my favourite primary explosive

[pdb]

I use diazoperchlorat-3-nitroanilin associated with PETN for making detos. It's a cheap, easy-to-prepare primary explosive, with a remarkable initiation power, greater than fulminates and metal azides. However, it has not found its way in industry because it doesn't pour easily. Although it is not a problem for my detos, I would like to explore ways to obtain a cristallized size-controlled product. I never heard of any solvent, but my idea is to prepare it in another medium than water, maybye in ethanol.

Does anyone know and use this compound ? Would be delighted to exchange experience about it.

[Microtek]

This sounds interesting... By which standards is it easy to prepare ? Which precursors are you using ? ( it can be quite hard to make DDNP if you have to make the picramic acid yourself, even though the DDNP synthesis ought to be reasonably straight forward ).
Also, please share what you have about its properties ( both litterature and your own experiences ). For instance, is it sensitive to sunlight ( as I'm told DDNP is ) or degradation by O2 or CO2 from the air ? How about its DDT capability compared to azides or styphnates.
In short, I'd value anything you could provide as I'm always looking for a better primary.

At the moment, I'm using an intimate mix of silver acetylide-nitrate and MHN ( 1:1 by weight )
which is made by extremely rapidly stirring ( electric paddle ) a suspension of MHN in silver nitrate and then ( still with stirring ) bubbling acetylene through then liquid until the soln just clears of the turbidity.
This composite is sufficiently powerful to initiate PETN even when using less than 0.02 g, but cannot do so in coloumns of less than 1-1.5 mm diameter. HMTD can, and lead azide probably can as well, but I've run out of NaN3 so...

[pdb]

You prepare it from 3-nitroanilin, HClO4, HCl & NaNO2: 1ml HClO4 (70%) + 1ml HCl (30%) inA in 50ml water (you can thus use much less concentrated acids). Add 1g 3-NA, which will easily dissolve. Prepare a solution of 1g NaNO2 in 20ml water. Both solutions in an ice bath until they reach 0°C, then mix them together at once, and you will get a pale-brown precipitate in the minute (do not let it unattented for hours, as bigger crystals would grow and spontaneously explode- I experienced it the first time). Filter, wash and dry. DPNA is a brown powder, altough the literature mentions it as a white compound (I only used very pure precusors), which detonates in the smallest quantity, without noticeable initiation phase.

It is cited in Urbanski and mostly German books, as well as in some French ones. I had a comparison with azides and fulminates, but cannot retrieve it right now. In fact, most authors recognize it great initiating value, but do not give much information (vod, sensitivity...). My own experiments show you can initiate PETN with as little as 5mg DPNA (less if confined).

I kept a sample for 6 months at sunlight without noticing any loss in quantity or in power, although it sligthly darkened. I have no idea about O2 and CO2 possible impact.

I made Ag acetylide years ago, but abandonned it after a while, as well as all other mineral compounds in favor of DPNA. I think DPNA deserves more attention.

By the way, has anyone got the CD issued by the Picatinny Arsenal ? Would be interested to get a copy to replace my old paper edition...

[nbk2000]

If you've got access to those chemicals, then it sounds like it'd be good, but how many of us do? 3-nitroaniline and perchloric acid aren't exactly OTC ingrendients you know.

[Mr Cool]

Sounds scary to me!! I really don't like diazo compounds...

As I have mentioned before, these (http://orders.mkn.co.uk/cracker/fillings/snaps) work well. I've seen them sold for £6 for 144, and the explosive extracted from two of them (= a few mg) will reliably initiate PETN. I know that the explosive inside is unchanged after about ten years if it is left in place in the cracker snaps (ie, dark), because the first ones that I used were about ten years old, it is quite sensitive to friction (hence its use in cracker snaps), and it detonates immediately from flame (apparently no DDT phase), but it is quite insensitive to shock.
I've used it in 2mm columns (edit: 2mm diameter, not height), but it could be used in smaller tubes for sure, since the primary did not occupy the whole of the 2mm diameter.

Safe, powerful, reliable, and available cheaply OTC :). You might want to experiment with them, Microtek...

[pdb]

To nbk2000: yes, I access such chemicals (including fuming HNO3) throuh a friend's company.

MrCool: 1) you don't have the pleasure of making your own primary ex 2) use caution as the stuff you get from these crackers might well be AgONC, with which I had several accidents in the past 3) do not generalize: this diazo compound is said raisonnably stable in the literature.

[Mr Cool]

1) I have the pleasure of making my own primary whenever I want (-- (http://www.boomspeed.com/mrcool/Azide.jpg)), but now I don't have to if I only want to try one quick charge.

2) "use caution as the stuff you get from these crackers might well be AgONC" - Caution is used with everything, that's common sense in this hobby. It seems to me like silver acetylide nitrate, but I haven't tested. It certainly seems different to the explosive in these (http://www.sillyjokes.co.uk/p-jokes/surprise/fun-snaps.html), which can be extracted with ammonia solution and is apparently AgONC, although that could easily be due to the different physical characteristics.

3) I wasn't generalising; I don't like diazo compounds! Well, I'm OK with DDNP, but that doesn't have a typical diazo structure.


I'm sure it is stable, and if it works for you then that's fine. I was just saying that I don't like diazo compounds, and suggesting the cracker snaps as a primary for Microtek, and others, who might not be able to make anything better than peroxides.

[pdb]

That's fine.

For myself, I HATE peroxydes for their great unstability, inability to store ans weak initiating power. If I couldn't access to most chemicals, I would rather focus on the good old mercury fulminate, as mercury can been found quite easily. Altogether, the detos wiil be more reliable and safer.

[Microtek]

Well, I have access to many chemicals, including precursors to the diazo compound that pdb mentions - but not anything that is labeled "toxic". "harmful" - no problem, "carcinogenic" - likewise, but that "toxic" group includes some useful substances....
Anyways, the thing is that I require primaries of such high performance that even dextrinated lead azide is not good enough ( undextrinated is fine, performance wise, but the crystals are rather large and besides I don't like the way lead azide is degraded by the air ).
I was thinking of trying those azo-clathrates from Mr Anonymous on the other forum, but I haven't gotten round to making some more NaN3.

Remarkably, HMTD can do most of the things lead azide can, and is more stable in the air ( of course, HMTD has its share of problems such as inability to make DDT in small amounts, high sensitivity, highish vapour pressure, etc. ).

So, I suppose I'll try out both DNAP and the azo-clathrates to see what is best.

[Jumala]

I´m going around some time with an idea for a simple but powerful detonator .
I also don´t like peroxides and complicated primarys.

Save, powerful and reliable sounds very good for me.
So I remembered an old thread of wantsomfet where he detonated ANNM with 3,5g of fine KClO4/Al flashpowder. (No need of a classic primary).

PETN is a medium sensitive explosive (20cm with 2 Kg hammer) and much more sensitive than ANNM. So it must be easy to make detonators from 2g PETN and 1g Flash in a Al tube or empty shell. I would put some BP on the flash for better igniting and thats all.
KClO4/Al Flash is very stable. The military use it in M80 or DM12 in germany which can be stored for years.

My problem: I have no PETN and no place to test it.

Perhaps can a PETN owner spend some time for a test?

[pdb]

Attn Microteck: please keep me abreast of your test with DPNA. You should like it !

Attn Jumala: to initiate PETN in such a way, you will need a critical mass whose amount heavily depends of the confinement you will be using for making your deto. It might work, but for sure such deto will not be reliable at all, hence useless in my opinion. If you don't like complex primaries, just stick to Mercury fulminate..east

[grendel23]

I have made the azo-clathrate described by Mr Anonymous. The preparation went easily, the only difficulty was getting the very slow addition rates, one drop every several seconds, with my separatory funnel, next time I will use a buret instead.
I have not made DNAP, so I can't compare it to my clathrate, but the claims made in the patent and Mr Anonymous post are consistent with my experience. The clathrate will DDT in very small quantities, and is effective in compound detonators with a PETN base charge. I have not tried to quantify the minimum amount needed, but I have had no failures with 150-200mg combined with 750mg of PETN.
At 200mg each, I will get over 100 detonators out of 5.3g of NaN₃, not bad.:)
Here (http://www.geocities.com/sulfuric23/azoclath.jpg) is a picture of my stash. (copy and paste URL)

edit:

Here are the patent (http://patimg2.uspto.gov/.piw?Docid=03431156&homeurl=http%3A%2F%2Fpatft.uspto.gov%2Fnetacgi%2Fn ph-Parser%3FSect1%3DPTO1%2526Sect2%3DHITOFF%2526d%3DP ALL%2526p%3D1%2526u%3D%2Fnetahtml%2Fsrchnum.htm%25 26r%3D1%2526f%3DG%2526l%3D50%2526s1%3D3431156.WKU. %2526OS%3DPN%2F3431156%2526RS%3DPN%2F3431156&PageNum=&Rtype=&SectionNum=&idkey=6AB600E844C0) and thread (http://www.sciencemadness.org/talk/viewthread.php?tid=501) describing this compound.

[pdb]

Grendel23, I'm sorry but cannot find Mr Anonymous' recipe with the search fonction. Would you find posting it in your next message ? Thx

[nbk2000]

I keep telling people this, but no one seems to listen

SEARCH! That includes the internet in general, not just us.

Use google, the term azo-clathrate, and you'll see what you can find if you just look for it yourself. :rolleyes:

Thanks (notice it is NOT spelt "thx")

[Microtek]

Allright, now I've concluded my test-synthesis of DPNA:

I was unable to find 3-nitroaniline at the lab, so I had to go a couple of steps back and start from benzoyl chloride ( not much more accessible to the average member I suppose ).


Benzoyl Chloride --> Benzamide:
- 4 mL benzoyl chloride was added dropwise with stirring to 20 mL of the strongest possible aqueous ammonia. Temp was maintained at 5-8 C throughout, and conversion of the acid chloride to the amide ( pure white flakes ) was instantaneous.

- The product was recrystallized from hot water ( though not above 80 C as the amide may hydrolyse to benzoic acid at ca. 100 C ) to obtain slightly more than 4 g pure benzamide.

( when drying the benzamide temp was kept below ca 50 C to minimize conversion to benzoic acid )

Benzamide --> 3-nitrobenzamide:
- 4 g benzamide was dissolved in 24 mL 96 % H2SO4 and cooled to 5 C

- 9 mL 62 % HNO3, cooled to -10 C was added dropwise with magnetic stirring while keeping temp below 8 C.

- After addition, mix was stirred another 10 min, and then soln was poured onto 80 g ice and stirred vigorously to precipitate a voluminous off-white solid.

- This was filtered off and washed several times with cold water and then added to about 25 mL alcohol and stirred for about an hour.

- 70 mL water was added slowly to the stirred alcohol soln ( which didn't dissolve all ) to precipitate the product which had by then attained a much more dense structure.
2.15 g 3-nitrobenzamide was recovered after drying.


3-nitrobenzamide --> 3-nitroaniline by Hofmann rearrangement:

- 6 mL 15 % NaOCl was diluted to 41.5 mL with water, and 1.0 g NaOH was dissolved in it.

- The soln was stirred magnetically and 2.0 g 3-nitrobenzamide was added in one portion.

- The temp was immediately increased to 80 C, and held there for 30 min by use of a paint stripper gun. During this stage, the solid nitrobenzamide was dissolved and the soln changed colour from pale yellow to deep orange.

- After the 30 min, temp was lowered to 50 C ( the product began to settle out ) and 1.05 g Na2S2O5 in 13 mL water was added to reduce remaining hypochlorite and stop further reaction ( to 3-nitrobenzoic acid ).

- Mix was cooled to 0 C and filtered.

- Product was recrystallized from 93 % ethanol to recover 0.4 g 3-nitroaniline ( this was extremely wasteful; lots of the product crystallized slowly in the filtrate, but my goal was the highest degree of purity rather than yield so...)


3-nitroaniline --> DPNA

- 0.6 mL 60 % HClO4 and 0.5 mL 30 % HCl was added to 25 mL water along with a stir bar.

- In another beaker, 0.5 g NaNO2 was dissolved in 10 mL water.

- These to solns were placed in the freezer until temp had reached 0 C.

- 0.4 g 3-nitroaniline was dissolved in the dilute acid.

- With rapid magnetic stirring, the NaNO2 soln was added in one portion to the acidic soln, and within about 10 seconds, a white precipitate formed.

- Stirring was continued for 5 minutes and the product was collected by filtration. It was then washed in the filter with water until nearly neutral.

I haven't weighed the product as it isn't fully dried but it is a pure white powder, very similar in appearance to HMTD and when dry it detonates very violently on contact with flame even in pin head-sized amounts. It makes DDT almost, but not quite, as fast as silver acetylide-nitrate.


Further testing to follow.

[pdb]

Microtek, bravo !

Quite a long way but you made it. It would be very interesting if you could made some comparison tests with other primaries as regards to DPNA initiating power, which I think is very high. As said before, I succeeded to initiate PETN with 5mg loads only.

Another useful objective would be to find a way to obtain it in a more crystallized shape. Ideas are welcome...

[Microtek]

I have done a little preliminary testing of the compound. Firstly, I tested friction sensitivity by placing a few grains on a steel anvil and grinding them with a ceramic pestle. I took a few strokes with about 3-5 kilograms of weight applied to get them to explode. For impact sensitivity, a few grains were placed on the anvil as before, and the pestle was used to hit them with increasing force. It took about the same force as tapping someone on the shoulder when you are angry ( very scientific unit of measurement don't you think ? ). By comparison, HMTD was not set off by the grinding test, but rather smeared out over the surface of the anvil, and took a somewhat harder hit with the pestle before exploding.
On the other hand, when I later tested the flame sensitivity by compressing a small amount in a straw and exposing it to the spit of a thin BP fuse, it did not respond. Adding a little lead styphnate ( about 0.1 mg is more than enough ) on top solves this problem.
I then tested initiating power in a 2 mm diameter straw by lightly pressing a 1 mm coloumn DPNA on top of moderately pressed ( 250 psi ) PETN and adding 0.1 mg lead styphnate on top. This was enough to detonate the PETN which exhibited the same performance as usual. Considering the low density of the DPNA powder, and its similarities to HMTD, a loading density of 0.8-0.9 g/cc is assumed. This would give a charge weight of 2.5-2.8 mg.

I then investigated the possibility of binding the DPNA with NC. In the course of this study, I discovered that acetone is an excellent solvent for DPNA and that the solid that remains after evaporation of the acetone retains the characteristics of DPNA.
As a consequence of this discovery, I have been thinking that it may be possible to moderate the sensitivity of DPNA by dissolving it in acetone along with PETN, MHN, ETN, etc and co-precipitating by adding the solution to rapidly stirred water. Also, adding NG to an NC bound primary has in the past proven to desensitize the compound.

Furthermore, my interest in diazonium compounds was piqued by this activity so I did a search on the patent databases. On espacenet, I found a russian patent ( RU2080320 ) which patented the use of 2,4-dinitrobenzenediazonium perchlorate as a low sensitivity, high performance primary explosive. The patent was largely written in russian, so I couldn't understand much of it, but I would think that it could be prepared just like DPNA but from 2,4-dinitroaniline.
For this reason I have been researching a synthetic route to that precursor and have settled on Acetanilide --> 2,4-dinitroacetanilide --> 2,4-dinitroaniline --> DNBDP

[pdb]

Microtek, I wish I could devote as much time as you do to experimenting.

Your assessment of the minimum load to initiate PETN confirms my own experience with DPNA (<5mg). In the same conditions, how much of the so-called double salts did you need ?

About your empiric measurement of mechanical sensitivity, I wonder I there would be any way to find a used Julius Peter apparatus, or build something resembling it that could reliably compare sensitivity of various primaries ("absolute" measurement doesn't make much sense as it heavily depend on the crystals shape and size).

I didn't have a chance to test DPNA solubility in acetone, but when making detos with PETN, I use acetone and had noticed that it didn't only moist DPNA, but seemed effectively to dissolve it. Your confirmation is a hope that we might find a way to obtain a product with a better apparent density and better "pourring" specs.:)

[pdb]

By the way, I forgot to post the reaction equation:

C6H4(NH2)(NO2) + HCl + HClO4 + NaNO2 -> C6H4(N=N-ClO4)(NO2) + NaCl + 2 H2O
138 -> 249.5

you should in theory get 1.8g DPNA from 1g 3-nitroanilin. In fact, I never exceeded 55% of the theorical yield, i.e. roughly 1 for 1 in weight. The colder, the better.

[Hystrix]

Originally posted by Microtek
Furthermore, my interest in diazonium compounds was piqued by this activity so I did a search on the patent databases. On espacenet, I found a russian patent ( RU2080320 ) which patented the use of 2,4-dinitrobenzenediazonium perchlorate as a low sensitivity, high performance primary explosive. The patent was largely written in russian, so I couldn't understand much of it, but I would think that it could be prepared just like DPNA but from 2,4-dinitroaniline.

This patent contains no description of preparation. It's only pointed there that raw materials are commercially available. Also it's written that stuff is thermally stable (230 deg. C. vs. 169 for DPNA), less sensitive to impact (18 cm vs. 9 for DPNA). Its VoD is 7.0 km/s (while DPNA has 5.8), and 14 mg of stuff is required for TNT detonation (vs. 45 mg of DPNA).

PS Impact sensitivity is for 1 kg; 50% of explosions

[KABOOOM [pyrojustforfun]]

Microtek that method was very impressive.
a cheaper way to get benzamide:
you add benzoic acid (commenly available) and H2SO4 to MeOH, warm this for a while, pour the whole sol in water, filter and collect the methyl benzoate, dissolve it in alcohol bubble dry NH3 to get an alcoholic sol of benzamide... or u may wanna nitrate the benzoic ester to methyl m-nitrobenzoate then convert it to its amide.
also instead of converting PhCOOH to PhCONH2 then nitrating, why not doing the reverse? (nitrating PHCOOH then converting to its amide in the same way I mentioned for PhCOOH) preparation of 3,5-DNbenzoic acid isn' very hard...

extracted from vogel (http://bcis.pacificu.edu/~polverone/vogel.html) :

IV,44. m-NITROANILINE
Prepare a solution of sodium polysulphide by dissolving 40 g. of crystallised
sodium sulphide, Na2S.9H20 (1), in 150 ml. of water, adding 10 g.
of finely powdered sulphur, and warming until a clear solution is produced.
Heat a mixture of 25 g. of m-dinitrobenzene (Section IV,12) and 200 ml.
of water contained hi a 1-litre beaker until the water boils gently : stir
the solution mechanically. Place the sodium polysulphide solution in a
dropping funnel and clamp the funnel so that the end of the stem is
immediately above the beaker. Add the sodium polysulphide solution
during 30-45 minutes to the vigorously stirred, boiling mixture, and boil
gently for a further 20 minutes. Allow to cool; this can be accomplished
more rapidly by adding ice. Filter at the pump and wash with cold
water. Transfer to a 600 ml. beaker containing 150 ml. of water and 35 ml.
of concentrated hydrochloric acid, and boil for 15 minutes ; the m-nitroaniline
dissolves leaving the sulphur and any unchanged ra-dinitrobenzene.
Filter and precipitate the w-nitroaniline from the filtrate by
the addition of excess of concentrated aqueous ammonia solution.
Filter off the product and recrystallise it from boiling water. The yield of
m-nitroaniline (bright yellow needles) is 12 g. ; m.p. 114°.
Note.
(1) Crystallised sodium sulphide is very deliquescent and only a sample which
has been kept in a tightly-stoppered bottle should be used.

Methyl m-nitrobenzoate.
In a 1 litre round-bottomed or bolt-head
flask, fitted with a mechanical stirrer, place 102 g. (94 ml.) of pure methyl
benzoate (Section IV, 176) : support a separatory funnel containing a
mixture of 62-5 ml. of concentrated sulphuric acid and 62-5 ml. of
concentrated nitric acid over the mouth of the flask. Cool the flask in an
ice bath to 0-10°, and then run in the nitrating mixture, with stirring,
whilst maintaining the temperature of the reaction mixture between 5°
and 15° ; the addition requires about 1 hour. Continue the stirring for
15 minutes longer, and pour the mixture upon 700 g. of crushed ice.
Filter off the crude methyl m-nitrobenzoate at the pump and wash it
with cold water. Transfer the solid to a 500 ml. bolt-head flask and stir
it with 100 ml. of ice-cold methyl alcohol in order to remove a small
amount of the ortho isomeride and other impurities. Filter the cooled
mixture with suction, wash it with 50 ml. of ice-cold methyl alcohol, and
dry in the air. The practically colourless methyl m-nitrobenzoate weighs
115 g. and melts at 75-76° ; it is sufficiently pure for conversion into

IV,168. 3,5-DINITROBENZOIC ACID
Method 1. Dissolve 50 g. of pure benzoic acid in 230 ml. of concentrated
sulphuric acid in a litre flask equipped with a ground-in condenser. Add
73 ml. of fuming nitric acid (sp. gr. 1 • 5) a few ml. at a time. Shake the
flask well and cool in ice water during the addition ; much heat is evolved
and a clear yellow solution results. Add a few fragments of porous porcelain
and heat the mixture gradually on a water bath to 100° during 45
minutes. At 70-80° the reaction may (and usually does) become vigorous ;
moderate, when necessary, by cooling the flask in cold water. Maintain
the mixture at 100° for 15 minutes with occasional shaking, and then
transfer it to an oil bath at 100° ; raise the temperature to 130° over 30
minutes and keep it at 130-140° for 1 hour. Allow the flask to cool:
crystals commence to separate at about 90°. When cold, pour the reaction
mixture into 3-4 litres of ice water, filter the separated crystals, wash
with water, and dry. The yield of 3 : 5-dinitrobenzoic acid, m.p. 204°,
is 50 g. : this acid is pure enough for most purposes. Upon recrystallisation
from 50 per cent, alcohol (4-5 ml. per gram), the m.p. is
raised to 207°.
Method 2. This preparation should be carried out in the fume cupboard
since nitrous fumes are evolved. Place 62 g. of benzoic acid and
300 ml. of concentrated sulphuric acid in a 2-litre round-bottomed flask,
warm on a water bath with shaking until the benzoic acid dissolves, and
cool to 20°. Add 100 ml. of fuming nitric acid (sp. gr. 1-54) in portions
of 2-3 ml. Keep the temperature between 70° and 90° by means of
external cooling with cold water ; avoid the evolution, in other than small
quantities, of brown fumes. Cover the flask with a watch glass, and allow
to stand for 1 hour or overnight. Heat the flask on a water bath for
4 hours ; considerable quantities of nitrous fumes are liberated, v Allow
to cool to room temperature, preferably with mechanical stirring, when
yellow crystals will separate from the solution. Add a further 75 ml.
of fuming nitric acid ; heat the mixture on a water bath for 3 hours, then
in an oil bath at 135-145° for 3 hours. Allow the reaction mixture to cool
and pour it into a mixture of 800 g. of finely-crushed ice and 800 ml. of
water. Allow to stand for 30-60 minutes, filter off the crude 3 : 5-dinitrobenzoic
acid at the pump, and wash it with water until free from sulphates.
Recrystallise the crude acid (66 g. ; m.p. 201-202°) from 280 ml.
of hot 50 per cent, alcohol. Collect the recrystallised material and dry
in the steam oven. The yield of 3 : 5-dinitrobenzoic acid, m.p. 207°,
is 62 g.

you can even diazotate picramide! (needs conc acids).

some questions:
1. what if there are more amino groups in the ring (in meta positions)? hmm..
2. any info or experiments on using diazonium nitrates as primeries?
3. I guess when using less acids and lower concentrations u get triazens. are these primary explosives? (I assume they are, but wanna make sure) at least they don't need HClO4

[Microtek]

Philou was of the opinion that HClO4 could be made from KClO4 + HCl in water ( in an equilibrium ). This would mean that, as a HCl / HClO4 mix is already used, KClO4 and conc HCl might work as well.

Edit: I suppose that the perchlorate must be much more insoluble than the chloride, so it doesn't matter were the ClO4- ion comes from.

[Microtek]

After a bit of experimenting, I think I have succeeded in making 2,4-dinitrobenzenediazonium perchlorate.

My starting point was acetanilide, but many other precursors could be used instead.

Acetanilide --> p-nitroaniline:

- 0.9 g acetanilide was dissolved in 1.5 mL conc H2SO4

- 1.5 mL conc H2SO4 was mixed with 0.5 mL 62 % HNO3 and added dropwise to the first soln with stirring and cooling. Temp was kept below 20 C

- After addition was complete, mix was stirred an additional 10 min, and then 10 mL ice water was added with stirring. This precipitated a large amount of pale yellow solid.

- Mix was then heated to reflux and held there until the solid had dissolved and a sample of the mix was completely soluble in water ( approx 15-20 min )

- Mix was cooled and then neutralized slowly with 10 mL conc ammonia water. This precipitated o- and p-nitroaniline which was filtered off.

- The crude product was slowly recrystallized from 2 mL hot ethanol and p-nitroaniline was recovered as long needles ( ortho- isomer is much more soluble ).


p-nitroaniline --> 2,4-dinitroaniline ( and some 3,4-dinitroaniline )

- 0.5 g nitroaniline was suspended in ca 3 mL glacial acetic acid, and a little conc H2SO4.

- 0.2 mL 96 % HNO3 was mixed with ca. 3 mL 96 % H2SO4 and was added to th NA suspension with stirring, keeping temp below 15 C.

