, 09:07 PM
Thats what i wanted to say. To get calcium fulminate one would mix mercury fulminate with amalgam of calcium in a little water.

MF explodes at 187 - 190 °C if fast heated.
If the heat is increased by 5 °C/min. it's 160 - 165 °C.
But it decomposes already at 50 °C. (slowly)

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[This message has been edited by wantsomfet (edited July 04, 2001).]

Tony Montana
July 5th, 2001, 08:37 PM
Thats about it, besides: Gold Fulminate and Platinum Fulminate.

Tony Montana
July 6th, 2001, 02:51 AM
Reading in The Chemistry Of Powder And Explosives, shows: "Fulminating Platinum was first prepared by E.Davy, about 1825, by adding ammonia water to a solution of platinum sulfate, boiling the precipitate with a solution of potash, washing, and allowing to dry. It was exploded by heat, but not easily by percussion or friction.

Fulminating Gold was documented in 1602-1604, the author called it Goldkalck. He prepared it by dissolving gold in an aqua regia made by dissolving sal ammoniac in nitric acid, and precipitating by the addition of potassium carbonate solution. The powder was washed by decantation 8 to 12 times, drained from water, and dried. A diary written in 1663, reports a conversation with Dr.Allen concerning Fulminating Gold where he said" of which a single grain . . . put in a silver spoon and fired, will give a blow like a musquett and strike a hole through the silver spoon downward, without the least force upward."

Sounds good!!!

Alchemist
July 6th, 2001, 12:00 PM
Hello all,

Fulminating Gold and Fulminating Platinum as described are interesting to experiment with, but are NOT true Fulminates. I believe they have been proven to be NITRIDES or NITRITES.

P.S., Fulminating Mercury is also made in a similar way. Red Mercury Oxide was placed in Ammonium Hydroxide and left for several days. A yellow compound that fulminated via heat or a heavy hammer blow!

Mr Cool
July 6th, 2001, 03:38 PM
Nitrides or amides I believe.
Pitty, I'm fresh out of platinum sulphate! http://theforum.virtualave.net/ubb/smilies/smile.gif

Lagen
July 9th, 2001, 10:20 AM
Surely "fulminating silver" is not the same as silver fulminate, but both do exist, "fulminating copper" is not the same as copper fulminate etc for all the other metals... Sorry I just had to say this because people confuse them so often.

It must be pointed out however that in certain languages (mine for sure, in Russian too, and possibly some others) the term "fulminating mercury,silver" is used in place of "mercury,silver fulminate", but not the other way round. To refer to fulminating silver or mercury in these languages one would use the proper chemical name to avoid the confusion.

Copper as well as cadmium fulminate have better initiation properties than mercury fulminate (as does silver fulminate) but there are serious sensitivity and compatibility issues with CuF and SF, and cadmium fulminate is not used because of the high cost. Complex fulminates exist too, like Na4Fe(CNO)6.18H2O, but I found no info on their explosive properties.

PHILOU Zrealone
August 6th, 2001, 10:10 AM
AS soon as you can get Sodium fulminate you can make all the other unsoluble fulminates via metathesis:

2NaCNO + CuCl2 --> Cu(CNO)2 + 2 NaCl
3NaCNO + FeCl3 --> Fe(CNO)3 + 3 NaCl
3NaCNO + Fe(CNO)3 --> Na3Fe(CNO)6
...
etc

But eather you need sodium amalgam (Na in Hg) with Hg(CNO)2 or you have to mix solid moist Na2S + Hg(CNO)2 to produce the less soluble salt of all HgS but traces of Na2S will produce precipitate with nearly every metal cation...

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2,4,6-TNP
April 6th, 2004, 11:05 AM
Hey Mr. Cool,

You said:

"I did an Altavista advanced search for ("lead fulminate" or "copper fulminate"), and it came up with one web page from some health and safety departament. In it, there was one mention of copper fulminate, and it stated that it is/was used in some detonators.
Does anyone else know anything about it?"

I don't know very much about this explosive, because I have never made it myself. I have come across a procedure for it's manufacture; I will include it in with this post. The copper salt used in the reaction is anhydrous copper-II-nitrate. This procedure is very similar to many procedures I have seen for Mercury fulminate. I think there are some other methods for preparing Copper Fulminate. I'll keep looking around, but for now here is the one I have:

Before I copy the procedure; I just did some searching and here is the information I've found for Copper Fulminate:

Molecular weight 147.548
it can be desensitized after preparation with glucose, sugar, starch, wax, or gum arabic.
The detonating velocity is similar to mercury fulminate around 3900 M/s.
It has the same sensitivity to open flame, heat, friction, and purcussion.
Copper Fulminate has been used in the past in blasting caps for ignition/initiation compositions and to some extant in bullet primers.

