Lead Styphnate suitable primary?

[HVD]

Is there any reason why Lead Styphnate (extracted from rifle primers) could not be used as a primary in a detonator? Say in place of HMTD or AP?

Surely it's easier to extract some from primers, and have a commercially made high purity compound than go to all the effort of making, filtering and washing some homemeade (and maybe impure) primary explosive?

It's D.V. is around 4900 ms and HMTD is around 4500 ms (data from Mega's site) so it even sounds more powerful.

Anyway if anyone has any experiences making detonators with this stuff, especially if it was extracted from rifle primers, then please post.

Thanks in advance
HVD

[Mr Cool]

It has quite a low energy, but I'm sure it could be used if you could safely open up primers.

[mongo blongo]

It also has good flame sensitivity. It is commonly mixed with Lead Azide for this purpose. It should work quite well but be careful opening up those primers.

[Helos]

But a guess is that each primers contains very little of the explosive and therefore it is not an smart idea?

[DBSP]

It's a hell of a job but it can easily be done safely by drowning them in acetone before opening them.

I't nothing I'd recomend, better to put some effort in nutrolising you homemade stuff instead.

[Microtek]

Lead styphnate is quite easy to make from resorcinol; if anybody is interested I can go into details.
But before I do this, I must say that it is not at all suitable as primary. It does not initiate PETN if that explosive is pressed even moderately, thus 1 gram lead styphnate did not initiate PETN pressed at 2000 psi. If you recall, I have made some tests to find out if the product from acetone + HCl + H2O2 was DPPP or just AP. One of the tests was to use supposed DPPP as base charge and lead styphnate as initiator and if less than about 5 mm3 styphnate was used, the base charge did not detonate.

[green beret]

I havent ever made lead styphnate, but I know for a fact that (australian) commercial dets. have PETN as a base charge with ASA as the primary, ASA is a mixture of lead styphnate and aluminium, I dont know how much of ASA is used to set off the PETN but I do know that the base charge of PETN is around 0.45 grams, depending on detonator strength. The ASA is a nice lemon colour and cast into the det somehow, probably using a binder of some sort, it sparkles in the sun too. I also do not know the ratio of Aluminium to Lead Styphnate, but I will try and find out.
This probably hasn't helped much but I thought you might like to know.

[Mr Cool]

ASA is Azide/Styphnate/Aluminium, so again the lead styphnate is just added to increase the flame sensitivity of the lead azide. I can't remember what the aluminium is for...

[Microtek]

Aluminium is added to increase initiation capacity, most likely by increasing explosion temperature. In the usual ASA mix, lead azide is by far the major component - about 80 % if my memory serves.

[zeocrash]

the US army Blasting caps use lead styphnate in a 3 part series
__________________________
.......|########|@@@@@@@@@|
....1..|####2###|@@@@3@@@@|
_______|________|_________|

Part 1 is lead styphnate, that is easily ignited by an electric match or fuse.
part 2 is lead azide more powerful than part 1
part 3 is RDX designed to give out a large shockwave and garentee ignition

Now the only question i have now is where do i get magnesium styphnate from/how do i make it (its the only thing i havent got)

<small>[ January 14, 2003, 03:03 PM: Message edited by: zeocrash ]</small>

[stanfield]

even in the Acros orgaics catalog (2000+ pages) I wasn't able to dig up this product ! it's a bitch to find...

I'm interrested too in lead styphnate but this bloody magnesium styphnate is the major problem !

bye !

<small>[ January 14, 2003, 04:15 PM: Message edited by: stanfield ]</small>

[megalomania]

If I am not mistaken you can make magnesium styphnate from a magnesium base and styphnic acid. Try mixing a solution of styphnic acid with magnesium carbonate or hydroxide.

[IPN]

If you haven’t noticed a synthesis for styphnic acid can be found over here:

<a href="http://www.powerlabs.org/chemlabs/styphnic.htm" target="_blank">http://www.powerlabs.org/chemlabs/styphnic.htm</a>

I´m soon going to get my hands on some resorcinol (200g) so I can test the preparation of SA.