- After addition, a further 2 mL conc H2SO4 was added dropwise and mix was left to stir for 30 min.

- Mix was drowned in water and basified with ammonia water which precipitated the product.

- The crude product after washing and drying, was added to 25 mL water with 0.5 mL 60 % HClO4 and 0.5 mL 30 % HCl and was found to be insoluble. ( The reason for this was that I was unsure of whether the p-nitroaniline was converted to dinitroaniline or not; dinitroaniline is much less soluble in aqueous acid than mononitroaniline ).

- The suspension was filtered and the solid was washed with water and then ethanol.
Yield: 0.30 g

After drying, the product was going to be diazotized, but due to the very low alkalinity of dinitroaniline, the reaction needs to be performed with nitrosylsulfuric acid:

2,4-dinitroaniline --> 2,4-dinitrobenzenediazonium perchlorate:

- 1 mL 96 % H2SO4 was cooled in ice and with stirring, 0.15 g NaNO2 was added in small portions, keeping temp below 10 C.

- Stirring was maintained for 10 min after end of addition.

- Beaker was transferred to a 15 C waterbath and allowed to come to room temp with stirring. Then, the temperature of the waterbath was raised very gradually ( over ca 20 min ) to 65-70 C and maintained at this temp until all had dissolved.

- The mix was then cooled to 20 C which caused NaHSO4 to precipitate.

- 0.3 g 2,4-dinitroaniline was added with magnetic stirring in very small portions, taking care to avoid any clumping of the solid. Temp was kept at 20-30 C.

- 4.5 g crushed ice was added to the soln to quench the reaction while stirring was maintained. The soln was then filtered to remove a small amount of insoluble matter, and 0.2 mL 60 % HClO4 diluted to 5 mL was added in one portion.

- Stirring was maintained for about one minute and then stopped. When the soln was then swirled a little, a fairly large amount of solid crash precipitated from the liquid.

- The solid was filtered and washed, and a small amount was dried on filter paper to determine some properties.


It is a pale yellow solid which pops when ignited if slightly moist but detonates with even more vehemence than DPNA when dry. It reliably makes DDT in even single grain amounts just like silveracetylide nitrate.
In the qualitative sensitivity tests it performed much better than DPNA: When hit repeatedly with ceramic pestle on steel anvil with about as much force as you would use for knocking on a door, it eventually exploded.
When ground with the pestle on the anvil, it did not explode even when I really leaned on it, but was smeared out instead.
I have not tested initiation capacity yet, and may not be able to for a few days.

[pdb]

Kabooom:

any info or experiments on using diazonium nitrates as primeries?

Instead of DPNA, it's possible to prepare diazonitrate-3-nitroaniline in the same way; but this compound is said to be extremely sensitive (a shock wood against wood is sufficient to make it explode) in an early 1900's German book.

[Al Koholic]

Hi all! I've enjoyed this thread a lot and have some info that you all might find somewhat relevant.

Step 1) Naphthalene --> mononitronaphthalene via dissolving the naphthalene into glacial AcOH and then adding a mix of H2SO4 and HNO3, heating at steam bath temp for 30 minutes and precipitating.

Step 2) Oxidation of this product via KMnO4 to yield 3-nitro-phthalic acid.

Step 3) Dissolve this product in glacial AcOH and react with either ammonium carbonate or I suppose you could bubble in NH3 gas to prepare 4-nitro-isoindole-1,3-dione

Step 4) React this with CaCl2, NaOH at 100C to yield 2-amino-6-nitro-benzoic acid

Step 5) Treatment with H2SO4 decarboxylates this compound to 3-nitroaniline.

I think this route is also quite attractive because of its simplicity and ease of conditions and reactants. What do you think of this proposal Micro?

[Microtek]

I think you would at least have problems with mixes of isomers. For instance, in the nitration step. Also, does KMnO4 work for oxidative cleavage of the ring in naphthalene ? The books I have mention this reaction with conc H2SO4/HgSO4 or O2 and V2O5 in the vapour phase, but no KMnO4. Maybe it is because these methods are more desirable in industrial setups, but I would have thought that something as simple as permanganate was worth mentioning...

[Hystrix]

2 Al Koholic:
I think such ideas can be applied to high explosives but not to primers. You will obtain potentially highly sensitive compound with unknown by-products and you won't know its sensitivity correctly. This product may be extremely sensitive and weakly initiative at the same time.

2 pdb:
afaik diazonium nitrates are worse than perchlorates 'cause they have weaker initiativity and can be "deadly pressed" (similar to mercury fulminate).

[Marvin]

Al Koholic,
Vogel has a method for alpha nitronapthalene, didnt think it required acetic acid, why do you think this would help? Product at low temp and short time will be virtually all alpha. If seperating is required the alpha is steam volitile along with remaning napthalene and the beta isnt.

Ok, now cleaving the other ring with NaOH/KMnO4 is fine in theory. Should work ok in practice, acid oxidation probably wont work very well. When you have a NH2 group on a napthelene ring, KMnO4 will cleave that ring, and when you have NO2, it will cleave the other ring. Now you have 3-nitro-pthallic acid. If this doesnt work well, you can cleave napthalene, and then nitrate but watch out becuase it nitrates very readily to mainly the 3 nitro derivitive.

Ok, now you start to lose me. You're dissolving in acetic acid again, and adding ammonia. Why do you think this wont simply form a salt with acetic acid? I dont follow.

Ok, assuming you form nitropthallimide, I dont follow this next step either. Reaction with calcium chloride and sodium hydroxide, was this supposed to be a hoffman rearangement with hyperchlorite and hydroxide? Would this only work with a primary amide? Why would it go in one direction only, ie away from the nitro group?

NExt step, you are decarboxylating with sulphurc acid instead of the more usual hydroxide method, is this best considering if it works it will be forming a salt at the same time?

Very interesting start, but the rest rather confuses me.

[pdb]

Microtek, I have tested DPNA solubility in acetone, and I estimate it in the range of 50-60gr DPNA per liter at 20°C.

So far, all my trials to obtain bigger crystals have failed (by cooling and/or dilution with water).

[Microtek]

Bigger crystals ? I am more interested in getting smaller crystals ( not that they aren't small to begin with but the smaller the better ) to reduce sensitivity. I have thought about coating crystals of different explosives such as alfa-HMX ( or other porous explosives that are reasonably insoluble in acetone ) with DPNA in order to get an insensitive ( to mechanical stimuli ), powerful compound.
I tried mixing about equal volumes of DPNA and PETN with a drop of acetone and kept mixing while the acetone evaporated. The resulting cake was easily broken up when not quite dry and, after drying fully, exhibited very high brisance even in small amounts ( ca 5 mg ) when contained, but only crackled when ignited in the open.
Unfortunately, it was still rather sensitive to impact, but not quite as much as straight DPNA.

[pdb]

Sorry, Microtek, I didn't express myself correctly. I am trying to modify the DPNA crystals' shape inorder to improve its "pouring" performance, so as to facilitate its loading while making detos for instance. Given the current nature of precipitated DPNA (needles, it seems), I think this improvement -if proven possible- will not occur without growing the crystals' size. But I may be wrong.

Anynews about 2,4-dinitrobenzenediazonium perchlorate ?

[Microtek]

So, what you need is spherical "crystals" ? I think spherical gives the best flowing characteristics.

About the dinitrobenzenediazonium perchlorate ( DBP ): It initiates at least as well as DPNA, though I haven't made actual quantitative tests; I have just used it with PETN. The method for diazotizing came from a book on dye chemistry and was specifically for 2,4-dinitroaniline, but after I had collected the initial batch of crystals and the filtered mother liquor had stood for a while, a second crop precipitated. I collected this in a second filter and found it to be non-initiating in nature, so I think that it must be impurities in the dinitroaniline or come from loss of nitrogen from the diazocompound.

[pdb]

Right: spherical crystals give "pourability" and ensure a good natural sensity. Something like AgN3 re-crystallized from NH4OH, which from these criteria is the nest among all the primaries I have prepared so far.

Regarding DBP, I am tempted to prepare some, starting from commercial grade 2,4-dinitroaniline but am wondering if it is worthwhile the trial, compared to DPNA's performance.

[Microtek]

I would say that if you have access to 2,4-DNA then it is worth it, mostly because of the decreased sensitivity compared to DPNA. Performance wise it should be better as well ( 14 mg DBP to initiate TNT vs 45 mg for DPNA ). The only drawback of DBP compared to DPNA is that it is slightly more bothersome to diazotize via nitrosylsulfuric acid than with simple HNO2, but it is not particularly difficult and doesn't take a long time either.

[Rosco Bodine]

[QUOTE]Originally posted by grendel23
I have made the azo-clathrate described by Mr Anonymous. The preparation went easily, the only difficulty was getting the very slow addition rates, one drop every several seconds, with my separatory funnel, next time I will use a buret instead.


grendel23 ,

If you remove the stopcock plug from the funnel ,
you can make a small "trickle notch"
in the edge of the bore in the plug with a needle file
or a very small drill bit so that a clean cutoff is prevented .

Then a second notch must be cut on the other end of the
bore of the opposite side of the plug , ( on a diagonal through the bore ) .
Study the way the valve works
and you will see how to do this modification successfully .

[pdb]

Microtek, I received 100g of 2,4-dinitroanilin and am about to try preparing 2,4-dinitrobenzenediazonium perchlorate.

However, I would like to know if before going the nitrosylsulfuric acid way, you had a chance to try the method used to make DPNA.

Also, what do you think of the equation:
C6H3(NH2)(NO2)2 + H2SO4 + NaNO2 + HClO4 -> C6H3(N=N-ClO4)(NO2)2+ NaHSO4+2 H2O

Which according to you trial, should be achieved in two steps:
2 H2SO4 + NaNO2 -> NaHSO4 + HNOSO4 + H2O

C6H3(NH2)(NO2)2 + HNOSO4 + HClO4 -> C6H3(N=N-ClO4)(NO2)2+ H2SO4 +H2O

[Microtek]

The problem with doing it the usual way, is that 2,4-dinitroaniline is simply too insoluble in water, and that dilute acids are not strong enough to protonate it to the anilinium ion. There is a discussion of this in one of the dye-chemistry books that Polverone has made availible.

Regarding the equation, the reaction actually takes three or four steps:
- Preparation of nitrosylsulfuric acid.
- Addition of dinitroaniline to form dinitrobenzenediazonium sulfate.
-( dilution and, if neccessary, filtration to remove unreacted dinitroaniline ).
- Addition of perchloric acid or sodium perchlorate to precipitate insoluble DBP.

[pdb]

OK, that makes sense.

However, I thought the filtration step was required to remove NaHSO4, not dinitroaniline in excess. Does that mean that NaHSO4 dissolves when you diluate the solution ?

[pdb]

Microtek, at last I found some time to try the synthesis of 2,4-dinitrobenzenediazonium perchlorate.

Firstly, I tried the same process than with DPNA, using concentrated acids (HCl 38%, HclO4 72%): as you had predicted, I couldn't achieve dissolution of 2,4-dinitroaniline.

Therefore, I scrupulously followed your way:

Everything went smoothly, according to your own detailed description of the process. In the last step, I obtained an abundant precipitate in 45secs after addition of the perchloric acid. This precipitate turned the solution in beige. However, once filtrated and washed on filter, the sediment appeared to be bi-colored, i.e. dark beige on top and pale beige or even white in the inner layer ! It is not the first time I have to deal with a bi-color sediment on filter and I hate it as it is difficult to know where the contamination come from (air oxygen ? hydrolysis ?). I started to let it dry, and it seemed that the brown portion was getting darker… I decided to wash it another time, without waiting for complete dryness. Surprisingly, this time the filtrate came very dark brown (I thought the filter had got an hole –which proved untrue after checking). I chose to stop washing and let the precipitate dry: again, there are distinctively two colors, a pale beige and now a very dark brown. When it is dry, I will try to isolate a little of each to check its behaviour.

[Microtek]

Strange....
Mine had a uniform yellow/orange colour which it retains today, more than 4 months after it was prepared.

[pdb]

Microtek, although I use 99% pure dinitroaniline, working with this kind of substance is sometimes confusing because of their dyeing power... So I will make another try, and this time I will filtrate just after the precipitate appears, in order to avoid any possible by-reaction (this time, I had maintained stirring 10min after precipitation).

I found no difference between the different flavours -colorwise- of the sediment... they all pop violently, without DDT since still moist.

Do you see any other way to preparate it besides the nitrosylsulfuric acid one ?

[pdb]

Microtek, I made a second batch.

I multiplied your own proportions by 4, but slightly decreased the amount of dinitroaniline, which allowed me to skip the first filtration, as there were no insoluble matter.

This time, from the moment the dinitroaniline had been diazotated by the nitrosylsulfuric acid, I took appropriate precautions in order to keep temperature in the [0°,5°C] range until final washing, so as to avoid any possible decomposition of the product with production of N2.

It worked perfectly and I got on the filter a pale lemon yellow precipitate, homogeneous in color. But the trouble soon began: minute after minute while I was still washing with ice distillated water, the precipitate began to darken, at least in surface, and turned brown in less of 5 minutes. Simultaneously, the filtrate, initially pale yellow, turned also darker.

I stopped washing and let dry. With evaporation of the water, the sediment became more pale and ended as a beige powder, agglomerated in a layer easily secable.

But the worst is to come: when ignited by a flame, an amount of the size of a match head –which is not that little for a primary- would violently pop, with a luminous flash, without DDT. In fact, it reminds me Hg(ONC)2, without the little cloud of smoke…

I suspect it would easily go DDT if confined or in bigger quantity, but the same amount of DPNA –and even a tenth of it- would detonate with impressive mechanical effect.

So, what is wrong ? Why do we disagree so much about its behaviour ? I double checked I was using 2,4DA and not 2,6.

I also left a tiny amount overnight in a few ml of water, and the next day it was almost all gone, and the water had turned brown ! I do not want to bother you with this, but if you want to do me a favour, would you mind put a tiny sample of yours in water, to check if it colours the water and if it eventually dissolves ?

I was so frustrated that I undertook preparation of azo-clathrates with Pb(NO3)2 and got a nice easy flowing bright yellow powder. But besides the fact that its sensitivity to flame avoids addition of lead styphnate, its sensitivity to mechanical stress remains high and not so different from pure lead azide, limiting its interest (might be the reason why these compounds did not show up in public papers since the 1969 patent).

[Rosco Bodine]

(SNIP)
I was so frustrated that I undertook preparation of azo-clathrates
with Pb(NO3)2 and got a nice easy flowing bright yellow powder.
But besides the fact that its sensitivity to flame avoids addition
of lead styphnate, its sensitivity to mechanical stress remains high
and not so different from pure lead azide, limiting its interest
(might be the reason why these compounds did not show up
in public papers since the 1969 patent).

What most probably limited the interest in the azo-clathrates is
technical obscurity more than any technical deficiency .

By understanding the process by which they are made and then
adjusting the synthesis to produce a desired clathrate type ,
the properties of the clathrate produced can be varied , and
that includes sensitivity to impact , which is directly related
to crystalline size for the azo-clathrates in the same way as is
true for other primary explosives . You trade bulk density for
lower impact sensitivity by making the azo-clathrate in smaller
crystalline form . Lower temperatures and more concentrated
solutions favor smaller crystals , while higher temperatures and
less concentrated solutions favor larger crystals . This is a general
rule for such syntheses and for all crystallizations .

Lead azide itself is not unduly sensitive to mechanical stress if
the crystal size being used is appropriate for the application .
That is what makes possible its use in firing trains in artillery
shells , where it must not detonate prematurely from the shock
of the projectile being fired . Even mercury fulminate has been
used in that regard , and fulminate is far more sensitive than
azide . So crystalline size and form is a definitive factor for
the practicality of a specific compound to a specific application .
The same importance of crystalline form and size is equally true
for secondary high explosives , where all the factors relating
to the explosive are directly related to the crystalline form .

My own sample of the 4/12 azo-clathrate was yellow , free-flowing
microcrystalline powder , similar to what you described .

The 4/11 azo-clathrate as made by the patents instructions
gives a lower density product in lower yield . The acetate
containing variant of the patent is a fluffier powder still .

Don't be too hasty in making negative general conclusions until *after*
you do more extensive experiments regarding that class of compounds
which have been so little reported in the literature .

The truth is that the azo-clathrates are probably the highest art
in the way of initiating explosives which are attainable from
relatively simple precursors and using simple equipment .

There are marginally superior initiating explosives which are known ,
but the added effort and expense for the production of those
tetrazole and triazole derivatives and other "exotics" is unjustified
except for certain highly specialized applications .

[pdb]

Rosco Bodine, you know your subject pretty well, and it is a real pleasure as it is not always the case on this forum.

To be sure I properly understand your ideas, I would try to sum them up by saying that the interest of using the azo-clathrates lies in the fact that by varying the precursors and/or the experimental conditions (temperature, stirring, concentrations, timing), they offer much more room than lead azide alone to modify and control the specifications of the final products… Right ? I would fully agree with that, but on the other hand I am not so sure that in the real life most of the requirements cannot be met by conventional products… But for the sake and pleasure of experimenting, the clathrates are definitively great stuff, and I swear I will not mention them any more without a minimum of respect !

However, I cannot agree more with your comments about the race towards costly exotic tetrazoles and the like.

Regarding the only flavour I made so far (example 5, i.e. with Pb(NO3)2), I was surprised (and a little disappointed) to see that tiny amounts would deflagrate iso detonate, when in the same quantity lead azide would naturally detonate: the picrate and nitrate show there an "extinguishing" effect (improper spelling and wrong term, but I have no dictionary handy) on the azide that I wouldn't have suspected. By the way, do you have any data about its initiating power ?

[Rosco Bodine]

Rosco Bodine, you know your subject pretty well,
and it is a real pleasure as it is not always the case on this forum.

Credit what I know to surviving forty years of experiments beyond my first
synthesis of mercury fulminate and being disappointed with its explosive
properties in small amounts . The operative term for tiny critical mass for
primary explosives is "unequivocality" . Higher unequivocality is not
necessarily desirable , especially because it often introduces other
undesirable properties . The idea of the clathrates is to somewhat
"tame the wild beast" that is lead azide , without breaking its legs .

To be sure I properly understand your ideas, I would try
to sum them up by saying that the interest of using the azo-clathrates
lies in the fact that by varying the precursors and/or the experimental conditions
(temperature, stirring, concentrations, timing),
they offer much more room than lead azide alone to modify
and control the specifications of the final products… Right ?
Exactly , you can make an azo-clathrate more or less unequivoval ,
and vary its other properties to suit your requirement .
I would fully agree with that, but on the other hand I am not so sure that in the real life
most of the requirements cannot be met by conventional products
What "conventional" products do you mean ?
But for the sake and pleasure of experimenting,
the clathrates are definitively great stuff,
and I swear I will not mention them any more without a minimum of respect !

However, I cannot agree more with your comments about the race
towards costly exotic tetrazoles and the like.

Regarding the only flavour I made so far (example 5, i.e. with Pb(NO3)2),
I was surprised (and a little disappointed) to see that tiny amounts
would deflagrate iso detonate, when in the same quantity lead azide would naturally detonate: the picrate and nitrate show there an "extinguishing" effect (improper spelling and wrong term, but I have no dictionary handy)
on the azide that I wouldn't have suspected. By the way, do you have any data about its initiating power ?

You would understand better the DDT "phenomena" from experiments
with lead styphnate / lead azide mixtures . A similar "detuning" of
the lead azide will occur with mixtures rich in lead styphnate .
Tetracene and DDNP mixtures with azides show the same effect .

Actually the DDT "critical mass" is very small and is not undesirable .
If microdetonators are being made , a hotter clathrate or silver azide ,
or an exotic would be better .
It is possible to make a 4/17 chlorate containing clathrate which is plenty hot ,
but for safety and general use , the 4/12 nitrate compound is
plenty enough energetic to do the job of safely initiating even picric acid
as a lightly compressed charge in a plastic detonator casing .

If you make a small pellet of the 4/12 with dextrine , the DDT quantity
is what ten or fifteen milligrams in open air ? Confined , the DDT critical
mass is much smaller . Unequivocality is something desired not to be
absolute , as for the tiniest single crystal to detonate , because in
practice it is a *mass* of many crystals which will comprise the charge ,
and the safety as well as the performance of that mass of crystals is what
is the "business" performance of that composition .

The "phlegmatizing" effect is intentional and is part of the improvement
over straight lead azide , which is "too unequivocal" for safe use .
Think of the azo-clathrates as a firing train contained within each molecule ,
where just the right amount of azide is contained as an encapsulated ,
stabilized , more user-friendly form .

[grendel23]

My azo-clathrate (4/12) will DDT in amounts of around 25mg or so, when bound with a little dextrin first, that is plenty hot for me.
There is data on initiation efficiency in the original patent, 16mg to initiate PETN or RDX, this may not correspond exactly with the material which Rosco or I have made, but it does indicate these are very potent compounds.
I agree with Rosco that this is probably the most useful high performance primary around; ease of synthesis, easily obtained precursors, good stability, reasonable sensitivity, desirable physical properties (free flowing powder), much lower static sensitivity than straight lead azide, flame sensitive (no need for lead styphanate), very economical (24g primary from 5.3g NaN₃), and world class performance.
There are other materials with some of these traits, but I am not aware of any that posses them all.
The only caveat is that the precursors are very toxic.
For any of the members who wish to make the jump past organic peroxides and start making compound dets, this is a good choice.

[Rosco Bodine]

One real advantage of the azo-clathrates is their storage stability
even under adverse conditions . I have samples made several years
ago and stored outdoors where temperature ranges from -10 C to 60 C
along with humidity of the tropics , and the material remains
unchanged from the day it was made . Lead azide stored under the
same conditions steadily deteriorates . From what I have observed ,
the azo-clathrates are absolutely storage stable . You can prepare
the material and it doesn't slowly decompose , but remains useful ,
preserving the investment of time and effort which was put into
the synthesis . Detonators in which the azo-clathrate is loaded
would likely retain their "freshness" and power , indefinitely .

[pdb]

Rosco Bodine, I wouldn't be able to write as good poetry as some others, but I do share your fascination for primaries, and azo-clathrates, because of their sophistication, will be come for me a new land of exploration.

You would understand better the DDT "phenomena" from experiments
with lead styphnate / lead azide mixtures . A similar "detuning" of
the lead azide will occur with mixtures rich in lead styphnate .
Tetracene and DDNP mixtures with azides show the same effect.

I have been doing numerous tests with such mixtures and others over more than 25 years now, so I am full aware of this so-called "detuning" effects. My surprise just comes from the fact that I would have tought that the relative proportion of lead azide entrapped in the complex would have transmitted to it the capability of easy DDT. Which shows, another time, how suspicious I have to stay vis-à-vis my intuition…

The operative term for tiny critical mass for primary explosives is "unequivocality".

I can translate the term in my own language, but am still not sure of the idea you put in (is it of your own invention ?): are you meaning that when assessing the critical mass, one must choose the value giving 100% DDT iso 50% ? Or what ?

It is possible to make a 4/17 chlorate containing clathrate which is plenty hot.

Would you mind explain the operative principles, in particular do you need first to prepare Pb(ClO3)2, or can you use another chlorate salt (K, Na) sometime in the process ?

What about a perchlorate flavour ?

Have you ever tried also to substitute Ag to Pb ?

Coming back to the nitrate 4/12 compound, how can you be sure that it is not contaminated with free precipitated lead azide ?

[Rosco Bodine]

The term "unequivocality" for a primary is indeed a term that
I found the need to invent . Sorry for creating any confusion for
using my own terminology . In using the the term "unequivocality" ,
what I mean is that property of a primary explosive related to its
"minimum critical mass for DDT" .

An unequivocal primary explosive would be a material which has no
DDT minimum critical mass but is so "hot" that even a single tiny crystal
detonates directly . Absolute unequivocality would be a single molecule
of detonation "critical mass" for DDT , or complete DDT irrelevancy .

I hope that explains the term "unequivocality" as I have used it .

The observation which I have made is that even lead azide does not demonstrate
single crystal unequivocality to high order detonate , but does show unequivocality
in single crystal amounts to low order detonate . From there , increasing the
amount of charge , while keeping to an efficient "column diameter" for the charge ,
there is reached a high order "transition threshold" where
a sudden jump in the output energy occurs . The same characteristic
increase in output from a low order detonation to a high order detonation
is a general rule in my experiments for many explosives , primary explosives
and also for secondary explosives . That consistently observed low order
to high order transition is a distinctly separate phenomena from DDT .
A detonation sequence actually goes through about four distinct stages
to reach a self-sustaining high order velocity and final output from a
well designed detonator . Some or all of these accellerations may occur
within the individual elements , including the primary explosive . The
self-accelleration of a good primary is important , but so long as it is
*reasonably rapid* , then you will have a good initiator .
What my experiments have shown is that the geometry of the "pellet"
of the initiator should be regarded as a "ribbon charge" sitting atop
the base charge , with from one quarter to one half an additional quantity
of primary in excess , to allow for the "accelleration run" where the ignition
is followed by DDT and then the transition to high order , which carries through
the remainder of the pellet of primary , that portion functioning as the "ribbon charge" .
The output transition I describe can be observed with HMTD detonators
and also fulminate caps , where sand tests will show the output "jump" for
incrementally increased charges . DDT is just one initial step of the
detonation sequence . The rapidity of the acceleration from low order to high order ,
can more than "make up the difference" in a composition , where the operative factor
is what is the performance of the whole "pellet" of the initiator in tandem
with the base charge . The unequivocality of the primary is therefore not at all
the most important concern in a conventional sized or a large sized detonator .
Only in a microdetonator , where the size constraint is a factor ,
would there be a need to "nitpick" concerning how many milligrams
of which primary is "better" for that use . Anyone who is of the opinion
that straight lead azide is somehow "better" than an azo-clathrate because
straight lead azide is a more unequivocal primary , is welcome to use
straight lead azide . For a short term storage , or hermetically sealed cap ,
or for some specialized microdetonator application , straight lead azide
or silver azide may certainly be superior .