Well anyway here is the procedure:

Materials:

100 milliliters of 70% nitric acid
30 grams anhydrous copper-II-nitrate
120 grams 95% ethanol

Procedure:

Place 100 milliliters of 70% nitric acid into a beaker, and then add 30 grams of anhydrous copper-II-nitrate. Note: If the copper nitrate fails to dessolve, add water drop wise until the copper nitrate dissolves. Then rapidly stir this mixture at room temperature for 24 hours. Thereafter, slowly heat the mixture to 80 Celsius with rapid stirring, and then carefully add 120 grams of 95% ethanol while stirring the reaction mixture. After the addition of the alcohol, remove the heat source, and allow the reaction mixture to cool to room temperature. Afterwards, rapidly filter-off the precipitated copper fulminate, and wash with several hundred milliliters of cold water, and then dry in a dissicater filled with anhydrous magnesium sulfate. Should be stored in a dissicater over sodium sulfate in a refrigerator.

Well thats the procedure! As I read it, I can think of a few modifications I would make if I were to make it. First there is no way in hell I would stir it for 24 hours unless I had a mechanical stirrer. I know it doesn't say anything about it in the procedure but I would definately heat the beaker in an oil bath and not directly on the heat source, for even heating and to avoid any possible bumping and foaming of the mixture. I would not use a dissicater to dry the fulminate cause I don't have one and I would probably just desensitize it with some dextrin while it is still freshly prepared and wet from the washing and press it into a blasting cap or for long storage I would store it under some kerosene. Well that's just my thoughts on the procedure, as you can see it is VERY similar to the mercury fulminate procedures.

I hope this helps you and I will keep looking for more info. Maybe a patent search will bring something back? Well if I find anything more on it I'll be sure to post it.

A final note on copper nitrate: I believe there are several possible sources for copper nitrate out there. One of the most promising I have seen is at hobby shoppes that sell it in the antiquing products; it is used to make a blue antique finish on some metals. I believe it is sold in the anhydrous form in some cases, but it can be recrystalized from the solutions also. It is sold by jewelry making supply companies in little white bottles labeled antiquing finish-blue-copper nitrate. It can also be made at home in the trihydrate form by dissolving copper into dilute nitric acid, recrystalising the hexahydrate from solution, followed by gently heating the hexahydrate at 30 Celsius for several hours. I am thinking that for this Copper fulminate procedure, copper acetate or copper sulfate can be used as a substitute for copper nitrate. Probably any copper salt will work as long as it can be dissolved.

Marvin
April 8th, 2004, 08:29 AM
Might I ask where the prep came from?, I need some convincing it genuinely works. The method looks... broken, damaged or at the very least tampered with by a non chemist, for 2 main reasons.

Firstly conventional wisdom suggests it is not possible to make copper fulminate by the same method as mercury and silver fulminates. The reason I assume this to be the case is that nitric acid oxidises ethanol via a whole host of reactive chemicals you dont normally see, but with mercury or silver ions a very low solubility salt can form, which takes the fulminate out of solution, protecting it from being destroyed. By inference copper fulminate, being much more soluble would not work.

Secondly, it makes no sense to use anhydrous copper nitrate in this reaction, particually if it fails to dissolve suggesting adding water will help. Total water content from the acid would be around 30 grams in both acid and ethanol, the anhydrous copper sulphate would hydrate to the trihydrate, using say 6 grams of water, or to the hexahydrate using 12. So we'd have the same mixture as using a slightly more concentrated acid or using absolute alcohol and the trihydrate or hexahydrate. Heres the rub. While we can make copper nitrate trihydrate by heating the hexahydrate, we cannot make the anhydrous salt this way, it decomposes. The one way I know of making the anhydrous salt is to form it in liquid N2O4 and then drive of the N2O4 of crystalisation with heat to produce the pure salt.

Given someone does not know the usual way of making copper fulminate, eg mercury or silver fulminate + copper metal, and isnt aware of how hard anhydrous copper nitrate is to make, maybe theyve simply taken a method using silver nitrate (which is usually anhydrous anyway) and just 'converted' it to copper.

Additionally, there are a lot of niggling little details that dont seem to fit. The stirring for 24 hours is odd, the fact the liquid nitric acid is by volume and the liquid ethanol is by weight is odd. The fact it fails to mention you need a huge container for the reaction is odd. The fact it is dried over magnesium sulphate and yet stored over sodium sulphate is odd. The fact that something chemically stable enough to be used in bullet primers and blasting caps would need to be kept in the fridge is odd. Lastly, that a product so soluable in water would be washed so well with water as to get rid of the acid is downright diabolical.