I hope it will be worth of trying.

[Microtek]

The procedure on powerlabs is inferior. Try this instead:

- 1 part resorcinol is dissolved in 1 part warm water and 7 parts 62 % HNO3 is added while temp is kept between 35 and 40 C.

- This solution is added drop by drop with stirring to 20 parts of H2SO4 while temp is kept below 50 C.

- When addition is complete, the soln is left at room temp for 30 min with occasional stirring.

- Soln is drowned in 1.5-2 times its own volume of ice and water and the precipitated product is collected on filterpaper.

- The product needs to be washed carefully to be free from residual acids and oxidation products.

In my experience this is the best way to avoid oxidation and runaway and even so, some oxidation will take place and colour the soln red or black. Trinitro resorcinol is very insoluble in water, not at all like picric acid, so more water can be used without losing much product.

The conversion to lead styphnate goes as follows:

- 1.2 g TNR is suspended in 3.5 mL H2O and 0.42 g MgCO3 is added.

- Heat steadily to 60 C with stirring and after a minute at this temp, filter off any insoluble matter ( there won't be any if the synth has been done carefully ). (I)

- Prepare a soln of 1.66 g Pb(NO3)2 in 3.5 mL H2O. (II)

- Heat (I) to 80 C and add one drop of HNO3 62 %.

- Add (II) to (I) dropwise with stirring while keeping the temp at 80 C

- When addition is complete, filter off the product and wash thoroughly.

Note that all azides react with acid to form gaseous HN3 so if the styphnate is to be used with lead azide steps need to be taken to avoid this.

[zeocrash]

ok

only 1 question
where can i find/how can i make rescorcinol

[IPN]

Message edited for not revealing a chem.supplier
to the kewls.

<small>[ January 17, 2003, 02:34 PM: Message edited by: IPN ]</small>

[davismn]

I just wanted to say that the procedure presented by Microtek is far better than powerlabs. My yield was almost twice as good as before using his procedure.
Also I didnt have any magnesium carbonate around to make the magnesium stynphnate intermidiate, so I decided to nuetralize it with excess ammonia. The solution heated up a bit so I left it alone for a night. The next morning I had huge crystals of ammonium stynphate on the bottom of my beaker. In order to get them to redissolve I heated the solution and then added lead nitrate. Immedietly I got a milky brown precipitate. I filtered the precipitate, dried it, and sure enough it was lead stymphate(when I took a lighter to a small portion of it, there was a big pop followed by a puff of smoke). So any one who doest want to use the magnesium stynphate intermidiate, ammonium stynphate is a viable alternative.
By the way Im a first time poster so I would just like to add that Ive been enjoying the inteligent conversations that have gone here for some time, keep up the good work!

[Mr Cool]

That has to be the first time I've come accross something where adding a hydroxyl group decreases solubility in water, from TNP -> TNR.

Resorcinol can be found in a two-part glue, the other part being mainly paraformaldehyde. It's commonly used for boat repair I think, it's a wood glue.

I'll try that method with phenol to make TNP Microtek, as I always get a fair amount of oxidation with my current method. Phenol should be less prone to oxidation than resorcinol...

[IPN]

Microtek:

That procedure you described seemed to work really well; I had a good yield from 5g resorcinol, 35ml 60% nitric acid and 100ml 98% sulphuric acid.

Tomorrow I will make some lead styphnate from it. I will share the results then.

Btw. Is it ok, if my styphnic acid is dark red?

<small>[ February 21, 2003, 10:17 AM: Message edited by: IPN ]</small>

[Microtek]

Yes, mine is too. I think it is an oxidation product that gives that red colour and it has such a strong dyeing effect that it is practically impossible to was the colour away. You'll be dissolving the TNR anyway when making lead styphnate.