The general method for some of the variants of the azo-clathrates is
described by the patents . To form the chlorate variant which I mentioned
requires changing the proportions of the precursors accordingly , and the
chlorate is derived from sodium chlorate or potassium chlorate in reaction
with the corresponding equivalent of added lead nitrate to the system ,
which results in lead chlorate forming in solution . This is analogous to
the acetate containing variant described in the patent , where sodium
acetate contributes the acetate ion to an added amount of lead nitrate .
The 4/17 chlorate variant is one of the many "designer" variations which
are possible . Do not hold me to the 4/17 figure for the chlorate variant ,
4/16 may be closer to the truth . I have not completed long term storage
tests and periodic microscopic examinations to bear out my preliminary
identification of the crystalline material . The subject of a microscope
brings the answer to your final question . When you have a microscopic
examination of crystalline material that is uniform through the sample ,
crystals that are "clean" and consistent in appearance and do not
change color or granulation over time , it is a "pretty good" confirmation .
Add other factors like no change in weight over time , no development
of odor or other observed physical change , and it is sufficient for
reasonable certainty that you actually do have what you think
you've probably got . I generally don't post a formula for a synthesis
which has been done only once and so far that applies to the 4/17 chlorate
variant . I'll think about it , but really the 4/12 nitrate was a subsequent
choice for improved safety considerations , and is really in no need of
improvement , to my thinking . I wasn't keeping the best secret for myself ,
but posted the synthesis for the more proven and better researched 4/12
variant .

About the perchlorate variant , no I haven't tried it but did think about it
when I was making the 4/17 chlorate variant . I was mostly looking
at clathrates for which all precursors were OTC . The perchlorate would
probably be more stable and have a better oxygen balance , so it is a
good idea . I have some ammonium perchlorate on hand so I may
give it a try . If you wish to experiment with the azo-clathrates ,
you will find that a modification of the patents method gives better yields
and results . First form the basic lead picrate / lead nitrate double salt ,
then add any other constituent lead salts to form the parent clathrate ,
and then very very slowly , introduce the azide to its saturation limit .

I haven't tried introducing any silver compounds in the azo-clathrate ,
nor can I conceive what would be the purpose of introducing silver .
So far I have only worked with several of the lead containing complexes .

[pdb]

I hope that explains the term "unequivocality" as I have used it .

OK, I can capture now what "unequivocality" means for you, although I hardly see the connection with the linguistic root (it is a critic of my own lack of knowledge).

The observation which I have made is that even lead azide does not demonstrate single crystal unequivocality to high order detonate , but does show unequivocality in single crystal amounts to low order detonate .

Me too, I have noticed a transition with a blue flame (I think) in some instances. But, regarding the detonation order, what about lead azide long needles you can obtain by superposing 3 solutions (Pb nitrate, Na nitrate, Na azide) and letting diffusion do its task, although they will detonate spontaneously if left in the solution beyond a certain size: how would you call their detonation regime ?

The same characteristic increase in output from a low order detonation to a high order detonation is a general rule in my experiments for many explosives , primary explosives and also for secondary explosives .

Yes, best illustration is nitroglycerin. But in my opinion, it differs from what one can observe with primaries. If for instance you ignite a column of Hg fulminate loaded in a tube, you will observe a jump from deflagration to detonation after a short distance: in this case, would you call deflagration "low order detonation" or would you claim there are really two detonation regimes (which I didn't observe).

The rapidity of the acceleration from low order to high order, can more than "make up the difference" in a composition, where the operative factor is what is the performance of the whole "pellet" of the initiator in tandem with the base charge . The unequivocality of the primary is therefore not at all the most important concern in a conventional sized or a large sized detonator .
Fully agree with that.

Only in a microdetonator , where the size constraint is a factor ,
would there be a need to "nitpick" concerning how many milligrams
of which primary is "better" for that use .

Fully agree again.

To explain some of my previous questions, I have to say that my interest is twofold: on the one hand, I need to make safe and reliable detonators, and DDT is certainly not the criteria I use to pick up the primary (unless the latter is incredibly difficult and/or costly to prepare). I would use dextrinated lead azide or DDNP until I met DPNA (see 1st post in this thread), which I particularly like because of its remarkable initiating power (<5mg for PETN). On the other hand, I am quite fascinated by the capability of some primaries to detonate in the tiniest amounts in the open air –it's just a "game", no practical application is sought. I would cite Ag fulminate (but I stopped "playing" with it after numerous accidents), Ag acetylyde, DPNA etc… However, in spite of the documentation I have gathered along the years, I didn't find much about detonation mechanism of micro charges. I tried to launch a thread about it months ago, I failed:

http://www.roguesci.org/theforum/showthread.php?t=3191

The general method for some of the variants of the azo-clathrates is
described by the patents .

I am sorry, I hadn't read yet the patents issues by Mr. Kennedy previously to its '1969 one before asking you.

To form the chlorate variant which I mentioned requires changing the proportions of the precursors accordingly , and the chlorate is derived from sodium chlorate or potassium chlorate in reaction with the corresponding equivalent of added lead nitrate to the system , which results in lead chlorate forming in solution .

Yes but it you make the synthesis with this mixture, which ion would prevail ? What about the risk of a mutual contamination in such a complex structure as a clathrate ?

When you have a microscopic examination of crystalline material that is uniform through the sample , crystals that are "clean" and consistent in appearance and do not change color or granulation over time , it is a "pretty good" confirmation . Add other factors like no change in weight over time , no development of odor or other observed physical change , and it is sufficient for reasonable certainty that you actually do have what you think you've probably got .

Mmm… yes, I can understand you cannot go further in absence of spectography equipment, and your confirmation is certainly sufficient as regards to practical use of the compound. However, have you tried to prepare 4/12 with an excess of lead and azide in order to voluntarily contaminate the compound, to check if you could really detect it through the means you mentioned ?

The perchlorate would probably be more stable and have a better oxygen balance , so it is a good idea . I have some ammonium perchlorate on hand so I may give it a try .

I have perchloric acid.

I haven't tried introducing any silver compounds in the azo-clathrate , nor can I conceive what would be the purpose of introducing silver .So far I have only worked with several of the lead containing complexes .

My suggestion just comes from the "tradition", which is that when experimenting any primary with a heavy metal ion, one would try other heavy metals of the traditionnal family (Ag, Pb, Hg, Cu & more exotic ones).

[Rosco Bodine]

The root word "unequivocal" describes a definitive status about anything
which is absolutely free from any uncertainty or ambiguity .
In my experience , I searched for a word which would seem correct
for describing scenarios involving primary explosives which progress
to *high order* detonation even in very small quantities which are
in the range of a few tens of milligrams .

Applying that standard , silver fulminate is an unequivocal primary ,
but mercury fulminate is not . Neither are lead styphnate nor
basic lead picrate unequivocal primaries , even though they do
undergo DDT in milligram amounts , the detonation is low order
and incapable of shock initiating most secondary high explosives .

When I think of unequivocal primaries , I am speaking of the sorts
of materials where a small pellet in the range of a few tens of milligrams
will high order detonate , particularly if unconfined , and will
demonstrate its velocity with an ability to cleanly cut a clear
opening in a thin aluminum witness plate . A charge half the
size of a BB which shows metal cutting brisance when flame
initiated , is in my estimation and comparisons with many energetic
materials , an "unequivocal primary explosive" , unequivocal meaning
there's no *ifs* , *ands* , or *buts* about the material ....
it is for damn sure explosive :)

Yes there are two detonation regimes for many if not most explosives .
I don't just claim that to be true , but declare it is a certain fact
also observed by many others and confirmed by many tests on
many explosives . If a flammable explosive is ignited , and a sufficient
amount of the material is present in the correct shape and with the
right amount of confinement , the ignition will be followed by a deflagration
accellerating to detonation . The first evidence of detonation may be
a low order detonation , particulaly common for a flame initiated ignition ,
and then that low order detonation can further accelerate to a higher
velocity "high order detonation" . So from ignition to high order detonation
involves four steps . For the steps to be completed , there must be present
a certain "crititcal mass" of the explosive , in a geometry which is also
favorable in regards to "critical diameter" . Density and crystalline form
are also factors . Density continuity , entrapped air , particle size ,
matrix geometry for mixtures , are other factors which have effect also .
Depending upon what combination of factors is present and the nature
of the initial stimulus which applies to that zone in the firing train ,
the behavior of the detonation can vary . For example , even though
some primaries are flame sensitive , the amount of primary required can be
reduced if it is not required to function as its own igniter , but is initiated by the
low order DDT detonation impulse from a flash igniter like lead styphnate
or basic lead picrate . In such a scenario , the primary does not need to
first ignite , then deflagrate and accellerate through two levels of detonation ,
because the flash igniter functions as a "hammer" which brings the primary
to immediate high order detonation , releasing its entire energy most
efficiently . A good flash igniter can make a primary which is not unequivocal
function as if it were , and can even bring some sensitive base charges
to high order detonation , without the presence of any conventional primary
being required . There are different ways which detonators can be designed
to function to exploit the properties of the materials used .

Regarding the azo-clathrates . I already answered your question about
the ion-exchange . Please study the patents including the earlier patents
regarding the non azide clathrates . The patents and some experiments
will explain it better than I can .

To answer your question about over-saturating the clathrate with lead azide ,
yes I have deliberately done that to see what would happen .
The excess lead azide forms a dusty co-precipitate which coats and mixes
with the crystals of the azo-clathrate . The free lead azide is lighter in color
and is visible as a contaminant mixed with the crystals . The free lead azide
also demonstrates its presence with gradual color change and darkening ,
over time for the sample exposed to the air . It is these observations
which serve as a visual indicator for approximately what is the saturation
limit of azide for a particular clathrate . If a synthesis is attempted and
there is evidence of oversaturation with azide , then the quantity of azide
should be reduced incrementally in subsequent syntheses until a level
of azide is reached where a clean crystalline product is obtained .

[pdb]

Well noted.

However, a mystery remains as to how an tiny amount of loose unequivocal primary (=not deliberately shaped as to make a pellet) can detonate with enough brisance to cut a thin metal sheet. The transition from low order to highr order detonation in a cylinder of HE is well known and explained in the literature, but it is a completely different phenomena: one can hardly see how a shockwave would propagate in a loose powder. And if one concludes that it is the result of successive ignitions of crystals by the crystals nearby, it doesn't explain the brisance observed (which is not a result of generated gas or dilatation of air, as silver acetylyde shows when exploding in vacuum).

Coming back to beloved clathrates, when you see the way followed by the successive patents, you may wonder which conditions are required to "build" such compounds, and, in the case of picrates, if, after adding another compound (lead azide) to the double salts, you can imagine doing so with another compound. In short, with 4/17, have we reached the limit where the structure cannot host another molecule of an already contained product or a new one ?

[Rosco Bodine]

The many possible factors involved in explaining detonation
have not been fully explained , that is for sure . Some theories
of my own include infrared transparency of the molecules allowing
multipoint simultaneous chain reaction propogation , reenforced
by the local gravity wave anomaly attendant to the mass changes
that are occuring from electron orbital jumps and photon emission .
There are also the supersonic shock waves which contribute
energy as they travel through a maelstrom of density changes
occuring in the material .

There may be some mathematical way to calculate exactly how many
of what specific molecules can be put together to form a stable clathrate ,
but the only way I have approached the synthesis is by trial and error .
The crystal geometry for a particular clathrate establishes a size limit
for the molecules it may adsorb , so indeed there is a mathematical rule
which governs a particular clathrate in how many of what sized molecules
it may adsorb . To write the equation which applies is beyond my knowledge .

[pdb]

Rosco Bodine, I happened to come across the following document while searching the Web for studies about detonics of micro-charges:

http://www.ceres.ifs.tohoku.ac.jp/~coe/mizukaki13c.pdf

It is not that valuable, but such studies seem to be so rare that they become noticeable !

[pdb]

Rosco Bodine, just to make you aware that I observed my first prepared clathrate with a microscop, and found out it was composed of tiny needles, some of them bright yellow, the other withe... It obviously not a clathrate but only an intimate mix of basic picrate and azide. I must confess I had lots of problems with the heating part of my stirrer, which prevented me from keeping temperature stable. I will redo once I have fixed this f... stirrer.

[Rosco Bodine]

The two essentials are accurately measured weights of precursors ,
especially the picric acid and sodium hydroxide , and *very* slow
constant rate , dropwise additions with good agitation , sufficient
to keep the crystals in suspension and not permit them to settle
and accumulate on the bottom of the beaker . You have to have
a good vortex in a tall form beaker , or use a propellor type stirrer
to achieve the good agitation required . You *may* be able to salvage
the batch by diluting it with water , or even better using the filtered
solution if you saved it , and just letting the suspension stir near the
boiling point for two or three hours , adding any makeup water
from time to time for evaporation losses . The reaction has to be
run near the boiling point with slow additions and good agitation
because of the very low solubility of the intermediate and even lower
solubility of the end product . Don't be discouraged or give up .
The process absolutely works and has been confirmed and reconfirmed
by myself and others .

Which clathrate variant did you attempt ?

Did you use the patent process or the modified method ?

[Rosco Bodine]

I must confess I had lots of problems with the heating part of my stirrer, which prevented me from keeping temperature stable. I will redo once I have fixed this f... stirrer.

If your stirplate has one of those percentage on/off type "rate controllers"
like on Thermolyne , Cimarec , and some others , maybe a Robertshaw controls
device , IIRC . They have a bimetal strip in the circuit which warms
up as it carries current and breaks the heating circuit through a pair of
silver button contacts , remaking the circuit on cooling just like the
flasher module in an automotive turn signal circuit . The control knob
simply increases the tension opposing the bimetal opening the contacts
so it has to get hotter , conducting current longer before it pops the
contacts open . Usually the problem is that the slight arcing of the
contacts erodes the contacts and widens the gap over time . Such
controls can be overhauled if you have the patience and skill .
Remove the knob and loosen the retaining nut underneath , disconnect
the wires and remove the control from the stirplate housing .
You can carefully pry apart the sheet metal prongs that retain the
bakelite control housing and get to the silver contacts inside to dress
them with a point file or a folded narrow strip of 220 grit sandpaper .
There should be a very light contact pressure when the control shaft
is rotated to the lowest setting of the "ON" range , and the contacts pop
open when cammed apart as the shaft turns to the "OFF" position .
You may have to slightly bend the bimetal strip to adjust for the new
gap after you clean the contacts , to get proper operation . It takes
maybe thirty minutes to overhaul one of these rate controllers if that
is the type you have .

P.S. There is a little spring inside IIRC , so you may want to put a baggie
around the switch to catch it when you slowly separate the housing ,
to spare yourself the proverbial "jack in the box" / now where did that spring
go sort of fiasco , that otherwise is guaranteed :D

[pdb]

Rosco Bodine; thanks for your tips about me stirrer. However, I need to replace it.

Which clathrate variant did you attempt ?

Did you use the patent process or the modified method ?

It was the 4/12 flavour with your improved method.

For sure, I will not discourage because my interest is sharp. But it will take some time... and I may not come back on this subject before some time. ;)

[Bert]

adding any makeup water
from time to time for evaporation losses .

As described by Mr. Anonymous, this procedure would take over 3 hours at near boiling temperatures. What would be a good level to maintain the "makeup water" at during this synthesis? Somewheres near the original 140 ml ???

[nbk2000]

Well there's definitaly need for primaries of such potency, as some things I'm reading about use primary charges on the order of a few milligrams for setting of the base charges of follow-through grenades and other modern munitions.

Tiny primaries are more robust to shock loading than larger charges, meaning more likely to survive slamming through a concrete wall long enough to explode inside the room, rather than outside or in the wall itself.

Tiny primary charges would also be desirable for shotgun grenades loaded with an IM explosive, to make them safer to fire, while still be reliable.

Too bad MEM's are out of reach (for now) of the "common" folk 'cause then we'd have all the fixings for microfuzes. :)

[Totally Off Topic]
Things with springs should be opened inside of a pillow case to prevent the "disappearing spring" trick. ;)

Speaking of measuring tiny things, I've obtained an OHAUS triple-beam scale, with .1 gram resolution, at a garage sale for cheapcheap.

However, the thing has a problem of sticking. :(

I haven't disassembled it yet, but it feels like the pivot is rusty or something like that, and keeping the beam assembly from freely moving.

Think this is something fixable, or are the tolerances such that it's hosed?
[/Totally Off Topic]

[Bert]

I've obtained an OHAUS triple-beam scale, with .1 gram resolution, at a garage sale for cheapcheap.

However, the thing has a problem of sticking. :(

I haven't disassembled it yet, but it feels like the pivot is rusty or something like that, and keeping the beam assembly from freely moving.
[/Totally Off Topic]

The pivot is likely dirty, or possibly corroded/bent from improper handling/storage. Careful dissassembly and probably a cleaning are in order, it isn't difficult. Carefully lift off the little silver covers on either side of the ballance point with a sharp instrument and take a look- (SHIT! I just found a dead fly in mine looking to see how!) If you need a new pivot assembly, Ohaus distributors can provide these.

[Bert]

You *may* be able to salvage
the batch by diluting it with water , or even better using the filtered
solution if you saved it , and just letting the suspension stir near the
boiling point for two or three hours , adding any makeup water
from time to time for evaporation losses .

Has this technique of salvageing a batch been shown to be effective, or is this a proposed experiment?

[Rosco Bodine]

As described by Mr. Anonymous, this procedure
would take over 3 hours at near boiling temperatures.
What would be a good level to maintain the "makeup water"
at during this synthesis? Somewheres near the original 140 ml ???

The total water in the combined solutions was 370 ml ,
so where are you getting your figure ?

[Rosco Bodine]

Has this technique of salvageing a batch
been shown to be effective, or is this a proposed experiment?

It is a logical proposed method of attempting to salvage the batch ,
since the clathrate is the least soluble material , it would probably
be the purified precipitate which would result from long stirring of
a suspension of its precursors which are more soluble and would
gradually dissolve , then precipitate as the clathrate complex .

In a way it is simply a continuation of the process which should
have originally gone to completion to form the clathrate , but
failed because of too rapid additions or inadequate agitation or
temperature . I have never had a batch go wrong , so there
has been no need to test such a method for driving to completion
an unfinished reaction . The salvage idea was simply a logical
proposed remedy worth trying .

[Bert]

The total water in the combined solutions was 370 ml ,
so where are you getting your figure ?
The initial Lead nitrate solution that all the other solutions are added to is 100 ml. I screwed up, I meant 100 ml.

I have never had a batch go wrong , so there
has been no need to test such a method for driving to completion
an unfinished reaction . The salvage idea was simply a logical
proposed remedy worth trying .

Fair enough- I wish I never had a process go bad!

As the reaction kinetics favor the desired product under the near boiling temp/rapid agitation it would seem like a good guess...

It would be desirable to attempt to recreate the original solution conditions if one had allready discarded the supernatant liquid? And the discarded solution after the reaction is mostly Sodium nitrate and a bit of Lead nitrate? Also, it would seem to be possible to just heat longer and stir harder to correct the procedure if one had realized a batch had gone astray before one had filtered it?

[Rosco Bodine]

The low solubilities of the intermediate and end product
requires special technique to be followed and there is no
way to hurry the process , it's just the nature of the
reaction kinetics to take time and high temperature for
the reactions to run to completion . More dilute solutions
might go a bit faster but will also produce larger crystals ,
so you can vary the conditions within reason to fine tune
the process to your liking .

So ,

With additions do go slowly ,
and keep the cauldron hot ,
while stirring not just a little ,
but for sure one hell of a lot :D

To be sure it's best to do it right the first time
than to try to backtrack and estimate how to
patch a reaction gone wrong . Yes it is possible
to observe the reaction and interrupt an addition
if the reaction is lagging , getting too thick to stir
well for example . Let it heat and stir awhile until
the mixture loosens up and then resume the addition .
Add a little water with an eyedropper or wash bottle
to do any "housekeeping" concerning crusted material
if needed . But really you guys seem to be making
a bigger deal of the details than necessary . The
process is really quite simple and straightforward as
organic syntheses go . Unless you do really sloppy
work it is difficult to botch this synthesis .

[freaky_frank]

My favorite is still AP just be carefull with it...easy to produce, cheap....and well it is dangerous as all primairy's exept this one, is crap because it isn't storeable for long but b/c it's so easy to make you just make some more again :)
And well I'm not allowed to make explosives from my parents, so it would actually be easier "to have some primairy lying around"...

[Bert]

The
process is really quite simple and straightforward as
organic syntheses go . Unless you do really sloppy
work it is difficult to botch this synthesis .

It's a little harder than making AP. But the results speak for themselves.
Witness plates are .020" T-1 (soft) Aluminum, 4" X 4" squares.

[nbk2000]

People always expect superior results from inferior performance.

In other words, if you want the best results, you have to put in the work.

There's nothing wrong with AP, as it is simple and easy to make, but if you want high performance in a small package, you'll have to put in that extra effort.

Besides, while standing in the line at the school cafeteria, you can totally trump the k3wLz bragging about their AP making skills when you bust out with the azo-clathrate microdets you make that are small enough to fit several on a dime. :p

[Mr Cool]

Hello :).

This seems like a good place to ask... I'm just wondering if anyone has any good info on tetrazole-based primaries? I have rather a large amount of 5-aminoT., not much to do with it though! The nitrate salt is fun, the complex formed with silver nitrate (and other transition metal oxosalts) is OK, but I'm sure this stuff has more potential. Ditetrazolyltriazine is surprisingly reluctant to detonate fully (just little "crack!" noises, and the grain hops around), and diazotetrazole is just scary.

All searches that I've been doing either result in something totally irrelevant, or formulations for non-azide gas generators...

So, anyone have patent numbers that they could direct me to? Preferably things that I can make from 5-aminoT., but I'm interested in any. I may be able to find a way to convert it. A way of making 5-nitroT. would be good...

Thanks :).

This has reminded me, I must try out some clathrates one day...

[Rosco Bodine]

GB185555
US1511771

GB195344

GB1069440
US3310569

[Mr Cool]

Thanks for those Rosco. I'll be trying a few out soon! I had a go at making azotetrazole today. I didn't have any permanganate to hand, so had a go at oxidation with acidified dichromate, but no luck :(. I'll get a little permanganate from the chemist's and play around a bit more. Not sure if to use it basified or acidified, but some experimentation should help there.

Well, I have good news!! Good news for me anyway, having lots of 5-aminotetrazole...

After using a better patent search engine, which I had until recently forgotten about (www.espacenet.net), I have discovered the process for producing the copper salt of 5-nitrotetrazole (and other salts therefrom) in >80% yield, using 5-aminotetrazole and sodium nitrite via the Sandmeyer reaction! It's so simple!

For anyone that might be interested, relevant patent numbers are:

US4552598
US4094879
US4093623
US2066954
GB1519796

The figures given in one patent indicate that silver nitrotetrazole is 4 times as effective at initiating tetryl than lead azide. Basic lead nitrotetrazole is as effective as lead azide, and the mercury salt is only a little less effective than the silver salt.

I still have some reading to do to get more information as to stability, but everything looks promising! I believe it was in one of the patents that Rosco posted that I read that tetrazole based explosives were "remarkably stable" (or words to that effect), but then again, they would say that...

Well, it's late now (even later than it should be because we put our clocks forward today. Or does that mean that it used to be earlier than it should be? Who cares, the effect is the same. I'll stop talking now), so no experimenting today, but tomorrow I should have some results. Unfortunately copper sulphate is one of those "boring" chemicals that I never think of as useful, so I'm not sure if I have any, but I'm sure I can find some somewhere...

[Mr Cool]

It seems that there is no OTC copper sulphate around here, so I'm going to have to make some. How mind-numbingly tedious :(.
Anyway, with luck I should have some CuNT by the end of the day!

(Sorry, my juvenile mind made me use that abbreviation...)

[Bert]

Copper sulphate is available as an algaecide frequently- Ask at a garden store that sells stuff for ornamental ponds.

[Rosco Bodine]

Copper Sulfate pentahydrate crystals are also sold by the pound
as a root killer for septic tank drainfield lines . You can get it in
plastic bottles at hardware stores .

[Mr Cool]

I looked high and low, far and wide for algaecides, but to no avail. The best I could do was Cheshunt compound to prevent damping off of seedlings. But it's only 15% copper sulphate, the remainder being ammonium carbonate, and no way was I paying almost £5 for 250g!
I could have gone out of town to a larger garden centre, but that would have taken longer than making it - which I have now done...

[pdb]

Years ago, CuSO4.8H2O was used to give a nice blue color to swimming pools. Who knows ? You can give a try...

It used also to be sprayed on grape plants so as to protect them from some insects. But I guess they now use much more specific and sophisticated mixtures...

[Mr Cool]

Well, nitrotetrazole is potent to say the least!