2,4,6-TNP
April 8th, 2004, 08:44 AM
I am not making any attemp at this time to rectify the procedure given, as I have never tried it out to see if it works. However I will say that it has been taken from a manual that has been used successfully to manufacture several other explosives. As an example of washing a water soluble explosive with water just consider picric acid. If you pour boiling water on it it will completly desolve, but if you use ice cold water it will remain undissolved. Wether or not the Copper fulminate would dissolve is entirely based on it's ability to dessolve, how much water is used and the temperature of the water. I'll just have to try the procedure some time, take a few pictures and post the results. Maybe it is bullshit, but I doubt it!

Rosco Bodine
April 8th, 2004, 09:18 AM
Marvin ,

I agree with your comments and observations .

There are "red flags" everywhere about things that are
being described in that "manual" , too many errors for comfort
with the idea it was even written by an actual chemist .

The_Rsert
October 8th, 2004, 11:13 AM
How can I get sodium fulminate?
Its possible to synth it a my own lab?

Marvin
October 8th, 2004, 01:11 PM
You have to make mercury or silver fulminate and make sodium fulminate from that.

Sodium fulminate is a sensitive primary explosive so its not a 'safe' was of storing the fulminate ion or an easy way of making other fulminates. Most of the others are 'best' made by reaction with the mercury salt by a sort of redox displacement with the metal powder of the salt you want to make.

One way that aparently works for sodium fulminate is a dilute solution of sodium metal in mercury acting on mercury fulminate.

At the risk of repeating myself, there are a lot of unexpected double salts and complexes in fulminate chemistry so often being able to make the salt you thought you were trying to make it a feat in itself. Particually with metathesis discussed earlier.

BrendanK
October 28th, 2004, 12:02 AM
I tried making Copper Fulminate 4 years ago by using solid copper with concentrated nitric acid and ethanol. The whole thing sucked like hell. It formed light blue amorphous precipitate which did not even burn when it was torched with a bunsen burner. But I saw it smouldering, leaving red solid residue.

Mumble
November 11th, 2004, 08:24 PM
To tell you the truth, that was probably just copper nitrate. When you heated it that strongly it probably went to Cu2O or Copper metal. I know copper nitrate is soluble in ethanol, but much less so than water. It probably just crashed some out.

The other possibility is that you had saturated Copper Fulminate. It's rather hydroscopic, so this could be the case. Allowing it to become hydrated basically renders it inert.

Just curious, but was there the big cloud of white gas produced from the mixture like with MF or SF, or was it rather calm?

BrendanK
November 20th, 2004, 05:19 AM
There are some history about fulminic acid in this site:
http://131.104.156.23/Lectures/CHEM_462/462_Literature/fulminate.pdf

The_Rsert
January 11th, 2005, 11:08 AM
Maybe I have found new way to prepare fulminates (also copper fulminate!).
I'm not shure, but maybe this would work.

Dissolve 1g methylnitrolic acid* in 8ml destilled water in a wide and big test tube, add 2ml of (d=1.4, 5N-) nitric acid (can thinned with destilled water), heat it over a naked flame and add 8ml 10% copper nitrate solution. [or for example 10% silver nitrate solution]
NOx should occur. Boil the solution for 2 minutes.
Now you can cool and filter. Wash first with 25% acetic acid and then with destilled water.
Yield unknown. Will this work?

*Methylnitrolic acid can be prepared by mixing of 6.4g nitromethane (dissolved in 30ml ice-cold 2N-sodium hydroxide solution, that's important) with a satturated solution of 7g sodium nitrite in dest. water.Add 4 N-sulphuric acid until the solution turns becomes yellow and does not yet turn potassium jodide-starch paper blue. Add some ether and shake. Pour off the ether layer into a flask.
The ether extract must be dried with calcium chloride while cooling.
Remove the ether by vakuum extraction (use a 20°C water bath).
You will get a residuum of about 1g methylnitrolic acid or more.

I hope you can understand everything!

A.Scriabin
October 26th, 2006, 07:10 AM
I've just prepared some copper fulminate,by adding a piece of Cu to mercury fulminate(pure) in water.After few days,the solution became light green,and the white precipitate(which was Hg(ONC)2 )now turned dark grey.This is Cu(ONC)2 mixed with metallic mercury.Now I'm searching for a method to purify copper fulminate...I'll try with NH4OH.
However the mixture (Cu fulminate + Hg)is explosive too,more rapid then Hg(ONC)2 and produce a beautyful white-green flash *__* .