[IPN]

Yes I was just worrying if there went anything wrong with my synth.
I must confess that i didn't add the resorcinol/HNO3 mix very slowly (about 2ml per 10sec).
Well I got 6,5g TNR from 5g resorcinol, not too bad!

Oh and a little question, can I make lead nitrate from lead oxide.
I guess it would be like adding NaNO3 solution to lead oxide and then filtering.
Or could the lead styphanate be made by simply mixing the lead oxide and TNR. I might be wrong though.

[kingspaz]

IPN, you'd have to add the lead oxide to dilute HNO3 and then evapourate the solution down to 1/4 of the original volume, then filter.
PbO + 2HNO3 ---> Pb(NO3)2 + H2O

[Microtek]

Pb(NO3)2 is very easy to make. Simply add some lead to 50-70 % HNO3 and heat to 50-60 C to get the reaction started. Lots of NOx will be evolved ( this can't be helped as the HNO3 nitrogen must be reduced in order to oxidize the free lead to Pb(II) ). Be sure to check the reaction often and be sure that the container is large enough to prevent the acid to spill out during the rather effervescent reaction.
If the reaction subsides, you may need to heat more or to add more acid. White precipitate will begin forming rather quickly as lead nitrate is rather insoluble in nitric acid, but don't stop the reaction before all the metallic lead has been dissolved. Then just keep boiling it until all the acid and water has evaporated ( but don't let the temp rise to above, say, 150 C ), let it cool down and add some alcohol to wash the product. Filter and wash again a few times. After drying you will have quite pure lead nitrate.

I think the PbO + 2 NH4NO3 --> Pb(NO3)2 + 2 NH3 + H2O reaction will give negligible amounts of lead nitrate ( as the insolubility of PbO will drive the equilibrium the other way, perhaps forming Pb(OH)2 ), but PbO + HNO3 will probably work.

[IPN]

I tried the PbO + 2HNO3 method.
When I added the HNO3 (which I have no more :( ) the PbO turned black and when I added some water to precipitate the lead nitrate it still remained black. No white stuff.

I wonder if I did something wrong?

[Microtek]

Water will not precipitate lead nitrate ! It is highly soluble which is why it is suitable for the reaction. You could also use lead acetate which is also water soluble.

[Sarevok]

Posted by IPN:
</font><blockquote><font size="1" face="Verdana, Arial, Helvetica">quote:</font><hr /><font size="2" face="Verdana, Arial, Helvetica">I tried the PbO + 2HNO3 method. When I added the HNO3 (which I have no more) the PbO turned black and when I added some water to precipitate the lead nitrate it still remained black. No white stuff.

I wonder if I did something wrong?</font><hr /></blockquote><font size="2" face="Verdana, Arial, Helvetica">Next time try to use Pb instead of PbO. Did your HNO₃ were concentrated? As I know, for this reaction the HNO₃ needs to be concentrated, but I can be wrong... I never used precious Nitric Acid to make Lead Nitrate. :rolleyes:

[IPN]

My HNO3 was 60%.

Well now I have a good amount of lead nitrate drying.
Here is what I did:

I filtered the solution after a little heating and boiled the filtrate to 1/4 original volume and took it outside to allow it to cool and then filtered and washed several times with alcohol.
-----------------------------------------------
Ok. Now I have about 1g of what I believe is lead styphnate and I have to say it is not very good at detonating anything exept HMTD (btw. my lead styphnate is yellow, should it be red?).

Im still drying my ammonium styphnate to compare it to ammonium picrate.
-----------------------------------------------
Ammonium styphnate is not worth to try. It didn’t detonate with 1,5g HMTD. It did burn though.

<small>[ February 25, 2003, 11:39 AM: Message edited by: IPN ]</small>

[IPN]

I had an accident few minutes ago.