I've just finished making a little of the acid copper salt. The reaction went without a hitch, and with some lovelly colours due to the various copper complexes formed at different stages. I can't say what the yield was, for the amounts I used were very small and impossible for me to measure accurately, but it looked OK. I'll make a larger batch at some point and find the yield.
It's currently in aqueous solution, on thursday (I'm going on a little trip tomorrow) I'm going to convert it to the sodium salt and do some experimenting with various compounds... It's my hope that the sodium salt will be suitable as a way to store it, in strong aqueous solution, so that other salts can be prepared as desired.
And at some point I'll do a few witness plate comparisons and post some pics...

[Rosco Bodine]

Let me make sure I understand correctly what you have reported .

After a cautious procedure on a small scale you were rewarded at
the end of the day with a small amount of wet CuNT . :D

And being well pleased with that result , you now propose
to enlarge the scale of your endeavor ,
excited at the prospect of getting increased amounts of wet CuNT ;)

Well , there's no doubt that you are on a promising course for a "favorite" !

ROFLMAO !!!!

[Mr Cool]

Further tests will be delayed - I stayed away longer than expected, and am hung over :(.

That's about right Rosco! I'm really gonna have to convert it to the sodium salt... this is a respectable place, you know! I'm sure there's a rule about not detailing experiences with lots of fresh wet CuNT... and I'm sure it would be illegal to post pictures of it, it's only a few days old! :eek:

[Mr Cool]

Right, I'm just about to try a larger batch. The method used will be taken from Example 6 in US4093623, scaled down to use 20g of copper sulphate (all that I have left :().
The error in my yield calculation will still be larger than I would like, but at least I'll have enough product to do something useful with.

[Mr Cool]

Right... I'm kinda half way through making it.
I accidentally used 100mL too much water in the nitrite/copper sulphate solution because I couldn't read my writing... the result was the the solution was too weak, making the CuNT ppte in the more gel-like, rather than crystalline form (read the patent, it seems stronger solutions make a better product). It's not too bad, but it did make the mixture very thick. This fact, coupled with the effervescence, resulted in gloopy wet CuNT going everywhere...

[Mr Cool]

It's being a real pain in the arse to get dry. I've been recrystalising like mad, not to get it pure, but in an attempt to get it into a nice crystalline form. I've tried various things, but the best I can do is to get it into a coarse paste, which holds lots of water between the crystals. So it is still very moist.
Another strange thing is, the crude product was pale blue/green, and gave a pale blue/green solution, and the recrystalised stuff is sky blue, and gives a sky blue solution :confused:. I'm not sure what change has taken place, but the recrystalised stuff certainly seems more like what is described in the patents. Have a look at the attached pic - the one on the left is the crude product, after being washed a few times, in dH2O. On the right is a sample of that crude product, after recrystalisation and washing, also in dH2O.
There was a small amount of gas evolution during recrystalisation (which was done using a water bath for heating, so was probably at around 80*C), I'm not sure if it was the product or impurities, but either way there was not enough decomposition to account for the colour change of the whole batch.

Also, I've been wondering about lead double salts... I've always been wanting a castable primary, or at least a primary which softens at higher temperatures, in order to make loading easier. Not much pressure would be needed, and it would set into a nice solid block. The thought came to me of using a lead double salt, in which one anion was that of a "normal" primary explosive, like azide, nitrotetrazolate etc, and the other was that of an oxidiser, eg chlorate, nitrate, perchlorate. Then this excess oxygen could be used to oxidise a binder, eg MNN, a nitrotoluene etc.
Just out of interest I worked out what proportions would be needed in order to create a mixture of lead nitrotetrazole chlorate and mononitronapthalene that was more or less oxygen balanced to CO and H2O. The result was 87.5% Pb(NT)(ClO3) and 12.5% MNN - more or less perfect proportions to give a nicely bound product.
Has anyone here tried this sort of thing? Do you think it would work? I have a suspicion that the binder would take away a lot of the primary's initiating capability, but I think it would be worth looking into...

[Rosco Bodine]

Lead Azide can be used as a filler in melt cast ETN ,
and it is a powerful mixture . There is probably a
better combination of nitroesters which could have
a stiff but gummy consistency upon hardeneing .
Maybe a combination of nitrolactose , ETN , and
a small amount of sorbitan tetranitrate would form
a decent energetic binder . Nitrocellulose or cordite
might be useful as an additive also .

Here's a patent reference for the tetranitrate of sorbitan ( not sorbitol )

GB924239

[Mr Cool]

Finally I got it dry. The yield was 30g, around 75%. Not at all bad considering I had that little spillage.
Here's that pic showing the colour change. Also attached is a pic of the dry yield, a saturated solution of the copper salt (from which it was recrystalised), and a photo of the copper salt in 150mL dH2O mixed with 8g of NaOH in 50mL of dH2O, in order to prepare the sodium salt. Unfortunately kitchen towels don't work very well for filtering out very fine CuO...

[Bert]

Have any of you used one of these constant addition funnels? (http://www.kimble-kontes.com/html/pg-299350.html) They are hideously expensive, but might be just the thing for a couple of procedures mentioned here. If you've used one, how reliable/durable are they?

[pdb]

I once had one, but I broke it during cleaning... and since I have been using a simple buret with a Teflon tape without problem. I think the expense is not worth the advantage of fixing the flow rate: do you often leave your apparatus unattented ??!

[Bert]

I have been using a simple buret with a Teflon tape without problem. I think the expense is not worth the advantage of fixing the flow rate: do you often leave your apparatus unattented ??!

How exactly are you using the combination of Teflon tape and a buret? I have tried Roscoe's idea of nicking the edges of the stop cock's plug on a standard dropping funnel, it works but the flow rate doesn't stay constant as the level of liquid changes.
(edit: pdb says he meant a Teflon TAP, as in a Teflon valve)

I can't leave such operations unattended. But I'd like to at least be able to
turn my back on them for a couple of minutes!

That aparatus did look very breakable, and hard to clean due to those thin glass equalizing lines. Plus it costs more than my entire glass inventory put together.

[Microtek]

I don't think it is critical to hold the rate of addition constant as long as it doesn't get too high. As drip rate will diminish as the liquid level drops, I don't think you have a problem.

[Rosco Bodine]

I don't think it is critical to hold the rate of addition constant as long as it doesn't get too high.
As drip rate will diminish as the liquid level drops, I don't think you have a problem.

Microtek is correct . It is not really critical for the addition rate to remain
exactly constant , and it is fine to make the initial drip rate adjustment on a
pear shaped addition funnel , and let the addition rate follow its usual
natural decrease as the liquid level in the funnel falls . A tall column
of liquid in a buret would have a significant rate change , but the addition
rate change is not any problem for a pear shaped funnel .

A magnetic stirrer hotplate and addition funnel is not even absolutely
required . The first time I made an azo-clathrate , it was made in a
jelly jar sitting in an inch of hot cooking oil in a small electric cooking
fryer having an adjustable thermostat . The stirrer shaft I used was a
section of an old hollow fiberglass arrow with the three plastic vanes ,
extending the shaft of a C-frame shaded pole fan motor which was
speed controlled by a lamp dimmer . I made a mounting bracket and
adjustable height support rod for the stir motor , from 3/8" water pipe
and a floor flange screwed to the top of a workbench . The additions
were made three or four drops at a time using an eyedropper , but
an old intravaneous solution bag and delivery tube would have saved
labor . Small plastic needle valves which fit aquarium tubing could
also be useful for an improvised addition funnel , using a turkey basting
syringe body as a reservoir , or even a small plastic squeeze bottle
having a dispenser tip .

Proper lab equipment makes things easier for having the right tools
for the job , but expensive equipment is not essential for a resourceful
person handy at improvising . So long as the reaction conditions are
met , the end product is exactly the same .

[Bert]

==========================<snip>=====================
an old intravaneous solution bag and delivery tube would have saved
labor .
==========================<snip>=====================
Proper lab equipment makes things easier for having the right tools
for the job , but expensive equipment is not essential for a resourceful
person handy at improvising . So long as the reaction conditions are
met , the end product is exactly the same .

Thanks, I thought of the disposable intravenous drip myself, and have a couple of contacts in the medical field who're going to grab a sample for me to play with.

Proper equipment is very nice... But a bit pricey, as I've found. A resource of interest to the cash strapped may be Lab X (http://www.labx.com/) Kind of like eBay, but for lab equipment only. I admit it, I'm a "tool freak". If I know how to use it, I want to have it available.

[Microtek]

Having looked at some of the tetrazole patants, I decided to try out some of the compounds. It seems like a very rich avenue of experimentation and while I agree with Rosco that the azo-clathrates are sufficient for most practical applications, practicality has never been my primary concern.

As my lab supplier doesn't sell tetrazoles I decided to try out the route over aminoguanidine which Mr Cool mentioned in the 5-ATZ thread.
So I ordered a few hundred grams of aminoguanidinium bicarbonate:

- 6.45 g aminoguanidinium bicarbonate was suspended in 7 mL H2O and neutralized with 5 mL 30 % HCl ( dropwise addition although it cooled down rather a lot during addition ).

- pH was checked with universal indicator strips and adjusted to ca pH 4.

- Another 5.3 mL 30 % HCl was added all at once.

- A soln of 3.5 g NaNO2 in 7.5 mL H2O was added from an addition funnel while stirring vigorously and keeping temp at 17-20 C with an ice bath ( no salt ). Addition proceeded smoothly with negligible evolution of NOx ( not visible and only just detectable by smell ) until the very last drops which gave the evolution of NOx which is typical of nitrite with acid. This likely signified that all the aminoguanidine had been diazotized.

- Stirring was continued for 20 minutes at 20 C after addition was completed.

- 4.9 mL 25 % ammonia soln was added all at once ( pH was measured at this point and was found to be ca 6-7 ), the flask was equipped with a condenser and the mix was heated to beginning reflux. It was held there for 2 hours.

- While still hot, pH was adjusted to ca 4 with HCl and ammonia water; ca 1.8 mL 30 % HCl was required.

- Mix was allowed to cool very slowly by turning off the hotplate but letting the flask stay on it. Once it had cooled to room temp, it was placed in the refridgerator until a temp of 10 C had been reached.
The product crystallized in very well defined plates beginning from ca 40 C.

- Almost all the mother liquor was easily decanted from the dense crystal mass, and 12 mL of H2O was added to remove co-precipitated chloride.

- Mix was heated to 45 C with stirring and was then allowed to cool to 10 C.
Not all of the product was dissolved in this operation.

- Product was removed by filtration and washed several times in the filter with cool water.

Yield was 4.96 g 5-ATZ*H2O or 99 % theory if 100 % purity is assumed.

I then converted 2.57 g of the 5-ATZ to nitrotetrazole using a virtually identical procedure to the one Mr Cool used. The reaction went very smoothly, and produced a large amount of pale green product in suspension. It was reasonably easy to filter most of the mother liquor off, but a lot of liquid did remain trapped. The product exhibits great differences in solubility at high and low temperature so recrystallization was easy and left a pale but clear blue precipitate.
I believe that the green colour may come from a residue of copper nitrite complex of some kind. The decomposition of this could possibly be responsible for the fizzing observed when recrystallizing.
Some of the product ( I tested both before and after recrystallisation; there is no difference ) was dissolved in hot, slightly acidic ( from HNO3 ) water and a soln of AgNO3 was added. Immediately white, amorphous precipitate appeared and was allowed to settle. It was filtered and washed and allowed to dry.

In the dry state silver nitrotetrazolate ( SNT ) is a very slightly off-white colour. It is responsive to flame from which it detonates with an even sharper and louder crack than lead azide.
It is somewhat sensitive to impact, a little more so than NG.
A sample of SNT was exposed to direct, strong sunlight for ca. 5 hours. No colour change or change in properties was observed.
A sample was placed on my hotplate which was turned full on ( it doesn't get so hot; it's a converted iron for ironing shirts etc. A thermometer placed on the surface shows a temp of 140 C ) and left for 20 minutes.
This caused the colour to darken somewhat and there may have been a slight weight loss, but there was no reduction in brisance of the sample.

All in all, I'd say that nitrotetrazolates are very promising primaries due to the easy of manufacture and the chemical stability due to NTZ being a very strong acid ( pKa = -0.82 , comparable to nitric acid ) with a low volatility unlike HN3. So no need to worry about toxic gas...

[Mr Cool]

Good work!

I like the sound of your method, avoiding the sodium salt. It's ridiculously annoying trying to recrystalise it. You have to chill the solution to get crystal formation, and without the ability to vacuum filter, most of the crystals dissolve in the liquid which they held between them as they warm up.
IIRC I left all of the sodium salt dissolved in about 20mL of water...

Yes, NTZ is a very strong acid - it's basically just one huge pi system made up of mainly very electronegative atoms, so the charge can be favourably delocalised all over the place.
Interestingly, the free acid has apparently been known to detonate spontaneously (at around 8.8 km/sec!).

[Rosco Bodine]

That is an interesting route to tetrazoles which has adaptability
to use of OTC starting materials , though it would involve several
synthetic steps from urea as the starting material . The tetracene
intermediate has interest itself , along with its perchlorate and
heavy metal salts .

Urea heated with silica gel leads to cyanamide . GB718934
Calcium cyanurate ( lime plus pool chlorine stabilizer )
on heating also leads to cyanamide . US3173755

Cyanamide reacted with hydrazine sulphate ( from urea plus pool chlorinator )
produces aminoguanidine which can be diazotized with
sodium nitrite ( meat preservative ) to tetracene . GB308179

For someone determined to use the most basic starting materials ,
such a route to tetracene and tetrazoles is workable without requiring
any ordered chemicals .

[Microtek]

I have recently prepared the cobalt salt of NTZ, just to see what that was like.
A small amount of NaNT was dissolved in water and added to a concentrated soln of CoCl2 in water. I found that concentrated solutions are necessary to get the CoNT to precipitate fast; dilute solns only give precipitate after some time.
The precipitate was ridiculously fine and took hours to settle. None of my lab grade filter papers stood a chance of filtering it out, so I had to construct a centrifuge to help me remove the NaCl byproduct and then dry the product directly.
CoNT is quite similar to SNT but slightly more reddish in colour. It is somewhat less sensitive to impact than SNT but about as responsive to flame. I haven't done any initiation efficiency tests yet.

[Rosco Bodine]

Might be worthwhile to look at the lead , cadmium , and barium
salts too .

[Microtek]

From reading Herz's old patent, it seems that the basic lead salt of NTZ is rather less attractive than the other heavy metal salts.
It seems to suffer from relatively high solubility and is less powerful than the silver salt. Of course, there may be sensitivity advantages but considering that CoNT is described as "practically insoluble" and PbNT*Pb(OH)2 as "difficultly soluble" and that I did have some of the CoNT redissolve when washing, it's a bit down my list at the moment.
I'll be trying the mercury salt though....

[Rosco Bodine]

The silver salt is probably the best of the bunch .
It is especially nice that the silver NTZ is not photosensitive .
That resolves a real gripe that applies with fulminate and
azide compounds of silver , and many other silver salts as well .
It would seem that if you are going to the expense of using
a silver compound as an initiator , that silver NTZ is a far
more justified use of silver than the alternatives .

Of the rest , nickel NTZ may be good too . For the
purpose of causing crystal modifications which
could have benefits , it may be possible to make
a mixed crystal or double salt of the silver and nickel
compounds . Other combinations of the NTZ salts
with each other , and double salts with other compounds
like styphnates could produce interesting materials .
Possibly , even a series of clathrates could arise ,
having NTZ internal components analogous to the azide
based clathrates . The performance of any such materials
would likely be very high in comparison with the better known
and more usual initiators .

It seems curious that there isn't much more published about the
NTZ based primary explosives , since the little that is published
indicates that the NTZ based primaries would likely offer
the highest performance and also have the stability required
for practical use . Economics alone is perhaps the reason
why mass production favors azide and lead based materials
for common articles of manufacture , and limits the use
of the NTZ compositions to "special" applications , probably
for mostly high end military ordnance where the economics
are not an issue .

[Microtek]

I agree that it seems odd that this class of compounds is apparantly not widely used, especially considering the great chemical stability ( and the photostability of the silver salt; that was the property I was most anxious about ).
However, apart from the economy of lead versus silver, there is also the thermal stability where lead azide outperforms SNT quite soundly.

[Rosco Bodine]

There is another compound which is worth mentioning
in connection with the matter of "exotic" primaries ,
and it is another one of the materials that result from
chemistry involving cyanamide derivatives .

Triaminoguanidine forms a series of stable explosive salts .
The perchlorate is reportedly fuse sensitive .

US2929699

There are many other patents which describe the
manufacture of the triaminoguanidine itself .

[Rosco Bodine]

This thread is one where some interesting discussion was lost
when the forum went down with data loss . I remember some
of the earlier discussion which was most interesting related to a couple
of compounds which are lead double salts involving tetrazole variants
and styphnic acid , which may be superior initiators to lead azide .

PATR vol. 9 page T-121 Lead Diazoaminotetrazolate Styphnate is an
interesting compound .

US2064817 supplies useful information for the precursor to this and related cpds.

US2090745 describes the simple Lead Diazoaminotetrazolate salt

US3310569 Crystalline Double Salt Pb Styphnate and Pb Nitroaminotetrazole
GB1069440 British patent same subject

[meselfs]

Very interesting...

Tetrazoles in general have a pretty high heat of formation, so it's no wonder these salts are pretty effective.

[Rosco Bodine]

Another part of the missing discussion mentioned heavy metal salts of tetracene .

GB412460 Gives details of synthesis

Tetracene is an intermediate in the synthesis of 5-ATZ described by Microtek .

PATR states that tetracene decomposes slowly to 5-ATZ after 3 days at 90 C .

US4024818 Describes a detonating composition useful in ordnance , which is
based upon mercuric-5-nitrotetrazole . The composition is sufficently
powerful that it functions as a single element charge with comparable
output but simplified manufacture over compound detonators having
plural element firing trains .

[The_Duke]

Well I have always stood true and faithful to either MF or HMTD. I like the qualities of both, I really like the fact that HMTD has a VoD of around 6000m/sec. But lately there has been much discussion about DPPP. I think that I might have to try the synthesis for myself first though. Who knows I might find a new favorite primary. :D

[Mr.ANFO]

Yes, I think you will find it very fun to make. DPPP is a yellow-green coloured material derived from Phorone HCl ( made via Acetone and HCl 35-40%)

[The_Rsert]

Is it possible to get 3-nitroaniline from p-nitroanilin?
Because I have acces to some p-nitroailine but not to 3-nitroaniline.

[Mr Cool]

I'd say the product from p-nitro would be less stable than that from m-nitro, since that nitro group will induce a positive charge on the carbon to which the (positive) diazo group is attached...
It *is* possible to convert one to the other, but it would be no easier than starting with something else. Diazotise, replace the diazo group with a chlorine, reduce to nitrobenzene with copper powder in aqueous ethanol, nitrate to dinitrobenzene, reduce one nitro group with a polysulphide, and there is your 3-nitroaniline. Hardly worth it, IMHO.

[The_Rsert]

OK, I see, it's too difficult :(
Is there another use for p-nitroaniline?

[Mr Cool]

Well yes! You can nitrate it further to get trinitroaniline (TNA) and even tetranitroaniline (TetNA). Both are powerful explosives, TetNA can be reacted further, with sodium azide, to get aminodinitrobenzofuroxan, which is powerful, stable and not very sensitive (whereas TetNA is powerful, but chemically reactive/unstable and quite sensitive since it has a nitro in the "wrong place"). TNA is weakly basic because of the amine, and so should form nitrates, perchlorates, picrates etc which should also be useful. And it can be converted to picryl chloride, which is a useful intermediate for all sorts of things...
p-NA is nice stuff to have around!

[The_Rsert]

Thanx!
Is there accurately described way to convert the p-nitroaniline in 3-nitroaniline?
Is there a good primary explosive made of the p-nitroaniline?

[The_Rsert]

Is there a powerful primary explosive, which is insensitiv to flame and friction but sensitiv to flame?
What's about lead2,4,6-trinitro-3-oxybenzoate (http://www.roguesci.org/megalomania/explo/oxybenzoate.html)? Is it powerful?
Because it's easy to prepare and the chemicals are very easy avaible.

[Rosco Bodine]

US3284255

Lead Azide and Barium Styphnate Explosive Initiator Composition
insensitive to impact , but sensitive to flame :D

Maybe this is what you mean ?

[Guerilla]

lead2,4,6-trinitro-3-oxybenzoate (http://www.roguesci.org/megalomania/explo/oxybenzoate.html)? Is it powerful?
Because it's easy to prepare and the chemicals are very easy avaible.

Actually the other main source material in that synth should be trinitro oxybenzoic acid instead of the Na-benzoate (which was affirmed in the old thread about this), making it a less attractive choice for that matter.

[The_Rsert]

This sounds very interesting for me:

"Silver styphnate: This compound is used as an alternative to lead styphnate in primer compounds. It is reported as being superior in performance and stability to lead styphnate, less toxic, but more expensive. It may be prepared by mixing a solution of styphnic acid in ethyl alcohol and adding a small quantity of sodium carbonate. The solution is then acidified with glacial acetic acid and brought to a boil. Add a small quantity of aqueous silver nitrate with stirring to complete the reaction. Allow the solution to cool to room temperature; crystals of silver styphnate should have precipitated. Filter to collect the crystals, wash them with water to remove soluble impurities, and allow to dry."

Has anyone more informations (exactly explosive features, lead-block-expansion, etc.) about silver styphnate?


A great mxture is lead methyldiisonitrosamine salt (PbMEDNA) and lead styphnate (70:30). For example only 0.09g are needed to initiate tetryl (source: US Patent: US1625966, http://l2.espacenet.com/dips/bnsviewer?CY=gb&LG=en&DB=EPD&PN=USUS1625966&ID=US+++US1625966A1+I+).

This has near the double power of lead azide, can be lighted by fuse and is less sensitiv/unstable!

Lead MEDNA" can be easily prepared by bubbling NO, N2O, NO2, etc. through a solution of sodium ethoxide in ethanol and mixing/shaking the solution of the precipated "sodium MEDNA" with a solouble lead salt. "Lead MEDNA" will be precipated:
See also:
http://www.roguesci.org/megalomania/explo/MEDNA.html

"Lead MEDNA
The lead salt of MEDNA can be precipitated by adding a lead salt solution, such as lead acetate, lead chlorate, lead perchlorate, or lead nitrate, to a solution of sodium MEDNA. This explosive detonates at 250 °C. It can be mixed with lead picrate or lead styphnate for use in detonators."

"Sodium MEDNA
Very slowly add 13.8 g of sodium metal in small portions to 300 mL of anhydrous ethyl alcohol and cool to 6 °C under nitrogen (If you have some sodium ethoxide handy that would do the trick since that is what this reaction makes, it is also safer). 38.4 g of acetone is added slowly with vigerous stirring as nitric oxide is passed in at 320 mL per minute for 140 minutes. A fine yellow solid should form and is collected on a Buchner funnel, then the damp solid is dissolved in 130 mL of water, made slightly acidic with glacial acetic acid, and heated on a steam bath until gassing ceases to come from the solution. The mixture is poured into 400 mL of ice cold ethyl alcohol to give 25.3 g of a brown solid which is recrystallized twice from a 2:1 ratio of ethyl alcohol and water to give a white solid which decomposes without melting at 225-260 °C."

Has anyone tried this?

[The_Rsert]

I have heard of military detonators used lead mononitroresorcinol.
Maybe it was in the http://www.sciencemadness.org/talk/viewthread.php?tid=2664 book. How can I prepare the mononitro?

What's about lead dinitroresorcinol? Has anyone information about this stuff?
Because, dintro resorcinol is much more easily to prepare than the trinitro.

[Bert]

I have heard of military detonators used lead mononitroresorcinol

I have heard of it used in percussion primers, not in detonators.

[Microtek]

The_Rsert: Trinitroresorcinol is by no means difficult to prepare if you have access to resorcinol and ordinary nitric/sulfuric acids. In fact, resorcinol is so reactive towards nitration that you have to be careful and use dilute acids to not get a runaway. I believe I have already posted the details of the method I used.

[The_Rsert]

I have pure resorcinol but I don't know why but I had some misfires with the synth. Next time I will try to make the dinitro resorcinol first.

I followed the german synthesis instructions of http://lambdasyn.science-hosting.de/synfiles/styphninsaeure.htm exactly. I will post some more pics of my extremly fine blood-red product, which is definitly not styphnic acid.

[Microtek]

That synthesis seems unnecessaryly complex, but even so, how do you know it is definately not styphnic acid ? The colour may be misleading as trace amounts of impurities may colour the product various shades of red. Mine is a kind of dusty brick-red powder. It is very insoluble in water, but can be dissolved as Mg-styphnate by adding MgCO3. This solution is blood red.

At any rate, here is the method that I used for making styphnic acid:
- 1 g resorcinol is dissolved in 1 mL warm water.
- 7 g HNO3, 62% is added dropwise with stirring while keeping temp between 35 and 40 C.
- This soln is added dropwise to 20 g H2SO4, 96 % while stirring and keeping temp below 50 C.
- When addition is complete, the mix is stirred for another 30 min without heating or cooling.
- Mix is then poured over about 100 g crushed ice to precipitate the product which is then washed carefully with cold water. Don't try to neutralize it; it is an acid after all.

[The_Rsert]

Thanks for the synthesis instructions.
I can say that it wasn't styphnic acid, because the product does not dissolve very good in MgCaO3 solution. The yield of my red product was also very low.
I used 70%+ nitric, which contains about 5% free NO2. Is it possible that the NO2 maybe oxidise the styphninc aicd?