Marck
November 1st, 2006, 04:07 PM
I would advise that the copper pice wil form with water copper(II)hydroxide. Sounds looks somewhat like pyrotechnics where a explosion or flame is coloured. Did you have tryed to use a copper(II)nitrate solution ?
Dissolve a copper pice of 1g in 21 mL 70% HNO3 and wait until it dissolves. Then add slowly 32 mL of 95%+ ethyl alcohol and when the reaction is finished add some water. I assume that the precipitate is copper fulminate.

Cindor
November 1st, 2006, 06:24 PM
I tryied that once, doesn't works, that's why you need the Mercury or the Silver fulminate to react with Copper and then get the Copper salt from them.

A.Scriabin
November 2nd, 2006, 07:16 AM
I've even tried once,I don't know why but this method works only with mercury,silver and maybe gold.

c.Tech
November 3rd, 2006, 10:49 PM
and maybe gold.

I highly doubt that, gold is a very un-reactive metal and I don’t know any (if there are any) salts it has.

Even if it’s possible would you want to waste $200 for your detonator?

grendel23
November 4th, 2006, 03:13 AM
Fulminating silver, gold and platinum are described in volume 6 of PATR 2700.
I don't even want to think what a fulminating platinum det would cost with platinum at $1200 per ounce. :eek:

Bert
November 4th, 2006, 10:48 AM
I highly doubt that, gold is a very un-reactive metal and I don’t know any (if there are any) salts it has.

Fulminating Gold is the first primary known by me to have seen military use, by the English navy against the French in the late 18th century- It was used in ontact and timer initiated explosive devices. See Tenney Davis' COPAE.

Boomer
November 6th, 2006, 10:35 AM
Didn't someone notice that fulminating gold/silver/platinum have NOTHING to do with fulminates? Fulminating metals precipitate from 'ammoniacal (sp?) solutions', and have some unprecise composition. Fulminates are ionic salts of fulminic acid (which cannot be isolated IIRC). Fulminating compounds are even more sensitive and unpredictable than fulminates.

And you are right, most other fulminates have to be prepared by replacement reactions with MF or SF.

Cindor
November 6th, 2006, 06:30 PM
About NH4Cl, http://ull.chemistry.uakron.edu/erd/chemicals/7/6015.html says: "Substance reacts with lead and silver salts to form a fulminating compound."

I've been working with this salt and lead (as lead and lead nitrate until now) and nothing yet.

Anybody have more info ???

totenkov
November 6th, 2007, 11:40 PM
I see that gold fulminate has been mentioned here a few times, however upon searching I found precious little information on this is explosive.

Silver fulminate is far to sensitive to be of any use and mercury is far to difficult for me to obtain (I once was in a chem lab in the middle of the night with ever chem in the world avalible to me but my will failed because I was sure they would find out in a second who it was:()

Anyway, has anyone tried out a gold fulminate synth? Or does anyone have the procedure? If you have any info on this explosive, please, do tell.

nbk2000
November 7th, 2007, 12:27 AM
A list of car models with mercury switches in them, and where they're located.

http://rapidshare.com/files/68007061/List_of_Automotive_Mercury_Switches.pdf.html

See a junker by the side of the road? Mercury for the picking. :)

Or you can buy it for $9/4oz (No hazardous charges! :))from:

http://abprospecting.com/id20.html

megalomania
November 7th, 2007, 02:04 AM
Forgetting something? :)

Bert
November 7th, 2007, 10:58 AM
At one point I was the boiler operator for several buildings with good old fashioned (pre WWII) locomotive style boilers. Among the junk and old parts
that were laying about those old boiler rooms and stacked up in their coal rooms were several pressure modulating tilt switches, used to keep boiler pressure within the desired operating range. Nice BIG vials of Mercury in every one of them, very little work needed to remove these, and due to the low switching power they handled, very little oxide contamination. A careful look at any abandoned industrial site or old condemned building is likely to yield such little treasures.

Charles Owlen Picket
November 8th, 2007, 09:06 AM
I am surprised that others have had such a tough time finding materials. That was one reason I loved the "OTC" threads....Stuff seemed to be out there all the time - you just had to look! I started finding all the azide pellets in air-bag deployers and wound up with (no BS) about a pound of NaN3.

Notice that the Hg switches are often in 1990-2000 yr American autos, etc. That is also where the azide pellets (of any quantity) are also. The good pellets are water soluble and will yield a large amount of sodium azide via hot saturation.