I had some lead styphnate probably spilled on my lab bench (I don’t know how) . I placed a small amount of HMTD to the corner of the bench (I like it when it burns with that yellow/red flame) and lighted it with a lighter without knowing that there was that lead styphnate and BANG!! The next thing I noticed was that my hand was universally black and my ears were ringing.
I had no idea how that styphnate got on the bench but I will never do anything like that again!

In fact now when I start to think of it I don’t consider it as an accident but rather an education, because now I now that my lead styphnate worked and I have to be careful with that.
But this certainly raised my respect to explosives.

Btw. does anyone now what are the products from the detonation of lead styphnate?

<small>[ February 27, 2003, 02:57 PM: Message edited by: IPN ]</small>

[a_bab]

Your hand became black because of the lead oxide and perhaps because of the unreacted carbon, although I cannot be sure.

<small>[ February 28, 2003, 03:30 PM: Message edited by: a_bab ]</small>

[Scorpion]

Hey IPN the Lucky Hand!

I think it was you who asked about the color of the crystaline lead styphnate...

Well, searching over a very serious source on the subject I've found two diffrent kinds of Lead Styphnate, one is the yellow most common and stable form, which is the one you gotten, but there also exist a red form (more unstable) of LS which is more sensitive to shock and friction.

Procedure for the red LS:

Place 800 ml of water into a beaker, while rapidly stirring the water, 24.4 grams of styphnic acid, and then 16 grams of sodium hydroxide. Then, heat the mixture to 7 Celsius while stirring. Then dissolve 70 grams of lead nitrate into 700 ml of water. Thereafter, place the heated styphnic acid/sodium hydroxide into a dropping funnel, and then slowly add, drop-wise, drop by drop styphnic acid/sodium hydroxide mixture into the lead nitrate solution while stirring the lead nitrate. Now, in the beginning, slowly add the acid/hydroxide mixture very slowly drop-by-drop until a small amount of an amorphous yellow precipitate forms. When this happens, stop the addition, and allow this amorphous yellow solid to crystallize as reddish-brown diamond shaped crystals. Where upon, add the acid/hydroxide mixture at a much faster pace, and continue the addition until all the mixture has been added. During the whole operation, stir the lead nitrate solution. After the addition , continue to stir the reaction mixture for 20 minutes, and then filter-off the precipitated lead styphnate. Allow it to cool to room temperature, and then wash with 200 ml of cold water, followed by vacuum drying or air-drying.

Comparing the two procedures (Yellow form vs. Red form) I see that the key on getting the red form of LS is the grade of dilution of the lead nitrate solution. In the case of the red modification the lead nitrate solution is less dilute. (i.e.: In the preparation of the yellow form 100 grams of lead nitrate were diluted in 2500 ml of water, against 70 grams of lead nitrate diluted in 700 ml of water for the red modification)

<small>[ March 15, 2003, 08:49 AM: Message edited by: Scorpion ]</small>

[shooter3]

I think you are all overlooking one important use of lead styph. If you want to use any kind of piezo crystal initiator, you would definatly want LS on the bridge wire(or spark gap). It's a sure fire way(pun intended) of getting things going.

<small>[ March 14, 2003, 09:15 PM: Message edited by: shooter3 ]</small>

[akinrog]

Dear Friends,

This is my first post. I hope nobody flares me up. But I would like to give an information about a procedure I saw somewhere which I cannot remember.

As you may know, picric acid may be prepared by oxynitration (I don't know exact word in English but it must be somewhat like oxynitration) of Benzen in the precence of mercury as catalyst. While looking at my notes, I saw a procedure which uses a similary oxynitration but of toluene into styphnic acid. But I have no means to verify if it's true. If this procedure is genuine, then preparation of styphnic acid shall become easier and more practical.

I hope this comment /bit of info is useful for this discussion.

Regards,

[Rosco Bodine]

Styphnic Acid will not result from the oxynitration of toluene .
The product from the oxynitration of toluene will be trinitrocresol
not trinitroresorcinol . Similar explosive salts can be made from
trinitrocresol , but they are likely less powerful in comparison ,
although I am not certain about this .