However, I will try you method and I will try Megalomania's method with dintro resorcinol. Maybe I will test the explosive features of the lead- dinitroresorcinat.

I found some again a interesting explosive:
On page 272 in the German "Meyer - Explosivstoffe" e-book (download here (http://www.sciencemadness.org/talk/viewthread.php?tid=2664)) they are talking about strontium diazodinitroresorcinate as a new good alternativ primary explosive in replacement of DDNP. And they said that it's sometimes mixed with zink peroxide and tetracene to improve it's features. That's anything.
I think, it should be possible to make this at home if you own the the needet chemicals.

Is copper styphnate a stable salt?

[The_Rsert]

How can I diazotise/diazotate (I don't know the right English word for it!) styphnic acid or dinitrophenol?
THX!

[Microtek]

You can't. There has to be an amino group on the ring for the nitrous acid to react with. You can reduce one of the nitro groups with sulfide to get the amino group and I guess that was what you meant in the first place right ?
Anyway, I would suggest you look at the synthesis of DDNP from picric acid and then just adapt it to the slightly different mol weight of your substrate ( styphnic acid or DNP ).

[The_Rsert]

Thanks Mirotek, I've not thought that it's so easy.
I will try it. At the moment, I have no sulfides but I will buy -or produce some soon if possible.

A simple "newbie" question:
Is the formula of DNR(dinitro resorcinate) C6H3N2O6?
If so, the mol weight is 199.0996 g/mol, right?

Thx!

[pdb]

To the ones (if any, besides Microtek) possibly interested in DPNA, I have improved the preparation process in order to obtain a more free-flowing product, with a higher yield. In fact, it's still far from recrystallized Silver Azide for instance, but much better than my very first DPNA crops. This is achieved by concentrating the reaction solution and using powered NaNO2.

- 0.62 ml HClO4 (70%, d 1.67) and 1.60 ml HCl (36%, d 1.18-1.19) are mixed together in 15 ml H2O at room temperature in a small Beaker
- 1 g 3-nitroaniline is introduced with stirring, and dissolution is achieved in a few minutes
- the solution is freezed until ice begins to form
- 0.53 g crystallized NaNO2 are then added at once, under strong strirring (magnetic stirrer)
- precipitation occurs almost immediatly and is complete in a minute
- once filtered, washed with water and dried, the DPNA obtained amounts 1.20 g, i.e. 66% of theorical yield (55% with the previous procedure).

Microscopic obsevation shows crystals are both smaller and more regular in shape and size. Macroscopic handling exhibits an increased flowing capacity and a better density for the same pressure applied.

[2,4,6-TNP]

Dear Rosco Bodine,

I am very interested in US3431156. It seems to me to be as
Mr. Anonymous says "a gold mine of information". The more I study US3431156 and the improvements to the 4/12 variety, the more there are two primaries that
stand out most to me. Those are [4 (Basic Lead Picrate-Lead Acetate--Lead Azide)-12 Lead Azide] example 2 and [4 (Basic Lead Picrate-Lead Nitrate--Lead Azide)-12 Lead Azide] example 5 of US3431156.

Notice how in the patent(and this may be a typo) that for the properties of
examples 1-16 it uses language like "sensitive, powerful, primary explosive"
and "sensitive, very powerful, primary explosive"! The latter being used to describe example 2 and 5, which I am the most interested in because
Lead Acetate and Lead Nitrate are much more accesable than the other
lead compounds used in the patent.

What I want to know is, have you found a clear overall advantage of the Lead acetate over the lead nitrate variant, or vice versa?

What I mean is, you said you have stored some of these examples over a period of time. Was there any difference in stabilty between example 2 and example 5?

Also on a matter of safety, what has been your experiance and feeling about the sensitivity and general handling of these compounds including pressing?

Also when jumping up to the 4/12s of these same examples was there any cleary noticeable changes in properties than the slight increase in overall power? Like changes in flame sensitivity or friction?

Thank you for your response!

[2,4,6-TNP]

Dear Rosco,

I would wait for your reply before posting again, but I don't want to lose my train of thought. It has been my purpose hear at the forum and in my own studies to make for myself a list of the most useful secondary explosives and firing trains for them. What I have come up with thus far is eight secondaries that are most appealing to me and that I percieve are the most powerful, easily made, stable, cheap, with unsuspicous precursors and so on. Here it is a list in alphabetical order:

-AN; Ammonium Nitrate
-ETN; Erythritol Tetranitrate
-HMX; Octogen
-MHN; Mannitol Hexanitrate
-PETN; Pentaerythritol Tetranitrate
-RDX; Cyclonite
-TNP; Picric Acid
-TNT; Trinitrotoluene

You will probably see that my list consists of the most common military and comercially used. My purpose was also to make a list of the very best primaries that I believe are the best; it is short:

-[4 (Basic Lead Picrate-Lead Acetate--Lead Azide)-12 Lead Azide] of the patent
-[4 (Basic Lead Picrate-Lead Nitrate--Lead Azide)-12 Lead Azide] also of the patent

Also, because I beleived the clathrates may not take the spit from a fuse readily or the heat from an electric fuse I tried to make a list of the best (ignition compounds and mixtures) I could find that were readily available to me. Here is that list:

-Basic Lead Picrate
-Black Powder
-Estes Model Rocket Powder( After being finely powdered)

In the firing trains I have considered using examples 2 and 5 of the patent I believe of the eight secondaries listed:

PETN
ETN
RDX
TNP
MHN

Would be the most suitable as base charges in a compound detonator and:

PETN
RDX
HMX
ETN
TNP
TNT
AN
MHN

would be the most suitable for use as main charges in my theoretical firing trains

It is not my hope, Rosco, that you will spoon feed me, but I would like to know what do you consider to be an economical yet undoubtedly reliable amount in milligrams of example 2 and 5 of the patent to initiate my listed base charges.
Again we have spoken before of column diameters ranging from 4-10mm what is the best?

I was hoping that as I begin to make these clathrates that you could give me some advice on some experiments to do to get a feel for their initaitory power using some of the base chages I have listed.

I would also like to hear from you about ignition charges used in blasting caps. The goal I have set for myself is to come up with a compound detonator with exact amounts of each component and method for there loading, so that I can end up with reliable detonators that are composed of substances that will be stable for basically my life time so they can be stored and used any time with unquestionable reliability. Do you think there is any need for an ignition charge when using the examples 2 and 5? If so would Basic Lead Picrate on it's own or in a mixture fit the bill for super storage stability and flame sensitivity or have you come across some other ignition compounds that I should consider? What I mean by ignition compounds is those compounds used to help ignite the 4/11 or 4/12 clathrates used in these firing trains

Thank you again for your responses.

P.S. Though my posts seemed aimed exclusivly at Rosco Bodine, I encourage all others with there helpful responses as well. Thanks

[pdb]

You seem to be wishing to redo the world, or at least this forum...

A few quick comments after a quick reading:
- add nitromethane NM to your list of secondaries
- delete TNT and Octogen, both being too costly to prepare (at least, Octogen would be worthwhile as a sample, given its outstanding VoD)
- Picric Acid is nowaday used as a precusor for primaries (clathrates...) and almost no more as a main charge
- you desire to focus on clathrates make sense, given all the flavours you can prepare to suit your precise needs, and thus justifies you discarding other valuable primaries
- yes, clathrates definitively require ignition charge: add Lead Trinitroresorcinate to your list of ignition compounds (best to use a lead salt if intented to load in contact with a clathrate, for safety and long-term storage)
- 4, 5...10mm are all suitable; you choice will likely be driven by the type of casing you will find available
- instead of searching compounds "stable for your life-time" (another Holy Grail...), you should make yours the golden rule of destroying your primaries and devices containing some every -say, one or two years. This will help your life-time last longer.

[Rosco Bodine]

Dear Rosco,
You will probably see that my list consists of the most common military and comercially used.
HMX is sort of a reach . I would add styphnic acid to the list .
My purpose was also to make a list of the very best primaries that I believe are the best; it is short:

-[4 (Basic Lead Picrate-Lead Acetate--Lead Azide)-12 Lead Azide] of the patent
-[4 (Basic Lead Picrate-Lead Nitrate--Lead Azide)-12 Lead Azide] also of the patent

It is not my hope, Rosco, that you will spoon feed me, but I would like to know what do you consider to be an economical yet undoubtedly reliable amount in milligrams of example 2 and 5 of the patent to initiate my listed base charges. Again we have spoken before of column diameters ranging from 4-10mm what is the best?
The amount of initiator chosen to be used will vary depending on the usual factors that are to be considered for the specific combination of materials in a specific device , and what your own tests show are threshold amounts can generally be at least doubled for reliable functioning , and much more than doubled if you like .
I tend to design using wide margins to assure reliability . 9.5 mm ( 3/8 " ) is a charge column diameter which I favor for detonators . Components are easier to work with at that dimension for improvised devices , and the performance is enhanced over smaller diameter devices .
I was hoping that as I begin to make these clathrates that you could give me some advice on some experiments to do to get a feel for their initaitory power using some of the base chages I have listed.
I haven't done extensive tests myself using these materials , sufficient to even consume the original samples . Basically all that I have done is a few tests sufficient for making the observation that they are reliable , good quality initiators which have desirable chemical and physical properties, and are not difficult nor expensive to make .

I would also like to hear from you about ignition charges used in blasting caps. The goal I have set for myself is to come up with a compound detonator with exact amounts of each component and method for there loading, so that I can end up with reliable detonators that are composed of substances that will be stable for basically my life time so they can be stored and used any time with unquestionable reliability. Do you think there is any need for an ignition charge when using the examples 2 and 5? If so would Basic Lead Picrate on it's own
or in a mixture fit the bill for super storage stability and flame sensitivity or have you come across some other ignition compounds that I should consider? What I mean by ignition compounds is those compounds used to help ignite the 4/11 or 4/12 clathrates used in these firing trains
I prefer to use a low order detonating flash igniter charge like basic lead picrate or the two others that I have mentioned , for the " hot start " it assures for the rest of the components in tandem . I believe there is also the benefit of some physical compression of the adjacent materials by the rising pressure from the
low order detonation of the flash igniter , which in effect "completes" the press loading of the remaining charge in situ , briefly before it is subjected to the impulse from the more rapidly detonating initiator charge . The initiator and base charge gets "squeezed" tightly by a relatively gentle pressure wave which physically compresses it , and then gets hit by the main detonation wave as the main intitator goes high order . That's my theory anyway . So high pressloading pressures are not required for loading a serviceable detonator , especially if a flash igniter charge is the first fire . Firmly loaded components are sufficient because the firing sequence itself presses the charge in the instant before it is detonated . It is a good practice to load the detonator charge in stepwise portions of one quarter to one half gram portions , firmly compressing each portion until the entire charge is loaded . Using this strategy of stepwise loading , and dealing with materials where the physical form is that of relatively fine granulation but " gritty " crystals , serviceable detonators can be made at the 9.5 mm column diameter by applying only 20 to 30 pounds of pin pressure to the
loading ram . Very lightly constructed presses and loading fixtures of an easily improvised nature may be used to achieve such minimum loading pressures . Even something as simple as one of the large size strap frame caulking gun type of loading press scenario can be used for increased safety , to achieve the
low pin pressure which actually puts these improvised detonators in the class which is often called " hand pressed " and possible to do absolutely manually , although that is not the preferred method for safety concerns , when a simple light duty loading fixture is so easily built for the task . A blast shield for a caulking gun type press can be as simple as a five gallon metal bucket with a hole cut in the lid , or an empty five gallon propane bottle with a hole cut in the top and if desired an access hatch cut from a section in the side .

If you want the simplest long term storage stable devices , then it seems to me the picric acid based detonator would fit that criteria . I have described the concept before and named the components where the base charge
is picric acid , and every other component in the firing train is also a picric acid derivative . It may have been in the " most versatile explosive " thread . In different threads I think nearly all of this stuff has been covered before .

Pasted below is the relevant quote from the earlier thread I mentioned above :

Picric Acid is undoubtedly the most versatile explosive .
Picric Acid is a fine high explosive by itself , and it is
the precursor for superior igniter and initiating explosives
that are also useful elements of a practical firing train .
Averaging all the desirable qualities and awarding the prize
to one candidate compound for overall usefulness , my vote
goes unequivocally to trinitrophenol . See references below .

Igniters :

US2175249 See example 2 for one of the best "first fire"
low order detonating flash igniters , a superbly useful
and easily made compound .
US3293091 See example 4 for a similarly useful different compound .
US1478429 See example 1 for the most simple and third variant which is the
parent compound for the two above compounds .

Initiators :

US3431156 Basic lead picrate / lead azide clathrates "azo-clathrate" primaries
These are worth the effort too .

Anyway , picric acid is a first class base charge for a detonator and if the detonator is properly designed it will indeed initiate anything you like and do a thoroughly good job . Sure you need more of picric acid than PETN , and it takes more intitiator to get the picric acid going , but once the TNP is doing its business of high order detonation , it is no slouch at all even in gram quantities , about delivering a brisant , metal shattering impulse and detonation wave of high energy and velocity . Among the common explosives that are also cheap and OTC , picric acid is a proven good performer . In a pinch it can even be detonated completely by 1.75 grams of TCAP in a " hand pressed " plastic bodied detonator capsule if the TCAP is given a " hot start " with a quarter gram ball of AP putty as the " first fire " . That was discovered recently by me for the 9.5 mm column diameter , in a non-reenforced detonator where the initiator was simply lightly pressed on top a 1.5 gram picric acid base charge , everything loaded into a 5 ml polypropylene culture tube . I had known before that in a strongly confined reenforced detonator that AP would initiate picric acid but it was a new development to secure a complete detonation of picric acid initiated by AP in the more simple non-reenforced detonator configuration . If ordinary AP will intitiate picric acid in a non-reenforced detonator , well then you can be assured that an azo-clathrate initiator will also do the job . One of the considerations for long term storage devices is the physical integrity of the pressed charge . Certain binders in trace amounts would likely be of benefit for maintaining the agglomeration of the pressed components , so that during many thousands of cycles of temperature changes , the expansion and contraction of the material doesn't result in a crumbling and density lowering of the pressed materials , but that they remain stable at the density they were originally pressed in the device .

[Rosco Bodine]

I use diazoperchlorat-3-nitroanilin associated with PETN for making detos. It's a cheap, easy-to-prepare primary explosive, with a remarkable initiation power, greater than fulminates and metal azides. However, it has not found its way in industry because it doesn't pour easily. Although it is not a problem for my detos, I would like to explore ways to obtain a cristallized size-controlled product. I never heard of any solvent, but my idea is to prepare it in another medium than water, maybye in ethanol.

Does anyone know and use this compound ? Would be delighted to exchange experience about it.

To revisit the beginning of this thread the compound being described and a
method for its synthesis in crystalline form is described in COPAE , page 442 .

The structural formula in COPAE incorrectly shows the nitro at the #2 position ,
which would be the derivative of ortho or 2-nitroaniline . But it is clear from
the verbal description of the synthesis starting from m-nitroaniline ( which is
3-nitroaniline ) that the nitro group for the diagram should be shown on the
#3 position .

Anyway the compound pdb describes at the beginning of the thread is the same
compound . Originally the compound is described by the Von Herz patent .
( German )

DE258679

[2,4,6-TNP]

Dear Rosco,

Thank you for your reply; I found the patents you listed very interesting
and helpful. I was especially interested in US2175249. As a result of my
studies and pursuit of a storage stable, and powerful coumpound detonator
I took your advice and came up with the following system. I have not listed
the amounts that are optimal, because I'm still working that out. However I am satisfied with the experiments I have done that the ignition charge has caused
the full ignition and resulting detonation of the lead nitrate based azo-clathrate ten out of ten times using an equal weight of each.
I chose barium chromate as an oxidiser because it is storage stable and non-
hygroscopic. It is also insoluable in water. As are all the components of the system except of course the Picric Acid which is no real problem in a hermetically sealed aluminum housing. I just thought that the ignition charge may be exposed to moisture over time since it is in contact with the fuse or electric match wich may have small pockets between it and the aluminum housing. So anyway here is the system:

Ignition Charge:

A finely amalgamated ignition charge consisting of:

70% Lead Nitrato-Bis Basic Lead Picrate of US2175249
15% Finely Powdered Aluminum
15% Barium Chromate

Initiating Charge:

An unequivocal initiating charge consisting of:

-[4 (Basic Lead Picrate-Lead Nitrate--Lead Azide)-11 Lead Azide] of US3431156

Base Charge:

A base charge consisting of:

High Purity Picric Acid

I found that to me all these compounds are very cheap in the quantity they are used and very simple to make.

I was wondering, Rosco, did you make the lead nitrate azo-clathrate as well
as the lead acetate azo-clathrate. I was just wondering. If so, did you find a difference in storage stability or crystal size. I've done the lead nitrate azo-clathrate and I'm impressed, I just want to know if the lead acetate azo-clathrate is worth the effort as well? If the lead acetate azo-clathrate is good I was thinking about trying a modification of example 2 of US2175249 by substituting lead acetate instead of lead nitrate to form an ignition charge.

Thanks again!

[Boomer]

Rosco wrote:
"I believe there is ... some physical compression of the adjacent materials by the rising pressure from the low order detonation of the flash igniter, which in effect "completes" the press loading of the remaining charge in situ.... The initiator and base charge gets "squeezed" tightly by a relatively gentle pressure wave ..... So high pressloading pressures are not required for loading .... serviceable detonators can be made at the 9.5 mm column diameter by applying only 20 to 30 pounds of pin pressure to the
loading ram."

I did not keep up with reading so I am late, but anyway...
I strongly doubt that the "compression" takes place the way you think. Even a low order detonation is supersonic by definition. It propagates so fast, the single crystals are consumed before they are pushed / compacted into the lower crystal layers.
I compared hand-pressed caps with vice-pressed caps, and the difference was amazing (there is a pic here somewhere) though the loading was identical.
To illustrate what I mean: fill a pipe with a base charge, pressing just enough to keep it together, but leave the bottom open. Initiate it at the top. If there was any compression prior to detonation, some material should be pushed out the bottom, which is never the case.

There is one type of cap where the effect you describe takes place though: A strong pipe with MHN as a base charge, followed by flash (or another fast burning mix). Here the MHN is detonated by the compression from the deflagrating mix. You can use less flash if you add sand or glass to the MHN, so additional friction is generated during compression. It is not the heat that starts the MHN, as they do not work if the pipe is left open at one end.

[Rosco Bodine]

Boomer : I have done many experiments with charges pressed
across a wide range of intensity , even up to the deformation limits
of the capsules , even for double walled capsules held in loading dies
and loaded at several thousands of psi . And I * know * from the
observed effects that at the larger diameters such as 9.5 mm that
" self - compression " does indeed occur , by whatever mechanism
and whatever theory applies . There is sometimes even an evidence
of a reflected wave detonation front which meets in the middle of the
length of the longer columns of a multigram base charge , signifying
that a sympathetic detonation was initiated at the bottom end of the
charge column and travelled upwards to meet the direct detonation wave
at a point maybe two thirds the distance down from the point of direct
initiation of the column . How that is explainable is another mystery
which I cannot explain except in terms of a physical movement of the
charge itself , as if it were a bullet fired inside a sand filled gun barrel .
Probably there is a more complicated explanation for the
mechanical effects I have observed , and the way I have explained it
may not be precisely technically correct , or an oversimplification to
account for the self-compression . It is something I see on witness
plates where a low order detonation produces a deep dent without
puncturing the sheet metal , even though the detonation wave was
supersonic , the physical movement of the target material is already
like a surfboard set in motion by a subsonic wave , before the supersonic
component comes speeding through . The inertia of the lower third
of the column of base charge crystals may be acting as an anvil or
sandbag , and be wedged laterally in the capsule by horizontal expansion
to act as a " false bottom " and create a " hot spot " for the detonation
as opposed to being evidence of a reflected wave . Whatever is the
correct explanation for such effects , I am not certain , perhaps a
combination of factors is involved . One factor I can see applies is
the crystal form and loose density of the charge material itself . The
benefit of a highly compressed charge in advance of any firing would
be much more of a requirement and make a much greater difference
in performance for a low density and fluffy powdered charge material .
But for certain gritty aggregates of charge material , there isn't so much
of a density increase to be obtained by highly pressed loadings .

In spite of your doubts , I can't think of a simpler explanation for the
effects I have observed . Some very high speed photography would
be needed to settle the question definitively .

[Rosco Bodine]

Dear Rosco,
Thank you for your reply; I found the patents you listed very interesting
and helpful. I was especially interested in US2175249. As a result of my
studies and pursuit of a storage stable, and powerful coumpound detonator
I took your advice and came up with the following system. I have not listed
the amounts that are optimal, because I'm still working that out. However I am satisfied
with the experiments I have done that the ignition charge has caused
the full ignition and resulting detonation of the lead nitrate based azo-clathrate ten out of ten times
using an equal weight of each.

What weights of charges and what column diameter are you using and what sort of capsule and pressing scheme ?

I chose barium chromate as an oxidiser because it is storage stable and non-hygroscopic. It is also insoluable in water. As are all the components of the system except of course the Picric Acid which is no real problem in a hermetically sealed aluminum housing. I just thought that the ignition charge
may be exposed to moisture over time since it is in contact with the fuse or electric match wich may have small pockets between it and the aluminum housing. So anyway here is the system:

Ignition Charge:

A finely amalgamated ignition charge consisting of:

70% Lead Nitrato-Bis Basic Lead Picrate of US2175249
15% Finely Powdered Aluminum
15% Barium Chromate

Initiating Charge:

An unequivocal initiating charge consisting of:

-[4 (Basic Lead Picrate-Lead Nitrate--Lead Azide)-11 Lead Azide] of US3431156

Base Charge:

A base charge consisting of:

High Purity Picric Acid

I found that to me all these compounds are very cheap in the quantity they are used and very simple to make.

I was wondering, Rosco, did you make the lead nitrate azo-clathrate as well
as the lead acetate azo-clathrate. I was just wondering. If so, did you find a difference in storage stability or crystal size.
I've done the lead nitrate azo-clathrate and I'm impressed, I just want to know if the lead acetate azo-clathrate
is worth the effort as well? If the lead acetate azo-clathrate is good I was thinking about trying
a modification of example 2 of US2175249 by substituting lead acetate instead of lead nitrate to form an ignition charge.

Thanks again!The compound I liked best was the 4/12 azo-clathrate ,
[ 4 ( basic lead picrate / lead nitrate / lead azide ) 12 ( lead azide ) ] . This
had a better density and power than the acetate variant , and is an improvement
over the 4/11 azo-clathrate of the patent . You don't want an azo-clathrate
for the igniter . It would not provide the benefit of the low order detonating
flash igniter and could prematurely shatter the upper portion of the capsule .

The barium chromate and aluminum are not really needed with
the lead nitrato-bis basic picrate . They probably do little to
enhance the initiation , since that particular igniter burns very hot
by itself and quickly goes to low order detonation with a dual
effect of both thermal shock and percussion which is more than
sufficient in either effect alone to cause the azo-clathrate to
initiate at high order , without ever actually being ignited first ,
which it could do very nicely too , if for some reason the first fire
was sluggish . There is a lot of redundancy in the first two elements
of such a firing train , which insures the reliability by simultaneously
providing three valid paths to detonation , any one of which can get
the job done .

Generally what goes into one of Rosco's #20 special engineers magnum compound detonators ,
is 2.5 grams of picric acid pressed firmly in .5 gram increments and topped with 1.5 grams
of the 4/12 azo-clathrate ( yes , a gram and a half ) likewise pressed .
This amount of initiator guarantees overdriving of the large base charge .

The firing squib is made from one of the little Christmas tree lamps
which has had the tip ground off using a a fine grit drum sander chucked
in a drill . I use a razor knife to cut a short bushing from some polyethylene
tubing which is 7/32 " bore and 3/8 " outside diameter , so that the bushing
is just a bit longer than the exposed section of the glass bulb . Then I
hold the end of the bushing against the edge of the flame from a propane
torch at a low idle setting to gently melt and just ignite the molten plastic ,
blow it out as if blowing out a candle and immediately shove the little
Christmas tree lamp inside the bore and twist it a half turn as the plastic
lamp socket seats into the molten polyethylene , which heat welds the
lamp socket to the bushing . I have a brass tube with a 3/8" bore and
a slightly flared " throated " opening handy , and while the plastic is still soft
from the heat welding , the squib assembly is shoved cool end first
inside the brass tubing quickly , and allowed to cool . The flare and the
bore of the brass tubing functions as a die to reshape the distorted portion of
plastic weld which bulged slightly outward when the pieces were twisted
together while very hot . When the piece cools it is pushed out of the
brass "die" with a dowel , and it is ready for loading with the igniter charge .
It takes a little practice to see just how long to "flame" the bushing ,
about three or four seconds while rotating it with the fingers , about
the same for performing the "twist weld" of the bushing to the miniature
lamp socket , and then without delay shoving the still soft part into the
brass tubing die to reform the weld area . The whole process takes
maybe ten , no more than fifteen seconds . One of those tapered plastic
dispenser tips which can be cut off to provide a smaller or larger opening
for applying a bead of glue or whatever else from a plastic squeeze bottle ,
can be cut to fit the bushing bore and fit snugly over the open end of
the tip of the miniature lamp . This will make a handy loading funnel for
filling the bulb with the igniter composition .

After the bulb is filled and the funnel removed , a piece of tape , or a 3/8" adhesive "marker dot"
can be used to cover the end of the loaded squib and retain the igniter charge while the squib
is inserted into the loaded detonator . The gap around the leg wires can be sealed with a
non-hardening elastomeric glazing or gasket compound which never sets up completely but remains sticky .
For really long term storage devices you may want to replace the vinyl insulated leg wires
with teflon insulated wire , since vinyl insulation will gradually embrittle
after maybe 15 years , but teflon is probably good for 75 years or more .

Spraying the vinyl insulated legwires with a urethane lacquer would probably
extend the storage life greatly , as would keeping the devices in a hermetically
sealed and dry container , stored with silica gel for example , in a dark and cool
place , not exposed to a steady supply of ozone from the atmosphere which
causes the degradation of plastics . The only potential difficulty I can foresee
is at the physical contacts where the bulb wires are pressed into the miniature
socket . After some years of storage , oxidation of the brass contacts might
require a higher firing voltage , unless these contacts were upgraded in advance
to being soldered connections . For the ultimate in bridgewire assemblies , it
is possible to use fine nichrome wire fed out coaxially from tubular stainless
support legs made from hypodermic needle tubing bearing multiple crimps ,
and the tubing then silver soldered to gold plated connectors equipped with
solder cups which receive the copper legwires . That specification is sort of
reserved for applications where extraordinary reliability and storage longevity
is required , such as for aerospace applications , ejection seats ,
spacecraft components , ect . , of course such a scheme will work just as
reliably for terrestrial applications if you simply must have the best and nothing
less will do :D

[2,4,6-TNP]

What weights of charges and what column diameter are you using and what sort of capsule and pressing scheme ?

I used for all 10 experiments 3/4 gram of the ignition charge I mentioned, 3/4 gram 4/11 lead nitrate azo-clathrate, and 1 gram pale, dry picric acid. I used a 5.56mm aluminum tubing with about a 5/10ths mm wall thickness. I can not be accurate as to how many pounds of pressure I used to press the charges. I just use one of those manual table mounted presses and put all my weight(150LBs) onto the handle while pulling myself down against the table. The ignition charge was not pressed at all but just poured on the clathrate and a fuse was inserted and the aluminum tube crimped with needle-nose pliers. Like I said they all detonated. They were placed in 5 gallon plastic buckets. After the experiments I used a spray bottle to finely mist the inside of the white buckets to see if any picric acid was in there, because water turns even small grains of PA a brilliant yellow. There wasn't any. Just black burn marks and damaged buckets.

The compound I liked best was the 4/12 azo-clathrate ,
[ 4 ( basic lead picrate / lead nitrate / lead azide ) 12 ( lead azide ) ] . This
had a better density and power than the acetate variant , and is an improvement
over the 4/11 azo-clathrate of the patent . You don't want an azo-clathrate
for the igniter . It would not provide the benefit of the low order detonating
flash igniter and could prematurely shatter the upper portion of the capsule .

You must of misunderstood me, what I meant was making an ignition charge of Lead Acetate-bis basic lead picrate instead of the lead nitrate of the patent.

The barium chromate and aluminum are not really needed with
the lead nitrato-bis basic picrate . They probably do little to
enhance the initiation , since that particular igniter burns very hot
by itself and quickly goes to low order detonation with a dual
effect of both thermal shock and percussion which is more than
sufficient in either effect alone to cause the azo-clathrate to
initiate at high order , without ever actually being ignited first ,
which it could do very nicely too , if for some reason the first fire
was sluggish . There is a lot of redundancy in the first two elements
of such a firing train , which insures the reliability by simultaneously
providing three valid paths to detonation , any one of which can get
the job done .

I was just following the patents advice, they did recommend page 2, line 30-40 that the main igniter be admixed with oxidisers such as potassium chlorate, barium peroxide, and calcium peroxide, and powdered metals of Zirconium, Magnesium, and aluminum. They gave as an example:

70% Picrate igniter
15% Potassium chlorate
15% Zirconium

I just figured it was to add some extra umph to the igniter.

Generally what goes into one of Rosco's #20 special engineers magnum compound detonators ,
is 2.5 grams of picric acid pressed firmly in .5 gram increments and topped with 1.5 grams
of the 4/12 azo-clathrate ( yes , a gram and a half ) likewise pressed .
This amount of initiator guarantees overdriving of the large base charge .

I was wondering do you use the same pressure on the azo-clathrate as you do in pressing the Picric Acid? Also like me do you just pour the igniter over the azo-clathrate without compacting it?

I have saved for myself a copy of the thread of Mr. Anonymous about moving up to the 4/12 clathrate, I will be trying that next, as I have thus far gone exactly by example 5 of the patent. I was just wondering if there is any special advice when making the 4/12 instead of the 4/11? What I mean is have you just followed Mr. Anonymous' synthesis to the word and letter or have you discovered your own special method?

Thank you again for your reply! :D

[Rosco Bodine]

The lead nitrato-bis basic picrate is good to go as an igniter and
pretty well state of the art as it is , needing no improvement .

The additives for the igniter are something for creating particles
of burning slag to increase the burning time for cartridge primers ,
and create multiple ignition points in a smokeless powder charge .
You don't need that effect in a blasting cap , just an intense heat
and low order detonation , from an easily ignited material .

For the smaller 1 gram base charge you are using , a 6 mm column is fine .
But what you have there is about like a commercial # 8 and won't do the
job well for most improvised AN explosives or for something difficult
to initiate like urea nitrate . Since the least amount of work is involved
in the loaded materials , I would always recommend a pretty heavy loading
for custom made detonators . That way the product of your effort is
universally applicable to anything you would want to detonate , and
would overdrive the more sensitive compositions where a smaller cap
would be adequate . It hurts nothing to use a bigger cap than needed .
But poor results can certainly occur from using a detonator that is just
adequate . So the error should be in the direction of using a heavier loading
than is required .

The initiator is pressed firmly on top of the base charge . The igniter is
always a loose charge . In a fuse cap I simply load a quarter gram of
the loose igniter on top of the pressed initiator . In an electric squib ,
just whatever amount of igniter fills the bulb is used , and no additional
amount of igniter is placed on top of the initiator , because the squib is
pressed firmly in contact with the initiator . When the squib is fired ,
the jet from the igniter easily blows through the tape covering and
sets off the initiator .

Mr. Anonymous and Rosco Bodine are aliases for the same person .

[2,4,6-TNP]

Mr. Anonymous and Rosco Bodine are aliases for the same person .

Forgive my ignorance! I knew there was something familiar about your writing style. I'd like to pay you a compliment: you have an excellant vocabulary, you are witty, and you know your topic well. It is always a joy to talk with you!

Have a beautiful, clam-happy day!

[Rosco Bodine]

Forgive my ignorance!
No problem , my first alias was created by the necessity of webspeak
for e-mail and all other internet service account designation requirements .
I trust also that on your birth certificate and drivers license your own
real world name is likely something different from " 2,4,6-TNP " :D
The internet has made " multiple personalities " of many otherwise ,
( or at least seemingly ) " sane " people who were single distinct individuals
before undergoing their imposed binary " ascension " to plural identities .
Let's face it that we have become significant forces in the universe when
we have become so huge that for those such as we are , only one name is
inadequate :D

I knew there was something familiar about your writing style. I'd like to pay you a compliment: you have an excellant vocabulary, you are witty, and you know your topic well. It is always a joy to talk with you!For years I struggled with self-doubts concerning my own excellence before becoming resigned to an acceptance of the truth that of course I am a gentleman and a scholar and one hell of an engineer ;)

Have a beautiful, clam-happy day!
Same to you .

Regarding your loading press , if it is an arbor press , you can make an
adapter socket to fit over the pinion shaft , and use a ratchet style
torque wrench to establish any repeatable loading pressure you choose .
You can even place a set of bathroom scales under the ram and determine
what sort of ram pressure corresponds to a particular letoff setting on the
torque wrench , and then do the math to know what torque setting will
result in a desired force being applied by the ram . In this way you can
make the pressing operations consistent , and know when you are applying
exactly the force you wish to apply in each operation .

Some of the heavy duty rack and pinion jacks which are used to raise and lower
the hitch on the towing bar of trailers might be useful in improvising a sort
of light duty arbor press for applying up to a few hundred pounds of pin pressure ,
and such an improvised press could be controlled using a torque wrench in
the same way .

[2,4,6-TNP]

Dear Rosco,

I am the one to agree, you were kind to post the lead nitrate 4/12 azo-clathrate
synthesis, but there is something important missing. You claimed you synthesisized Sodium Azide from over the counter shit. So let it be revealed to me this very day.

I am pathetic in my use of airbags, would it not be fitting for you to tell:

What are the over the counter precursors you used?

And the synthesis that is your finest?

If you were to post your sodium azide synthesis I would be honored and you would surely make my day.

I am sad because my azo-clathrate synthesis is thus far botched I'd say because of contaminents. Please telll me the proper synthesis. It is likely more economical than my airbag purchase and my dissappointing botching of my finest Primary thus far!

Thank you Rosco!

[Rosco Bodine]

At the risk of getting myself put on a bunch of peoples " shit list "
I am going to say you should probably stick with your airbag source
and try to quantify the composition of the airbag extract so you can
work better with it . On the scale of difficulty , 1 to 10 , an airbag
extraction is a " 1 " and a total synthesis of sodum azide is a " 10 " .

The sodium azide synthesis I devised has been described in summary fashion ,
but I never posted the synthesis as a 1-2-3 step by step Experimental . The
process involves first synthesizing Hydrazine Sulfate , and Isopropyl Nitrite .

The synthesis of the isopropyl nitrite requires sodium nitrite , which has limited
availability as a preservative used for canning or drying meats . It can be obtained
OTC but it requires some effort searching to find it , and sometimes it will be mixed
with sodium chloride and sold as a " meat pickling salt " , from which it would need
to be isolated . A butcher shop or meat packing plant would probably have on hand
the pure sodium nitrite , which they use in quantity as a minor ingredient in the
salting solution for processing tons of meats . Forklift pallets of hundred pound bags
are kept on hand at larger operations . I have seen it available as a " home canning "
supply item in five or ten pound bags , from " farm supply " type of businesses , but
I don't recall the details . I think I have seen it sold as a " hunters and outdoorsman "
supply item for making " venison jerky " and similar preserved meat foodstuffs , sold
as a mail order item by " safari / expedition outfitter " type of suppliers . So the
sodium nitrite can be found , but it takes some looking in the likely places to find
who has it for sale . Otherwise it is not OTC and has to be made by one of the known
methods from sodium nitrate .

Anyway , the synthesis of sodium azide requires glass and teflon reaction vessels ,
and is a bit complicated . It is done in a slightly pressurized sealed glass reaction
flask kept cold in an ice bath . The synthesis of the precursors and the sodium azide
itself pretty well requires proper lab equipment , or some very ingeniously improvised
substitutes . Even with the proper equipment , it is a lot of work . For example ,
using a 4000 ml erlenmeyer for making the hydrazine sulfate , and a 2000 ml erlenmeyer
for making the isopropyl nitrite , then a 1000 ml erlenmeyer for freebasing the hydrazine ,
and a 2000 ml three neck for the nitrosation reaction , a good three days work in the
lab gets you about 75 grams of sodium azide . There are easier things to make from
scratch , that's for sure . After doing the synthesis a few times , I realized that posting
the details as a step by step " Experimental " would likely invite people not having
either the knowledge or the proper equipment to get themselves hurt trying to perform
a synthesis which is hazardous in its every aspect , involving volatile and * extremely *
toxic materials , so as a matter of discretion I went no further in describing the process
in terms of a " recipe " , knowing full well that somebody having no business attempting
the synthesis would do so anyway , probably in an apartment or dormitory kitchen to
compound the danger even further . I posted enough summary information that I knew
any actual chemist reading what I wrote , would have sufficient information to duplicate
the synthesis , and also realizing it was best to leave it at that for knowing that people
requiring a six page step by step , simply don't have the " labsmarts " or the " chemspeak "
to understand and safely do the synthesis to a successful end .

I know it will sound conceited , but I already laid out the details for anybody qualified to
be doing that total synthesis of sodium azide , deliberately doing it in a way that those
folks who aren't qualified probably wouldn't understand half of what I said :D

The same strategy was applied to the disclosure of the other azo-clathrates . The
actual , for real , bona fide chemists out there will very quickly " catch on " , and those
who aren't , well they have no business proceeding until their knowledge is increased
to a level required for getting beyond that plain littered with carcasses where curiosity
killed many kindred cats of their same stripe :D .

Besides all that , it saves me a lot of typing :D

[Bert]

I am sad because my azo-clathrate synthesis is thus far botched I'd say because of contaminents.
I know of successful synthesis of the azo-clathrate by some using re-crystalized picric acid made from aspirin, home made Lead nitrate, OTC Sodium hydroxide and "recycled" air bag Sodium azide. Purity is not likely your problem if you did your work reasonably carefully. The close control of VERY SLOW addition rates, stirring intensity and temperature are the most difficult aspects of that synthesis.

That being said, I'd like to see the complete azide synthesis from OTC- Mega recently posted an outline of the process starting from hydrazine sulfate, but the process of producing the hydrazine sulfate itself was not described, also certain aspects were assumed to be common knowledge of the readers and so were minimaly addressed.

[Rosco Bodine]

I suppose I can at least compile some of the pertinent excerpts here
until I feel comfortable with the idea of laying out the step by step for
both the enlightened and the reckless :D . Anyone should be able to
extract the details from these excerpts and the relevant patents ,
which have also been posted before . I'll have to look later and post
the patent numbers for the pertinent patents .

http://www.sciencemadness.org/talk/viewthread.php?tid=757&*

Excerpt :

"These more dense and better quality hydrazine sulfate crystals perform much better in subsequent reactions where hydrazine is freebased from its sulfate, requiring only half the previously required amount of added water to create stirrable slurries with NaOH for methanol extraction of the freebase hydrazine hydrate. The more dense better formed crystals of hydrazine sulfate may be freebased to hydrazine hydrate by portionwise additions of solid NaOH, the water produced as a by-product of the freebasing being almost sufficient alone for creating a stirrable slurry capable of being extracted with methanol, taking up the hydrazine hydrate in methanol while leaving behind the sodium sulfate as an insoluble residue. In practice it has been found that only 10 to 12 ml of added water per mole of hydrazine sulfate is sufficient for the purpose of keeping the mixture in the form of a slurry able to be extracted easily by methanol in sequential portions which are decanted from the residue until the hydrazine has been effectively extracted from the insoluble residue of sodium sulfate crystals. Reducing the added water requirement to this small amount in the freebasing of the hydrazine has eliminated the need for elaborate dehydration schemes using alkoxides to obtain acceptable yields of sodium azide directly from the much drier methanolic extract of hydrazine hydrate.

For the synthesis of sodium azide, methanolic hydrazine hydrate extract is further basified to slight excess of an equimolar amount of NaOH and treated in the cold with a slight equimolar excess of isopropyl nitrite (preferable), or equivalent of ethylene glycol dinitrite, to consistently produce sodium azide directly, in 65 per cent total yield based on the hydrazine sulfate used for the freebasing of hydrazine hydrate into methanol. The improved freebasing technique using reduced added water provides a useful yield of sodium azide by a process which involves no hazardous distillations of hydrazine or other added tasks for chemical elimination of excess water. Isopropyl nitrite was found to have a low transesterfication activity on contact with methanol in thecold, with cooling provided by immersing the azide production flask in an ordinary 0 degrees cold water bath containing chunks of ice. With this cooling the partial pressure of methyl nitrite from transesterfication of the isopropyl nitrite was sufficiently low that the back pressure provided by immersing a vent line from the closed apparatus to a depth of sixteen inches into a water filled carboy prevented any free boiling away of the organic nitrite from the reaction producing sodium azide, until the reaction was very near its endpoint. After three hours reaction in the cold, the temperature was raised to boil away unreacted nitrite and the back pressure peak upon heating to drive the reaction to completion was raised to six feet of water, (about two and one half pounds per square inch of back pressure ), maintained for fifteen minutes, before gradually reducing the back pressure to atmosphere and allowing complete boiling off of any unreacted nitrite. An alternate attempt to freebase hydrazine hydrate and use isopropanol for the extraction failed because of the stratification of the liquid portion into two layers, leaving much of the hydrazine hydrate in the heavier more aqueous layer unextracted by the isopropanol. Full details for the synthesis of sodium azide will be provided in a later communication. This digression simply describes why the improved synthesis of the hydrazine sulfate is of special interest for producing the hydrazine sulfate in better crystalline form by a method which improves its usefulness particularly as a precursor material for OTC sodium azide, or when the purpose will be to freebase the hydrazine and extract it with methanol for any other use. "

http://www.sciencemadness.org/talk/viewthread.php?tid=253&*

Excerpt :
A practical method for pure crystalline sodium azide has been carefully worked out and tested by me and I have posted the general description both here and at E&W , but not yet given a detailed step by step . The method requires proper lab glass and teflon apparatus and a magnetic stirrer , and generally anyone having those things could duplicate
the process from my general description , so I never described it further . The method involves freebasing hydrazine hydrate from solid hydrazine sulfate with solid sodium hydroxide using a minimal amount of water just sufficient to initiate the reaction between the solids , the byproduct water from the freebasing being sufficient to result
in a just stirrable warm slurry of porridge like consistency , which consists of solid sodium sulfate and hydrazine hydrate in water . Alternate portions of the solids are added to the stirred reaction mixture along with just enough water added by drops to prevent the mixture from setting up solid . To perform this freebasing , I use a 1 liter erlenmeyer having a ground joint and glass stopper greased with silicone , and a three inch octagon stirbar , set upon a stirrer hotplate on low heat . Initially I put about half the solid hydrazine sulfate into the flask , dampened with a few ml of distilled water . The solid fine prilled NaOH
in an amount slightly over the amount of theory required for freebasing
all of the hydrazine in the total batch is preweighed and put into a plastic bottle with a dispenser tip having a snap cap , like a glue dispenser bottle where you can cut off the tip to size the delivery opening . This allows for the addition in portions of solid NaOH , and stoppering the flask and capping the plastic bottle of NaOH between additions to exclude moisture and air , which will otherwise complicate matters during the manipulations of these materials . When the first portion of hydrazine sulfate has become a thin slurry from additions of NaOH , the rest of the hydrazine sulfate is added and the additions of remaining NaOH continued , adding any minimal amount of water needed , by the eyedropperful , using only sufficient water to keep the mixture stirrable and prevent setup . Keeping the mixture hot , above the temperature where sodium sulfate transitions to a hydrated salt is required throughout the freebasing . After all the NaOH has been added , the mixture is kept warm and stirred for an additional ten minutes , and then extracted while still warm with succesive portions of methanol which takes up the hydrazine hydrate and water while leaving behind the anhydrous sodium sulfate byproduct . All of the methanol extracts should be done by mixing and decantation of the methanol
using four added portions about the same volume as the mixture being extracted .
Filtering will not work because of the air sensitivity of the hydrazine , and all manipulations should be done quickly
and stoppers put into place following transfers . Hydrazine is an efficient "getter" for oxygen and will actually pull a partial vacuum in a stoppered flask when it reacts with any oxygen in the headspace over the liquid .
The vapor pressure of the methanol fumes escaping helps provide a protective blanket against the air which is detrimental otherwise to hydrazine .

In the isolated methanolic hydrazine extract is dissolved a slight excess of
an equimolar amount of solid NaOH .

A corresponding slight excess molar amount of isopropyl nitrite is prepared separately .

When the methanol solution of hydrazine hydrate and NaOH is placed in a reaction
flask , setup for magnetic stirring and cooled by an ice bath , crystalline sodium azide
will precipitate in the cold mixture as isopropyl nitrite is gradually injected
below the surface near the bottom of the
stirred mixture . The reaction produces
pressure in the reaction vessel due to some transesterfication of the isopropyl nitrite to methyl nitrite . So the ground joints must be wired or clamped to prevent their being dislodged by the pressure . The pressure is regulated by
having a vent line immersed in water to
a depth sufficient that the head pressure
will just slightly be overcome and allow
a very slow bubbling from the end of the vent line . I made an improvised "tilt tube
manometer" for pressure regulation , by
duct taping a six foot length of 2 inch PVC
water pipe to the neck of a glass gallon jug and filled the entire thing with water .
The vent line was shoved down through
the pipe and to the bottom of the glass jug where the end of the vent line could be observed bubbling . By sitting the
jug on the ground and leaning the top
of the water filled PVC pipe against a wall
at whatever height was desired , the back
pressure on the reaction vessel could be regulated to allow only a slight venting
evident by observing the bubbling at the end of the vent line . Tilting the assembly closer to a horizontal position
lowers the venting pressure , while raising
it towards vertical raises the venting pressure . By use of this setup it is easy
to maintain a controlled and safe pressure
within the glass system .

The injection of the isopropyl nitrite into
the system was accomplished by using
a non-equalized addition funnel equipped
with a drip window and a teflon capillary
delivery tube . A few drops of methanol
was added to the isopropyl nitrite in the addition funnel and the methyl nitrite produced by transesterfication served to
pressurize the funnel after it was stoppered , the stopper retained by a spring clamp for any overpressure relief .
This setup allowed for slightly pressurized
delivery of the isopropyl nitrite , into the
cold and therefore lower pressurized reaction flask below .

A good yield of pure sodium azide was obtained by this method. "


http://www.roguesci.org/theforum/showthread.php?t=4238&highlight=isopropyl+nitrite&*

Excerpt:

"The value of hydrazine for our purposes is limited to the usefulness
of hydrazine as a precursor in the synthesis of several different types
of primary explosives . Such a need is satisfied by the use of
hydrazine sulfate directly in some reactions . Other reactions require
the hydrazine hydrate freebase which may be obtained from the hydrazine sulfate
by reaction of the solid with solid sodium hydroxide , and the absolute minimum
of added water to form a thick slurry of sodium sulfate crystals in hydrazine hydrate ,
which is taken up in successive portions of methanol . Proper technique and glassware
is needed for reactions involving the freebase hydrazine since it is destroyed
fairly rapidly by exposure to oxygen of the air .

For lab scale synthesis of hydrazine sulfate , the reaction of urea and
sodium hypochlorite is the best method . There is an extensive detailed
description at the Hive . That process is superior to any other published
method for lab scale synthesis of hydrazine from common materials .

The reaction of a slight excess of isopropyl nitrite with a cold methanol solution
of hydrazine hydrate and slight excess of sodium hydroxide , in a slightly pressurized
reaction flask produces a solid precipitate of pure sodium azide crystals in pretty good yield .
A pressure relieved , sealed glass and teflon reaction flask and addition funnel ,
with magnetic stirrer and an ice water bath is needed for performing the synthesis .

Regarding isopropyl nitrite ,

The isopropyl nitrite needed for the synthesis of sodium azide may be prepared
in advance and kept cold in the freezer , stored in a glass bottle having a teflon gasketed
threaded closure . The isopropyl nitrite may be made at salted ice bath temperature ,
by fairly rapid addition of a freezing cold mixed solution of aqueous 31.45% HCl and
a slight excess of theory of 70% isopropanol , to a well stirred freezing cold aqueous solution
of sodium nitrite in slight excess of theory which has been dumped onto twice its volume
of ice cubes in a flask which is cooled by a salted ice bath . The HCl in isopropanol should
be introduced through a small bore teflon tube extending downward to near the bottom
of the stirred mixture of ice cubes and sodium nitrite solution , or else it will decompose
the isopropyl nitrite which rises to the surface as it forms , if the acid mixture drops onto the
surface and contacts the free ester . It is very important for this reason to introduce the HCl in
isopropanol , near the bottom of the flask to avoid the decomposition of the product .
When all the HCl isopropanol has been added , the stirring is stopped and the isopropyl nitrite
top layer along with some of the lower layer of byproduct salt water is quickly decanted into a
prechilled separatory funnel , and the lower layer drawn off and discarded . The oily ,
bright yellow isopropyl nitrite layer is drained into a prechilled glass bottle having a
teflon gasketed closure , sealed only moderately tight to allow for a bit of overpressure relief
if needed , and stored in a freezer . The storage bottle and cap should be preweighed
so that the added weight of the isopropyl nitrite product can be determined , and it will be known
what molar amount is available for use of this precursor in further reactions . The isopropyl nitrite
fumes freely in the air , producing nitrous fumes from decomposition , as well as fumes from
the intact ester which has a volatility similar to ether . These fumes are highly toxic and physiologically active ,
as is the liquid ester itself so due caution should be observed to avoid inhalation or skin contact ."

Excerpt :

"The urea process was simply the method which appeared to be
most promising for a lab scale approach to producing usable yields
with economy , easily available precursors , and minimal equipment ,
while still being a relatively clean and safe process . I did look at
alternative methods , but the urea method became the clear preference
after all the factors were considered . The urea method works so
well that the synthesis should be confirmed and a technical writer
should do a proper writeup and have it added to the four volume Wiley
Organic Syntheses as an improvement over the older method , whenever
they next update their publication .

Azides were the principal reason for my interest in devising a good method
for lab scale production of hydrazine . And the first order of business
there was to devise a method for producing pure sodium azide directly
without any need for distillation of hydrazine . The freebasing and
methanol extraction of the hydrazine hydrate , followed by reaction in
the cold with isopropyl nitrite , satisfied the goal of producing pure
sodium azide in good yield by the most direct approach found to work .