Lead Styphnate has a lot of potential power but its self accelleration
is poor so its critical mass to high order detonate is several grams
with strong confinement . See GB139811 for relevant information
on use of lead styphnate as a single component detonator .

Mixing a more rapid self accellerating primary with the lead styphnate
or using as a top charge to kick the lead styphnate rapidly to high order
velocity is more economical . See GB142823 for details .

A mixture of 1 part lead azide with 2 parts lead styphnate is quite powerful .

other patents regarding lead styphnate are below

US1443328 original patent
US1999728
US2150653
US2295104
US2589703
US3041361
US3953486

GB187012
EP0070932

[akinrog]

Rosco Bodine:
You might be right. As I stated in my previous post, I have no means to verify it. However, I found the following link on styphnic acid synthesis during my google search. Hope this helps.
Regards
http://www.powerlabs.org/chemlabs/styphnic.htm

[Sir Dudalot]

I've used rifle primers for detonators before. To extract the lead azide/styphnate I "crimped" (can't really think of the word) them then pulled out the now loose anvil with a knife. After that I just scraped out the LA/LS. I always used it to initiate ETN in my dreams. I'd open 15 primers to detonate the ETN. It worked the first three times then had one failure so 20 should be more consistent. I can't see why it's that hard to get the stuff out. It was time consuming as hell, but simple. I just used a pair of pliers to smash the circle into an ellipse then smashed it back into a circle and the anvil would loosen up enough to pry it out easily.

[blindreeper]

I have done a pictorial on extrating lead styphnate from rifle primers. http://www.geocities.com/blindreeper_chemistry/LS.html
How much lead styphnate do think would be enough to initiate say, picric acid? I was thinking this would be a very powerful and stable cap; LS and TNP.

[HarmonyWave]

I've having some difficulties with the TNR synthesis given by Microtek.
Dissolving the resorcinol(it was 5g) in hot water, no problem of course.

But the drop-by-drop addition of 35mL 62% HNO3 gets out of control every time - tried two times.

At some point in the addition i experience runaway - a kind of sudden splattering effekt of black-n-red soln(assume traces of TNR and oxidation-products?) and a big cloud of NOx...
The temperature was kept between 30 and 40deg as written by Microtek (actually 34-36 at all time).

Anyone experienced the same? Sugestions to what i may be doing wrong.

Thanks
New poster. Be gentle.

[Microtek]

Firstly, if you get runaway, reduce the batch size. Secondly, if one part is 5 grams then 7 parts is 35 grams which corresponds to ca. 25 mL 62 % HNO3.
Did you agitate the resorcinol solution properly as you were adding the HNO3 ?

[HarmonyWave]

Well i gave it a occasionel swirl.. dont know if that is sufficient?
The resorcinol/HNO3 mix seems odd to me. The first time i tried, i did actually add all the HNO3 without a problem.

I watched it for a few mins, and no change in temperature was observed. After some longer time(5mins perhaps), right before i were to add it to H2SO4, it "blew up" as described before. Meaning great temperature rise in almost no time...

After the second "runaway" i did collect water insoluble material, a red powder when washed and dried, most likely TNR?, but i would very much like to control the reaction.

[Microtek]

The reason for the runaway reaction is that resorcinol, like phenol, is very active towards electrophilic substitution such as nitration. When HNO3 is added too fast, the heat released by the reaction accelerates the reaction even further. This feedback loop continues and, as the temperature rises, oxidation begins to dominate over nitration. This releases the clouds of NOx and destroys your product and reactants.
The idea is to add a little HNO3 at a time and then allow the resorcinol to react with what has been added before adding more. This way the produced heat has time to dissipate before the temperature rises too much.
If you add the HNO3 dropwise but without adequate agitation, it will not be able to contact the resorcinol properly and thus will not be able to react fast enough to be mostly spent by the time you add the next portion.
This means that there is a build up of HNO3 in the mix. The reaction will be slow to start but it will eventually react, particularly at the interface between the "HNO3 regions" and the "resorcinol regions". This reaction will evolve heat and the temperature differences will cause turbulence which will mix the reactants quite effectively.
This will cause a massive acceleration of the reaction - a runaway.