The alternative Hodgkinson patent process looks to be so simple that
I tried to replicate that reported work , but even after literally two dozen
experiments using the same or slightly varying conditions from those
reported by Hodgkinson , there was ZERO success in producing azides
by Hodgkinsons method , which I quite frankly believe to be fraudulent .
I even tried some significant variations applying my own ideas of how
to troubleshoot and modify the reaction conditions to achieve the desired
results , but nothing I tried worked , even when extremely close control
of pH , temperature , reaction concentrations and mixing parameters were
applied , negative results became the predictable outcome .

On paper and in theory the reactions work beautifully , but in the
reaction vessels , everything else but what you expect should happen
was the rule for "Hodgkinson type" hydrazine sulfate / sodium nitrite
reaction scenarios . Anyone who can make such a reaction produce
azides , should declare how the matter is accomplished , and take a
bow for discovering and sharing the secret . This puzzle has already
stumped and thoroughly humiliated both Rosco and Philou , so Marvin
you are invited and welcome to solve this enigma of molecule crafting ,
and please teach us what we want to know :D "

[Bert]

Thank you. I did assume that this series of synthesis without a proper fume hood and other protective and safety gear would be most foolhardy-

I was losing my mind trying to corelate the Scienc Madness/Mr. Anonymous posts and the E&W/Roscoe Bodine ones some days. BTW, I feel I'm fairly good at identifying writing styles (especialy technical writing) and had suspected the two were alter egos.
I have a hunch about other facets as well.

[Rosco Bodine]

A fume hood isn't required , but a closed reaction vessel equipped
with a vent line is needed for the nitrosation . A large centrifugal
blower can be used to pull a good draft across a work area and
discharge the vapors to a distance downwind . I also have a smaller
blower which draws its intake air through a twenty foot length of
flexible 4" round duct whose end is mounted in a ring which can
be clamped on the ringstand adjacent the opening of a reaction flask .
I light a stick of incense and place it nearby so that the streamer of
smoke gives a visible tracer for the airflow .

Run your hunches by me and I'll tell you if you are on the mark .

I'm actually a bit curious , particularly what the government type
snoopy lurkers may think of my little web published " science experiments " .

[2,4,6-TNP]

At the risk of getting myself put on a bunch of peoples " shit list "

If anyone, but the One God, puts you on their shit list I'd say there's no hope for them; A man who demonstrates wisdom and knowledge should never be mocked! ;)

I am going to say you should probably stick with your airbag source
and try to quantify the composition of the airbag extract so you can
work better with it . On the scale of difficulty , 1 to 10 , an airbag
extraction is a " 1 " and a total synthesis of sodum azide is a " 10 " .

Hearing this makes me thankful for the airbags. I admit that I have not reached a level of such excellence and knowledge to try to synthesize Sodium Azide myself. I accept the fact that I lack wisdom, knowledge, insight, discretion, prudence, discipline, and understanding. Though I am ignorant, I long for wisdom and understanding with all my heart. I seek it in the morning when I wake up, I search for it at midday, and in the evening my eyes look for it. Everywhere I search for wise men, even here at the E&W I look for them. When I think I have found one I love him and listen and watch very carefully. :)

Anyway, thank you Rosco for your reply. I do have one question for you. I do not mean to be a burden to you, it's not my purpose to wear you out. If it pleases you here is my question:

It is about recrystallizing sodium azide. I know sodium azide is highly soluble in water and slightly soluble in alcohol. I do not know very much about recrystallization. I have recrystallized acetylsalicylic acid by first dissolving it in warm 99% isopropyl alcohol, and then simply boiled off the alcohol and the ASA remained and was crystallized. I have recrystallized picric acid by desolving it in minumum amount of hot water, filtering and then cooling in an ice bath, which nicely caused it to crystallize. So I have observed a so called "boiling off" method and also a so called "cooling down" method. I have not been able this far to as you say "quantify the composition" of car airbags because of a lack of knowledge that I hope you will remedy. In my first attemp at synthesizing 4/11 lead nitrate azo-clathrate I simply crushed up sodium azide airbag pellets dessolved them in warm water filtered off the iron oxide and whatever else and measured off some of the solution to use for the synthesis based on what I estimated the sodium azide content to be. The synthesis was successful, but I could clearly see free lead azide under a cheap microscope. That is the method I have been using and its product with excess lead azide is what I used for the ten experiments using the white buckets. I was fearful about "boiling off" the sodium azide solution cause I thought it would decompose, and when I tried the "cooling down" method I hardly got any sodium azide to precipitate. This is my frustration, this is what is bogging me down! :(

As always, I thank you for your gentle reply! ;)

P.S. The reason for my question is this: I believe I will get the best results if I am able to weigh the dry crystallized sodium azide instead of trying to calculate the contents of a solution.

[Microtek]

I'd just like to point out that I have carried out the total synthesis of azo-clathrate all the way from aspirin, metallic lead, nitric acid, isopropanol, urea and hypochlorite ( and a few other trivial reactants ). I shall be the first to admit that it took some experimentation to get it right, but once you have the procedures pegged, it can be done quite routinely.
Most of the procedures are taken from Rosco's work but I have a few alterations which are advantageous to me, because of my supply situation:

1) Isopropyl nitrite is produced by nitrosation of IPA by N2O3 instead of HNO2 as follows: 43 ml HNO3, 50% is added to a flask along with about 10 g potato starch. The flask is equipped with a one hole stopper wit a hose inserted ( both hose and stopper should be somewhat acid resistant; PE will do ).
The flask is heated until the reaction becomes self-sustaining and the mix of NO and NO2 which is in equilibrium with N2O3 is bubbled through about 50 mL IPA. This IPA should be held in another flask equipped with a two-hole stopper because most of the isopropyl nitrite which is produced evaporates ( or maybe most of the nitrosation happens in the gas phase ) and the gaseous product is led into a flask filled with crushed ice.
Once the reaction is over ( it is a very steady reaction, and can be left alone ) that is, the generation of NOx has almost stopped, the product is easily isolated by the ordinary means.
While the describtion may seem long winded and complicated, it is in fact a very convenient method.

2) Production of hydrazine hydrate: 13 g hydrazine sulfate is placed in a suitable vessel along with 15 mL IPA, 99%. 4 g solid NaOH is added and the pellets are crushed and triturated with the HS. After a few minutes, the powdered reactants will attain the appearance of a paste as the produced NaHSO4 stubbornly holds on to the produced hydrazine hydrate. The paste is worked through a little more to ensure complete reaction, and then another 4-5 g solid NaOH is added and worked into the paste to convert the NaHSO4 into Na2SO4 which separates cleanly as a crisply dry powder.
The IPA solution of hydrazine hydrate is removed by decatation or with a syringe, and the remaining powder is extracted a further two times with 10 mL IPA.

The advantage of using only IPA is that there is no possibility of cross-esterification during the reaction of isopropyl nitrite with hydrazine hydrate, so there is no need to carry out the operation under pressure.
Also, the practically anhydrous conditions causes the sodium azide to precipitate completely and instantaneously from the reaction mixture as the nitrite is added.

[Rosco Bodine]

I'd just like to point out that I have carried out the total synthesis of azo-clathrate all the way from aspirin, metallic lead, nitric acid, isopropanol, urea and hypochlorite ( and a few other trivial reactants ). I shall be the first to admit that it took some experimentation to get it right, but once you have the procedures pegged, it can be done quite routinely.
Most of the procedures are taken from Rosco's work but I have a few alterations which are advantageous to me, because of my supply situation:

Necessity is the mother of invention . Convenience and expediency are close
family relations . What can't be properly engineered may be improvised , or
in a pinch even nigger rigged , when that's close enough for government work :D



1) Isopropyl nitrite is produced by nitrosation of IPA by N2O3 instead of HNO2 as follows: 43 ml HNO3, 50% is added to a flask along with about 10 g potato starch. The flask is equipped with a one hole stopper wit a hose inserted ( both hose and stopper should be somewhat acid resistant; PE will do ).
The flask is heated until the reaction becomes self-sustaining and the mix of NO and NO2 which is in equilibrium with N2O3 is bubbled through about 50 mL IPA. This IPA should be held in another flask equipped with a two-hole stopper because most of the isopropyl nitrite which is produced evaporates ( or maybe most of the nitrosation happens in the gas phase ) and the gaseous product is led into a flask filled with crushed ice.
Once the reaction is over ( it is a very steady reaction, and can be left alone ) that is, the generation of NOx has almost stopped, the product is easily isolated by the ordinary means.
While the describtion may seem long winded and complicated, it is in fact a very convenient method.

That is a good workaround for the situation where sodium nitrite is not on hand .
The sodium nitrite has been a difficulty also in other syntheses like DDNP , and
other diazotization or nitrosation type reactions such as for R-Salt . I actually
have a folder containing various nitrite patents and syntheses , including the
starch and nitric acid " nitrous gases " generation method which was used
by Griess in the original work discovering the diazotization reaction . IIRC it
is also possible to similarly decompose nitric acid upon addition of paraformaldehyde ,
which also produces formic acid as a useful byproduct residue .
I am presently spoiled by having forty kilos of food grade sodium nitrite on hand ,
so I haven't been pressed to look at the useful alternative methods , and it
pleases me to see that the alternative method you have described has also
proven useful . This workaround alternative really does put the synthesis of
any compounds requiring nitrite within easier reach , providing an alternate
route for the one precursor which could have difficult availabilty .


2) Production of hydrazine hydrate: 13 g hydrazine sulfate is placed in a suitable vessel along with 15 mL IPA, 99%. 4 g solid NaOH is added and the pellets are crushed and triturated with the HS. After a few minutes, the powdered reactants will attain the appearance of a paste as the produced NaHSO4 stubbornly holds on to the produced hydrazine hydrate. The paste is worked through a little more to ensure complete reaction, and then another 4-5 g solid NaOH is added and worked into the paste to convert the NaHSO4 into Na2SO4 which separates cleanly as a crisply dry powder.
The IPA solution of hydrazine hydrate is removed by decatation or with a syringe, and the remaining powder is extracted a further two times with 10 mL IPA.

The advantage of using only IPA is that there is no possibility of cross-esterification during the reaction of isopropyl nitrite with hydrazine hydrate, so there is no need to carry out the operation under pressure.
Also, the practically anhydrous conditions causes the sodium azide to precipitate completely and instantaneously from the reaction mixture as the nitrite is added.

You are absolutely correct and this is an extremely useful improvement .

I will have to try the use of IPA as the extraction solvent * again * .
Actually my original thinking was parallel to yours on this ,
for avoiding the transesterfication problem of methyl nitrite ,
which does complicate things when methanol is used for the hydrazine extraction solvent .
But I encountered a phase separation where the IPA would not mix with the slurry of solids
to form a single liquid phase and leave a solid residue of sodium sulfate .
I also exploit the half-neutralization of the low solubility hydrazine sulfate
to form the highly soluble dihydrazine sulfate and sodium bisulfate ,
to create a more fluid mixture and facilitate stirring , before adding
the remaining half of the solid NaOH to complete the freebasing
of the hydrazine hydrate and conversion of the sodium bisulfate
to the normal sulfate .

The reason for my phase separation problem I believe is that I did not attempt
to perform the freebasing of the hydrazine from hydrazine sulfate * already *
immersed in the IPA * before * the NaOH was added , but rather did the
freebasing in the aqueous system of the neutralization reaction's own byproduct water
along with a very small amount of added water . This created a persistent
aqueous phase reaction mixture which stubbornly resisted extraction by IPA ,
even when the phases were shaken together , the slurry remained a slurry
which refused to release its solids and contribute its liquid containing the
hydrazine hydrate to mix with the IPA and form a single liquid phase which
could be decanted . After observing this peculiar phase separation , I did
not try to isolate the problem with further experiments , but simply abandoned
the IPA solvent in favor of methanol , since methanol did extract the aqueous
phase cleanly and presented no phase separation difficulty . Now I know
that I abandoned IPA prematurely , and should have done further experiments
with the sequence and conditions for the freebasing of the hydrazine to see
if the persistent phase separation problem could be avoided .

Using IPA as the freebasing and * simultaneous * extraction solvent would provide
a reaction system which could be managed in an open beaker or
even an ordinary glass jar . An ordinary ice bath for cooling the reaction
mixture would probably still be a good idea since the isopropyl nitrite is
about as volatile as ethyl ether , and the formation of the sodium azide
is exothermic , which may cause unreacted isopropyl nitrite to escape a
too warm reaction mixture .

Another possibility that may be worth experimentation is that the formation
of the isopropyl nitrite may not have to be done as a separate reaction ,
but it may form in situ in the cold , basified hydrazine hydrate in IPA , as
the " nitrous gases " are simply bubbled through directly from the generator .
The isopropyl nitrite should react as quickly as it forms with the hydrazine
hydrate and NaOH to form the sodium azide directly . If this works as I
believe it probably would , you would simply bubble through the nitrous gases
from the generator until no more sodium azide precipitates , and then
filter the crystals .

These are very interesting developments . Interesting indeed .


2,4,6-TNP :

Pour your solution into a large shallow glass rectangular baking tray .
Place the tray on a heating pad and blow air across it with a small fan .
Evaporation produces crystals . Salt works have been around for
a few thousand years , and not one of them ever failed to work ,
so you can have confidence that yours will work as well :D

P.S. I don't mind a * few * compliments , even a pat on the back is okay .

But p l e e e e e ase don't be excessive with your praise .

It makes me feel like your dog is humping my leg :eek:

[Child-of-Bodom]

Sorry for bringing this thread back to basics, but Microtek or Pbd, did you ever had reproducable results with making 2,4-dinitrobenzenediazonium perchlorate? I have some 2,4 dinitroallinine, and I would like to give it a try and post results. (I have analar grade 2,4 dinitroallinine)
In the first post about 2,4-dbp, Microtek uses a very, very small amount of H2SO4 (1ml), may I ask how you stirred that?? In an eppendorf tube with a very, very small flea or something like that?
Pdb, you didn't post any succes here around 2,4-dbp, did you ever managed to get it to work, or did you give up? Thanks in advance for your answer.

[pdb]

In the first post about 2,4-dbp, Microtek uses a very, very small amount of H2SO4 (1ml), may I ask how you stirred that?? In an eppendorf tube with a very, very small flea or something like that?


Let us Microtek answer: he has his own secrets to (often) handle very tiny amounts of chems. For myself, I multiplied his proportions by 5, making handling of 5ml H2SO4 easy.

Pdb, you didn't post any succes here around 2,4-dbp, did you ever managed to get it to work, or did you give up? Thanks in advance for your answer.

I have prepared 2,4-dbp four times, and, surprisingly, my observations differ somewhat from Microtek's. Match-head size amounts of the stuff would deflagrate strongly with a very bright flash, when smaller equivalent amounts of DPNA would detonate with high brisance (Microtek is claiming exactly the opposite). However, 0.3 gr of each hand pressed in a 4mm straw give similar results on an iron plate. The power and brisance seem similar, however a few mg 2,4-dbp undergoes DDT, when DPNA, in quantities of the order of size of 1mg, straightly detonates.

The only way to solve this puzzle would be than a third fellow prepare some of this stuff. Will you be that one ?

[Child-of-Bodom]

The only way to solve this puzzle would be than a third fellow prepare some of this stuff. Will you be that one ?

If no-one will be earlier then this evening, then 'yes' :D . Although I do nót have 3-nitroaniline, so I cannot compare with DPNA :(.

Maybe a stupid question, but does the addition of NaNO2 to the SA release a lot of fumes?
I do not have a fumehood in my lab, so that means I have to do late-night experiments in other peoples labs...
----------
EDIT: Google and some common sence teached me some NO will form. I'll look for a free fumehood without much attantion, otherwise I'll postpone the experiment.

[Child-of-Bodom]

The only way to solve this puzzle would be than a third fellow prepare some of this stuff. Will you be that one ?

If no-one will be earlier then this evening, then 'yes' :D . Although I do nót have 3-nitroaniline, so I cannot compare with DPNA :(.

Maybe a stupid question, but does the addition of NaNO2 to the SA release a lot of fumes?
I do not have a fumehood in my lab, so that means I have to do late-night experiments in other peoples labs...
----------
EDIT: Google and some common sence teached me some NO will form. I'll look for a free fumehood without much attantion, otherwise I'll postpone the experiment.

[Child-of-Bodom]

The only way to solve this puzzle would be than a third fellow prepare some of this stuff. Will you be that one ?

If no-one will be earlier then this evening, then 'yes' :D . Although I do nót have 3-nitroaniline, so I cannot compare with DPNA :(.

Maybe a stupid question, but does the addition of NaNO2 to the SA release a lot of fumes?
I do not have a fumehood in my lab, so that means I have to do late-night experiments in other peoples labs...
----------
EDIT: Google and some common sence teached me some NO will form. I'll look for a free fumehood without much attantion, otherwise I'll postpone the experiment.

[pdb]

Maybe a stupid question, but does the addition of NaNO2 to the SA release a lot of fumes?

Add NaNO2 over a 15 minutes period, holding the beaker in an ice bath and stirring well, and you will not get NOx in noticeable quantity. A fumehood is thus absolutly unnecessary.

I would also advise that you don't exceed the amount of ice to be added in the procedure, and wash the precipitate once on filter with water sligthy acidified with HClO4.

[pdb]

Maybe a stupid question, but does the addition of NaNO2 to the SA release a lot of fumes?

Add NaNO2 over a 15 minutes period, holding the beaker in an ice bath and stirring well, and you will not get NOx in noticeable quantity. A fumehood is thus absolutly unnecessary.

I would also advise that you don't exceed the amount of ice to be added in the procedure, and wash the precipitate once on filter with water sligthy acidified with HClO4.

[pdb]

Maybe a stupid question, but does the addition of NaNO2 to the SA release a lot of fumes?

Add NaNO2 over a 15 minutes period, holding the beaker in an ice bath and stirring well, and you will not get NOx in noticeable quantity. A fumehood is thus absolutly unnecessary.

I would also advise that you don't exceed the amount of ice to be added in the procedure, and wash the precipitate once on filter with water sligthy acidified with HClO4.

[Microtek]

Well, it's not a secret really; it's just that I have furnished my lab to focus on "microscale" chemistry ( hence my name on the forum ). At first it was a necessity due to space limitations, but then I came to the conclusion that the best ways to stay safe when dealing with explosive or poisonous substances are to either handle them from far away or only handle very small amounts.
Since the first method is quite impractical, I chose the latter...

Anyway, the sulfuric acid was stirred by placing it in a tall, narrow ( 25 mm ) cylindrical glass with a flat bottom along with a 20 mm stir bar. There was obviously not enough acid to cover the stir bar, but as it reaches almost to the walls of the container, the contents are adequately mixed anyway.

[Microtek]

Well, it's not a secret really; it's just that I have furnished my lab to focus on "microscale" chemistry ( hence my name on the forum ). At first it was a necessity due to space limitations, but then I came to the conclusion that the best ways to stay safe when dealing with explosive or poisonous substances are to either handle them from far away or only handle very small amounts.
Since the first method is quite impractical, I chose the latter...

Anyway, the sulfuric acid was stirred by placing it in a tall, narrow ( 25 mm ) cylindrical glass with a flat bottom along with a 20 mm stir bar. There was obviously not enough acid to cover the stir bar, but as it reaches almost to the walls of the container, the contents are adequately mixed anyway.

[Microtek]

Well, it's not a secret really; it's just that I have furnished my lab to focus on "microscale" chemistry ( hence my name on the forum ). At first it was a necessity due to space limitations, but then I came to the conclusion that the best ways to stay safe when dealing with explosive or poisonous substances are to either handle them from far away or only handle very small amounts.
Since the first method is quite impractical, I chose the latter...

Anyway, the sulfuric acid was stirred by placing it in a tall, narrow ( 25 mm ) cylindrical glass with a flat bottom along with a 20 mm stir bar. There was obviously not enough acid to cover the stir bar, but as it reaches almost to the walls of the container, the contents are adequately mixed anyway.

[nbk2000]

Roscoe:

You can withhold information if you want to, in the belief that it will deter the 'unprepared', but they'll do it anyways, only they'll be guessing and that's what kills.

If they are fully informed, and see this involved process, that'll deter them if they're not serious about it, and if they are serious about it, it'll keep them from getting killed.

This is what's always bugged me about patents...the whole 'those skilled in the arts' bullshit.

How do you get skilled in the arts except to be trained by those who already know it, if no one is writing down what they know?! AAARRRGGHHH! :rolleyes:

Write down all you know about it, so others can learn, without the presumption of 'skilled in the arts' preventing the diffusion of the skills.

Nobody taught me about the hazards of distilling HCN or making mustard. Those I had to learn by nearly dying and scars I'll be bearing the rest of my life. I knew going in that the shit was dangerous, and took reasonable precautions, but it was the little details that got me, the kind of details that were never written down on the assumption of 'skilled in the arts'.

[nbk2000]

Roscoe:

You can withhold information if you want to, in the belief that it will deter the 'unprepared', but they'll do it anyways, only they'll be guessing and that's what kills.

If they are fully informed, and see this involved process, that'll deter them if they're not serious about it, and if they are serious about it, it'll keep them from getting killed.

This is what's always bugged me about patents...the whole 'those skilled in the arts' bullshit.

How do you get skilled in the arts except to be trained by those who already know it, if no one is writing down what they know?! AAARRRGGHHH! :rolleyes:

Write down all you know about it, so others can learn, without the presumption of 'skilled in the arts' preventing the diffusion of the skills.

Nobody taught me about the hazards of distilling HCN or making mustard. Those I had to learn by nearly dying and scars I'll be bearing the rest of my life. I knew going in that the shit was dangerous, and took reasonable precautions, but it was the little details that got me, the kind of details that were never written down on the assumption of 'skilled in the arts'.

[nbk2000]

Roscoe:

You can withhold information if you want to, in the belief that it will deter the 'unprepared', but they'll do it anyways, only they'll be guessing and that's what kills.

If they are fully informed, and see this involved process, that'll deter them if they're not serious about it, and if they are serious about it, it'll keep them from getting killed.

This is what's always bugged me about patents...the whole 'those skilled in the arts' bullshit.

How do you get skilled in the arts except to be trained by those who already know it, if no one is writing down what they know?! AAARRRGGHHH! :rolleyes:

Write down all you know about it, so others can learn, without the presumption of 'skilled in the arts' preventing the diffusion of the skills.

Nobody taught me about the hazards of distilling HCN or making mustard. Those I had to learn by nearly dying and scars I'll be bearing the rest of my life. I knew going in that the shit was dangerous, and took reasonable precautions, but it was the little details that got me, the kind of details that were never written down on the assumption of 'skilled in the arts'.

[Rosco Bodine]

Microteks variation of the method is a lot safer and less complicated ,
so it is a better candidate for " improvised sodium azide " .

Really I haven't kept any secrets about the experiments I have done .
I have simply never written down the synthesis as a step by step
experimental . But I did describe the conditions and the molar ratios .
That is often all the information which is given in many technical papers .

The most convenient synthesis for sodium azide is still something of a
work in progress . Microteks method and some experiments to follow
should pin down the details of a simple step by step which will be
another one for the books .

[Rosco Bodine]

Microteks variation of the method is a lot safer and less complicated ,
so it is a better candidate for " improvised sodium azide " .

Really I haven't kept any secrets about the experiments I have done .
I have simply never written down the synthesis as a step by step
experimental . But I did describe the conditions and the molar ratios .
That is often all the information which is given in many technical papers .

The most convenient synthesis for sodium azide is still something of a
work in progress . Microteks method and some experiments to follow
should pin down the details of a simple step by step which will be
another one for the books .

[Rosco Bodine]

Microteks variation of the method is a lot safer and less complicated ,
so it is a better candidate for " improvised sodium azide " .

Really I haven't kept any secrets about the experiments I have done .
I have simply never written down the synthesis as a step by step
experimental . But I did describe the conditions and the molar ratios .
That is often all the information which is given in many technical papers .

The most convenient synthesis for sodium azide is still something of a
work in progress . Microteks method and some experiments to follow
should pin down the details of a simple step by step which will be
another one for the books .

[nbk2000]

Because of the length of this thread, I've consolidated all the mentioned patents into the following list for ease of use.

When the subject of the patent wasn't clearly stated, I left it blank, rather than guess.

Copy is going in the Patents List thread.

++++++++++++++++++++++++++++

American Patents:

US1478429 Igniters
See example 1 for the most simple.

US1511771

US1625966 lead methyldiisonitrosamine salt (PbMEDNA)

US2064817 Precursor to Lead Diazoaminotetrazolate Styphnate and related cpds.

US2066954 5-Nitrotetrazole

US2090745 Lead Diazoaminotetrazolate

US2175249 Igniter Compounds
See example 2 for one of the best "first fire" low order detonating flash igniters , a superbly useful and easily made compound .

US2929699 Triaminoguanidine explosive salts .

US3173755

US3284255 Lead Azide and Barium Styphnate Explosive Initiator Composition

US3293091 Igniter
Example 4

US3310569 Crystalline Double Salt Pb Styphnate and Pb Nitroaminotetrazole

US3431156 Azo-chlathrates

US4024818 Detonating composition Mercuric-5-nitrotetrazole .