So, in short you must stir it much more effectively. Constant swirling will do the trick, but if you can get your hands on a stirring magnet, you can improvise a magnetic stirrer by mounting a bar magnet on a computer cooling fan.
The addition of the HNO3 can be done fairly rapidly if your agitation is good enough, for instance by constantly swirling the flask with the resorcinol solution and adding the HNO3 in small portions.

[peppovsky]

I also ran into runaways and splatters, exactly like HarmonyWave describes, in my two attempts of the synth - but I used a magnetic stirrer when adding the HNO3 to the water/resorcinol mixture - so one can't say there wasn't enough agitation. Also, I did add the HNO3 dropwise, and kept the temp in the 35-40 C the entire time. Are you sure that the problem is the lack of agitation? couldn't it be something else?

[Charles Owlen Picket]

Well he made that comment back 3 years ago so don't expect an answer too soon.....but the "nitrite" method eliminates that possibility. HOWEVER nitration of phenols are a vigorous reaction and much NO is involved....could that have been mistaken for a run-a-way????

This is a standard 2 step process wherein dinitroresorcinol monohydrate is first obtained and then utilizing dilute HNO3 (40%) brought to completion. This was the process used by the Western Cartridge Company, 10 November, 1942; patent available via USPO.

Note: highest level of temp should be 30 C during final phase. Patent warns of any temp in excess. The starting temp for the monhydrate should be 0 C. Basically the synth should be under 5 C during lab-level production.

Another dinitroso intermediate production method utilizing sodium NITRITE can be found from British patents via David Anthony Salter & Robert John James Simkins, application filed 30 May, 1973. This one involved high temps (80-90 C).....I have seen some of these synths and they are very tame & managable and the resultant material, quite spectacular in both yield and crystal construction.

These use dilute HNO3 and I would imagine you would need to WORK to produce a run-a-way.

[nbk2000]

Microtek is still around, just lurking now mostly, so he may reply if he wants to.

[peppovsky]

I was aiming towards an answer, I didn't really mind who would give it ;)

What I experienced was an acid splatter. In both times, when I finished adding the HNO3 to the water/Resorcinol solution, the temperature raised quickly a few minutes later (actually, in the second time it raised less then a minute after), and then the mixture was spitted all over the area, quite violently. It's a shit to clean, btw.

Can you please specify the patent numbers of those mentioned? I couldn't find them by keywords and date of submission. It would be quite helpful.
Also, do you advice to keep the temperature below 30 deg C the entire (62%) HNO3 addition?

[Charles Owlen Picket]

The material was application filings; so check the applications rather than the granted patents. I have worked with several styphnic acid synths and had success with most. However I would work with low temps if you are really getting splatter.....and look for contaminants as well.
Frankly I have not dealt with that issue. But I do remember there had been varieties of resorcinol available from needle crystals to rough chunky material.

The starting configuration of a material to be nitrated may have an effect on the process / outcome. Sighted source material is easily obtainable via Legard's books from the FTP (Prepretory Manual of Explos, etc).

Resorcinol is a quickly nitrated material; drop the temp WAY down and I'll bet you do fine.

[Enkidu]

Temperature is a tricky thing. You must know the reaction as the literature describes it, but hands on experience is often necessary to tweak the reaction's performance. Be wary of keeping your temperature too low. If it's too low, you can have a bunch of unreacted nitric acid in your reaction vessel. Then, if you add any amount of heat (or simply the exothermic reaction begins in earnest), you end up with an unstoppable, increasing reaction rate (i.e., a runaway).