US4093623 5-Nitrotetrazole

US4094879 5-Nitrotetrazole

US4552598 5-Nitrotetrazole

British Patents:

GB0185555
GB0195344
GB0308179
GB0412460 Tetracene salts
GB0718934
GB0924239 Sorbitan Tetranitrate (NOT Sorbitol)
GB1069440 Crystalline Double Salt Pb Styphnate and Pb Nitroaminotetrazole
GB1519796 5-Nitrotetrazole

German Patents
DE258679 m-Nitrobenzenediazonium perchlorate

[nbk2000]

Because of the length of this thread, I've consolidated all the mentioned patents into the following list for ease of use.

When the subject of the patent wasn't clearly stated, I left it blank, rather than guess.

Copy is going in the Patents List thread.

++++++++++++++++++++++++++++

American Patents:

US1478429 Igniters
See example 1 for the most simple.

US1511771

US1625966 lead methyldiisonitrosamine salt (PbMEDNA)

US2064817 Precursor to Lead Diazoaminotetrazolate Styphnate and related cpds.

US2066954 5-Nitrotetrazole

US2090745 Lead Diazoaminotetrazolate

US2175249 Igniter Compounds
See example 2 for one of the best "first fire" low order detonating flash igniters , a superbly useful and easily made compound .

US2929699 Triaminoguanidine explosive salts .

US3173755

US3284255 Lead Azide and Barium Styphnate Explosive Initiator Composition

US3293091 Igniter
Example 4

US3310569 Crystalline Double Salt Pb Styphnate and Pb Nitroaminotetrazole

US3431156 Azo-chlathrates

US4024818 Detonating composition Mercuric-5-nitrotetrazole .

US4093623 5-Nitrotetrazole

US4094879 5-Nitrotetrazole

US4552598 5-Nitrotetrazole

British Patents:

GB0185555
GB0195344
GB0308179
GB0412460 Tetracene salts
GB0718934
GB0924239 Sorbitan Tetranitrate (NOT Sorbitol)
GB1069440 Crystalline Double Salt Pb Styphnate and Pb Nitroaminotetrazole
GB1519796 5-Nitrotetrazole

German Patents
DE258679 m-Nitrobenzenediazonium perchlorate

[nbk2000]

Because of the length of this thread, I've consolidated all the mentioned patents into the following list for ease of use.

When the subject of the patent wasn't clearly stated, I left it blank, rather than guess.

Copy is going in the Patents List thread.

++++++++++++++++++++++++++++

American Patents:

US1478429 Igniters
See example 1 for the most simple.

US1511771

US1625966 lead methyldiisonitrosamine salt (PbMEDNA)

US2064817 Precursor to Lead Diazoaminotetrazolate Styphnate and related cpds.

US2066954 5-Nitrotetrazole

US2090745 Lead Diazoaminotetrazolate

US2175249 Igniter Compounds
See example 2 for one of the best "first fire" low order detonating flash igniters , a superbly useful and easily made compound .

US2929699 Triaminoguanidine explosive salts .

US3173755

US3284255 Lead Azide and Barium Styphnate Explosive Initiator Composition

US3293091 Igniter
Example 4

US3310569 Crystalline Double Salt Pb Styphnate and Pb Nitroaminotetrazole

US3431156 Azo-chlathrates

US4024818 Detonating composition Mercuric-5-nitrotetrazole .

US4093623 5-Nitrotetrazole

US4094879 5-Nitrotetrazole

US4552598 5-Nitrotetrazole

British Patents:

GB0185555
GB0195344
GB0308179
GB0412460 Tetracene salts
GB0718934
GB0924239 Sorbitan Tetranitrate (NOT Sorbitol)
GB1069440 Crystalline Double Salt Pb Styphnate and Pb Nitroaminotetrazole
GB1519796 5-Nitrotetrazole

German Patents
DE258679 m-Nitrobenzenediazonium perchlorate

[Rosco Bodine]

Attached is an English language patent by Von Herz similar
to the later German patent DE258679 m-Nitrobenzenediazonium perchlorate
above .

Also of interest regarding " iso-MEDINA " type compounds
from ethylene or propylene gas reacted with N2O3 in
ether or other inert solvent is

US1473825

[Rosco Bodine]

Attached is an English language patent by Von Herz similar
to the later German patent DE258679 m-Nitrobenzenediazonium perchlorate
above .

Also of interest regarding " iso-MEDINA " type compounds
from ethylene or propylene gas reacted with N2O3 in
ether or other inert solvent is

US1473825

[Rosco Bodine]

Attached is an English language patent by Von Herz similar
to the later German patent DE258679 m-Nitrobenzenediazonium perchlorate
above .

Also of interest regarding " iso-MEDINA " type compounds
from ethylene or propylene gas reacted with N2O3 in
ether or other inert solvent is

US1473825

[Child-of-Bodom]

I've tried 2,4-dbp, but I failed. I let 5ml H2SO4 and 0.75g NaNO2 react, reaction coole dwith ice, but it didn't dissolve all. After heating at 70°C for an hour a little bit was still undissolved.
Due to a lack of time, I let the mixture stand over a couple of days, then I added 1.50g 2,4 dinitroaniline, the ice and the dil. HClO4.
No precipitation was formed... Next time I will do the synthesis all in one... I keep you updated.

[Child-of-Bodom]

I've tried 2,4-dbp, but I failed. I let 5ml H2SO4 and 0.75g NaNO2 react, reaction coole dwith ice, but it didn't dissolve all. After heating at 70°C for an hour a little bit was still undissolved.
Due to a lack of time, I let the mixture stand over a couple of days, then I added 1.50g 2,4 dinitroaniline, the ice and the dil. HClO4.
No precipitation was formed... Next time I will do the synthesis all in one... I keep you updated.

[Child-of-Bodom]

I've tried 2,4-dbp, but I failed. I let 5ml H2SO4 and 0.75g NaNO2 react, reaction coole dwith ice, but it didn't dissolve all. After heating at 70°C for an hour a little bit was still undissolved.
Due to a lack of time, I let the mixture stand over a couple of days, then I added 1.50g 2,4 dinitroaniline, the ice and the dil. HClO4.
No precipitation was formed... Next time I will do the synthesis all in one... I keep you updated.

[2,4,6-TNP]

Dear Rosco Bodine,

When you were mentioning earlier in this thread that you believed
that an ignition charge is capable of compressing an adjacent primary
and base charge is the following patent anything of what you were
expressing? US6736068

[2,4,6-TNP]

Dear Rosco Bodine,

When you were mentioning earlier in this thread that you believed
that an ignition charge is capable of compressing an adjacent primary
and base charge is the following patent anything of what you were
expressing? US6736068

[2,4,6-TNP]

Dear Rosco Bodine,

When you were mentioning earlier in this thread that you believed
that an ignition charge is capable of compressing an adjacent primary
and base charge is the following patent anything of what you were
expressing? US6736068

[Rosco Bodine]

The patent is very similar , but describes the effect applied in
an unconventional detonator of the the " safety detonator " type .

Dyno Nobel is confirming the principle I stated concerning the
in situ compression of the remaining firing train elements by
the initial relatively gentle pressure which is first developed by
the gases evolved from a flash igniter , before its combustion
makes the transition to low order detonation . The patent
seems to relate specifically to the principle applied to a design
for a detonator which contains no unequivocal primary as an
intermediate element in the firing train . However the principle
of in situ compression during the "first fire" combustion applies
to any scenario where a flash igniter is used . That is precisely
one reason which accounts for the superior output from a cap
which utilizes a flash igniter , as compared with an otherwise
identically loaded cap which has no flash igniter , but has its
unequivocal primary fired directly .

I suppose I must plead guilty to running off at the mouth about
state of the art stuff :D , since that looks like a recent patent .

[Rosco Bodine]

The patent is very similar , but describes the effect applied in
an unconventional detonator of the the " safety detonator " type .

Dyno Nobel is confirming the principle I stated concerning the
in situ compression of the remaining firing train elements by
the initial relatively gentle pressure which is first developed by
the gases evolved from a flash igniter , before its combustion
makes the transition to low order detonation . The patent
seems to relate specifically to the principle applied to a design
for a detonator which contains no unequivocal primary as an
intermediate element in the firing train . However the principle
of in situ compression during the "first fire" combustion applies
to any scenario where a flash igniter is used . That is precisely
one reason which accounts for the superior output from a cap
which utilizes a flash igniter , as compared with an otherwise
identically loaded cap which has no flash igniter , but has its
unequivocal primary fired directly .

I suppose I must plead guilty to running off at the mouth about
state of the art stuff :D , since that looks like a recent patent .

[Rosco Bodine]

The patent is very similar , but describes the effect applied in
an unconventional detonator of the the " safety detonator " type .

Dyno Nobel is confirming the principle I stated concerning the
in situ compression of the remaining firing train elements by
the initial relatively gentle pressure which is first developed by
the gases evolved from a flash igniter , before its combustion
makes the transition to low order detonation . The patent
seems to relate specifically to the principle applied to a design
for a detonator which contains no unequivocal primary as an
intermediate element in the firing train . However the principle
of in situ compression during the "first fire" combustion applies
to any scenario where a flash igniter is used . That is precisely
one reason which accounts for the superior output from a cap
which utilizes a flash igniter , as compared with an otherwise
identically loaded cap which has no flash igniter , but has its
unequivocal primary fired directly .

I suppose I must plead guilty to running off at the mouth about
state of the art stuff :D , since that looks like a recent patent .

[2,4,6-TNP]

The patent is rather new. It has taken them all this time to get to
where they are in using "thermites" to cause the detonation of
secondary explosives with out the aid of a primary, and I'm still
not convinced that they have mastered the technique completly. My guess
would be that they may end up with quite a few low order detonations with
that setup (I don't know)!

The more I study the configuration you mentioned of
using a column diameter of 9.5MM and using:

- .5 grams of Lead Nitrato-Bis Basic Lead Picrate of US2175249
- 1.5 grams of -[4 (Basic Lead Picrate-Lead Nitrate--Lead Azide)-11 Lead Azide] of US3431156
- 2.5 grams of high purity picric acid pressed in .5 gram increments

I'd say it's hard to improve on it, and I don't have much interest in
using thermites in detonators when I can use the configuration above.

I have just one more question about it to complete my knowledge about
how to best make use of it. Is a .5 gram ignition charge optimal to best
"cash in" on it's ability to compress the primary and base charge, or is
more than a .5 gram ignition charge needed to achieve the densities
mentioned in the patent?

Edit: When I said " I didn't have much interest in using thermites in
detonators" I was not trying to in any way discredit the writer's
of the patent, niether was I implying that I believed there invention
was a "dud" or unreliable( I don't know). In fact what I truly think is
that it is a most excellent idea if they can get it to work reliably.

In the past, every designer seems to try to stray away from using
any large amount of a primary and have tried to eliminate their need
for primaries altogether for safety reasons. However in this patent
the revelation that a thermite ignition mixture can compress a high
explosive to a greater density than is possible by normal loading
methods while at the same time causing it to detonate may well
be the near future of large military bombs.

Just think, if the detonator described in the patent works reliably
what's to keep them from scaling it up all the way to a 2,000 Lb
bomb? This would be possible, because no primary explosive
would be involved and thermite compositions are very stable!
Imagine a 2,000 pound "detonator" of this type where
everything is scaled up; the ignition charge and the secondary explosive.
Theoretically, you could use the very large thermite ignition charge
to compress the entire contents of a 2,000 lb bomb, while at the same time
causing the densified (not a word) secondary explosive to achieve unheard of
detonation velocities in a conventional bomb. Who knows? This may be what the
U.S. military is testing right now or if they're not it may be profitable for them
to work on it.

I just don't know! If I knew more about the so called
"dead-pressing" of some explosives (Which I think is still capable of detonating)
I would have a better idea about the limits of this to create
a new era in military munitions; The idea of using a low
explosive to compress a high explosive to a density unachievable
in the factory and by the same causing it's detonation!
Just a thought!

Thank you for your reply! :)

[2,4,6-TNP]

The patent is rather new. It has taken them all this time to get to
where they are in using "thermites" to cause the detonation of
secondary explosives with out the aid of a primary, and I'm still
not convinced that they have mastered the technique completly. My guess
would be that they may end up with quite a few low order detonations with
that setup (I don't know)!

The more I study the configuration you mentioned of
using a column diameter of 9.5MM and using:

- .5 grams of Lead Nitrato-Bis Basic Lead Picrate of US2175249
- 1.5 grams of -[4 (Basic Lead Picrate-Lead Nitrate--Lead Azide)-11 Lead Azide] of US3431156
- 2.5 grams of high purity picric acid pressed in .5 gram increments

I'd say it's hard to improve on it, and I don't have much interest in
using thermites in detonators when I can use the configuration above.

I have just one more question about it to complete my knowledge about
how to best make use of it. Is a .5 gram ignition charge optimal to best
"cash in" on it's ability to compress the primary and base charge, or is
more than a .5 gram ignition charge needed to achieve the densities
mentioned in the patent?

Edit: When I said " I didn't have much interest in using thermites in
detonators" I was not trying to in any way discredit the writer's
of the patent, niether was I implying that I believed there invention
was a "dud" or unreliable( I don't know). In fact what I truly think is
that it is a most excellent idea if they can get it to work reliably.

In the past, every designer seems to try to stray away from using
any large amount of a primary and have tried to eliminate their need
for primaries altogether for safety reasons. However in this patent
the revelation that a thermite ignition mixture can compress a high
explosive to a greater density than is possible by normal loading
methods while at the same time causing it to detonate may well
be the near future of large military bombs.

Just think, if the detonator described in the patent works reliably
what's to keep them from scaling it up all the way to a 2,000 Lb
bomb? This would be possible, because no primary explosive
would be involved and thermite compositions are very stable!
Imagine a 2,000 pound "detonator" of this type where
everything is scaled up; the ignition charge and the secondary explosive.
Theoretically, you could use the very large thermite ignition charge
to compress the entire contents of a 2,000 lb bomb, while at the same time
causing the densified (not a word) secondary explosive to achieve unheard of
detonation velocities in a conventional bomb. Who knows? This may be what the
U.S. military is testing right now or if they're not it may be profitable for them
to work on it.

I just don't know! If I knew more about the so called
"dead-pressing" of some explosives (Which I think is still capable of detonating)
I would have a better idea about the limits of this to create
a new era in military munitions; The idea of using a low
explosive to compress a high explosive to a density unachievable
in the factory and by the same causing it's detonation!
Just a thought!

Thank you for your reply! :)

[2,4,6-TNP]

The patent is rather new. It has taken them all this time to get to
where they are in using "thermites" to cause the detonation of
secondary explosives with out the aid of a primary, and I'm still
not convinced that they have mastered the technique completly. My guess
would be that they may end up with quite a few low order detonations with
that setup (I don't know)!

The more I study the configuration you mentioned of
using a column diameter of 9.5MM and using:

- .5 grams of Lead Nitrato-Bis Basic Lead Picrate of US2175249
- 1.5 grams of -[4 (Basic Lead Picrate-Lead Nitrate--Lead Azide)-11 Lead Azide] of US3431156
- 2.5 grams of high purity picric acid pressed in .5 gram increments

I'd say it's hard to improve on it, and I don't have much interest in
using thermites in detonators when I can use the configuration above.

I have just one more question about it to complete my knowledge about
how to best make use of it. Is a .5 gram ignition charge optimal to best
"cash in" on it's ability to compress the primary and base charge, or is
more than a .5 gram ignition charge needed to achieve the densities
mentioned in the patent?

Edit: When I said " I didn't have much interest in using thermites in
detonators" I was not trying to in any way discredit the writer's
of the patent, niether was I implying that I believed there invention
was a "dud" or unreliable( I don't know). In fact what I truly think is
that it is a most excellent idea if they can get it to work reliably.

In the past, every designer seems to try to stray away from using
any large amount of a primary and have tried to eliminate their need
for primaries altogether for safety reasons. However in this patent
the revelation that a thermite ignition mixture can compress a high
explosive to a greater density than is possible by normal loading
methods while at the same time causing it to detonate may well
be the near future of large military bombs.

Just think, if the detonator described in the patent works reliably
what's to keep them from scaling it up all the way to a 2,000 Lb
bomb? This would be possible, because no primary explosive
would be involved and thermite compositions are very stable!
Imagine a 2,000 pound "detonator" of this type where
everything is scaled up; the ignition charge and the secondary explosive.
Theoretically, you could use the very large thermite ignition charge
to compress the entire contents of a 2,000 lb bomb, while at the same time
causing the densified (not a word) secondary explosive to achieve unheard of
detonation velocities in a conventional bomb. Who knows? This may be what the
U.S. military is testing right now or if they're not it may be profitable for them
to work on it.

I just don't know! If I knew more about the so called
"dead-pressing" of some explosives (Which I think is still capable of detonating)
I would have a better idea about the limits of this to create
a new era in military munitions; The idea of using a low
explosive to compress a high explosive to a density unachievable
in the factory and by the same causing it's detonation!
Just a thought!

Thank you for your reply! :)

[Rosco Bodine]

For the flash igniter in a fuse cap .1 gram of any Pb basic picrate type is plenty .
Using more , up to maybe .2 gram probably doesn't increase the output
of the entire firing train , and .5 gram is " doubly double " and then some
more beyond what you probably need .

In an electric cap , whatever amount fills the filament envelope is plenty .
Generally , .1 gram is a nice round number I have found works well and
provides a comfortable margin and .2 gram is as much as I'd ever use .

The important aspect for the flash igniter to quickly DDT to low order is
that it be used as a loose charge . Any pellet forming method applied
to the igniter composition will slow its DDT and increase the minimum
amount needed for reaching that DDT transition . Keeping this in mind
you can then fine tune the performance of the flash igniter to behave
as you desire . It depends on what is the nature of the adjacent material
and what effect you want to be delivered by the output of the " first fire "
composition , that determines how you configure the firing squib .

The column diameter for the firing train in a detonator has great bearing
upon the charge weights required to achieve a certain " volume geometry "
which is found to work efficiently in such devices . I have mentioned the
effect of initiators as being similar to the behavior and intended function
of a " ribbon charge " , where the directed energy is related to the geometry
of the layer , specifically the ratio of the thickness to the diameter for a
specific layer of initiating explosive .

Now for example say that at a 6 mm column diameter it is found that .5 gram
of some experimental initiator produces a pellet having an ideal geometry for
intiating the base charge at the same diameter . And lets say we intend to
scale up the detonator to a 9 mm column diameter , which is 1.5 times larger
in physical dimensions than the original 6 mm diameter test detonator . The
mind is tempted to believe that this is simple arithmetic , and that since the
larger detonator is 1.5 times larger then it should contain 1.5 times the charge
weights to maintain the charge geometry , even though that is a way wrong
" arithmetic " being applied to a * geometric * increase which is closer to 3.4 !

So to maintain the same charge geometry found to work well for the 6 mm column ,
and translate that geometry to a 9 mm column , all of the charge quantities for the
6 mm device have to be multiplied by 3.4 , due to the geometric nature of volumes
as they increase geometrically from increases in linear dimensions of containers .

Geometry is quite important for the firing elements in detonators , and so it becomes
clear that published figures regarding the performance of initiating explosives is
information which is only pertinent to comparisons performed in parallel tests done
under exactly the same conditions , at exactly the same column diameter where
different sample materials are compared to each other . Such information cannot
be directly translated to loadings and performance at any different diameters ,
where even a 1 mm change results in quite different characteristics because of
the altered volume geometry .

Anyway the point is , that for your own particular detonator design , you have
to test yourself the quantities and determine what are the threshold amounts
and extrapolated excesses you will employ for reliability . These firing trains
are indeed affected by small dimensional changes which have bearing on the
loadings found to be optimum . The exact loading figures for your particular
custom created design will therefore be absolutely unique to your device and
determined by your own tests . Whatever I tell you about such quantities is
something you should understand is then only a " ball park " generalization ,
and you may discover a variation on such figures from your own tests .

[Rosco Bodine]

For the flash igniter in a fuse cap .1 gram of any Pb basic picrate type is plenty .
Using more , up to maybe .2 gram probably doesn't increase the output
of the entire firing train , and .5 gram is " doubly double " and then some
more beyond what you probably need .

In an electric cap , whatever amount fills the filament envelope is plenty .
Generally , .1 gram is a nice round number I have found works well and
provides a comfortable margin and .2 gram is as much as I'd ever use .

The important aspect for the flash igniter to quickly DDT to low order is
that it be used as a loose charge . Any pellet forming method applied
to the igniter composition will slow its DDT and increase the minimum
amount needed for reaching that DDT transition . Keeping this in mind
you can then fine tune the performance of the flash igniter to behave
as you desire . It depends on what is the nature of the adjacent material
and what effect you want to be delivered by the output of the " first fire "
composition , that determines how you configure the firing squib .

The column diameter for the firing train in a detonator has great bearing
upon the charge weights required to achieve a certain " volume geometry "
which is found to work efficiently in such devices . I have mentioned the
effect of initiators as being similar to the behavior and intended function
of a " ribbon charge " , where the directed energy is related to the geometry
of the layer , specifically the ratio of the thickness to the diameter for a
specific layer of initiating explosive .

Now for example say that at a 6 mm column diameter it is found that .5 gram
of some experimental initiator produces a pellet having an ideal geometry for
intiating the base charge at the same diameter . And lets say we intend to
scale up the detonator to a 9 mm column diameter , which is 1.5 times larger
in physical dimensions than the original 6 mm diameter test detonator . The
mind is tempted to believe that this is simple arithmetic , and that since the
larger detonator is 1.5 times larger then it should contain 1.5 times the charge
weights to maintain the charge geometry , even though that is a way wrong
" arithmetic " being applied to a * geometric * increase which is closer to 3.4 !

So to maintain the same charge geometry found to work well for the 6 mm column ,
and translate that geometry to a 9 mm column , all of the charge quantities for the
6 mm device have to be multiplied by 3.4 , due to the geometric nature of volumes
as they increase geometrically from increases in linear dimensions of containers .

Geometry is quite important for the firing elements in detonators , and so it becomes
clear that published figures regarding the performance of initiating explosives is
information which is only pertinent to comparisons performed in parallel tests done
under exactly the same conditions , at exactly the same column diameter where
different sample materials are compared to each other . Such information cannot
be directly translated to loadings and performance at any different diameters ,
where even a 1 mm change results in quite different characteristics because of
the altered volume geometry .

Anyway the point is , that for your own particular detonator design , you have
to test yourself the quantities and determine what are the threshold amounts
and extrapolated excesses you will employ for reliability . These firing trains
are indeed affected by small dimensional changes which have bearing on the
loadings found to be optimum . The exact loading figures for your particular
custom created design will therefore be absolutely unique to your device and
determined by your own tests . Whatever I tell you about such quantities is
something you should understand is then only a " ball park " generalization ,
and you may discover a variation on such figures from your own tests .

[Rosco Bodine]

For the flash igniter in a fuse cap .1 gram of any Pb basic picrate type is plenty .
Using more , up to maybe .2 gram probably doesn't increase the output
of the entire firing train , and .5 gram is " doubly double " and then some
more beyond what you probably need .

In an electric cap , whatever amount fills the filament envelope is plenty .
Generally , .1 gram is a nice round number I have found works well and
provides a comfortable margin and .2 gram is as much as I'd ever use .

The important aspect for the flash igniter to quickly DDT to low order is
that it be used as a loose charge . Any pellet forming method applied
to the igniter composition will slow its DDT and increase the minimum
amount needed for reaching that DDT transition . Keeping this in mind
you can then fine tune the performance of the flash igniter to behave
as you desire . It depends on what is the nature of the adjacent material
and what effect you want to be delivered by the output of the " first fire "
composition , that determines how you configure the firing squib .

The column diameter for the firing train in a detonator has great bearing
upon the charge weights required to achieve a certain " volume geometry "
which is found to work efficiently in such devices . I have mentioned the
effect of initiators as being similar to the behavior and intended function
of a " ribbon charge " , where the directed energy is related to the geometry
of the layer , specifically the ratio of the thickness to the diameter for a
specific layer of initiating explosive .

Now for example say that at a 6 mm column diameter it is found that .5 gram
of some experimental initiator produces a pellet having an ideal geometry for
intiating the base charge at the same diameter . And lets say we intend to
scale up the detonator to a 9 mm column diameter , which is 1.5 times larger
in physical dimensions than the original 6 mm diameter test detonator . The
mind is tempted to believe that this is simple arithmetic , and that since the
larger detonator is 1.5 times larger then it should contain 1.5 times the charge
weights to maintain the charge geometry , even though that is a way wrong
" arithmetic " being applied to a * geometric * increase which is closer to 3.4 !

So to maintain the same charge geometry found to work well for the 6 mm column ,
and translate that geometry to a 9 mm column , all of the charge quantities for the
6 mm device have to be multiplied by 3.4 , due to the geometric nature of volumes
as they increase geometrically from increases in linear dimensions of containers .

Geometry is quite important for the firing elements in detonators , and so it becomes
clear that published figures regarding the performance of initiating explosives is
information which is only pertinent to comparisons performed in parallel tests done
under exactly the same conditions , at exactly the same column diameter where
different sample materials are compared to each other . Such information cannot
be directly translated to loadings and performance at any different diameters ,
where even a 1 mm change results in quite different characteristics because of
the altered volume geometry .

Anyway the point is , that for your own particular detonator design , you have
to test yourself the quantities and determine what are the threshold amounts
and extrapolated excesses you will employ for reliability . These firing trains
are indeed affected by small dimensional changes which have bearing on the
loadings found to be optimum . The exact loading figures for your particular
custom created design will therefore be absolutely unique to your device and
determined by your own tests . Whatever I tell you about such quantities is
something you should understand is then only a " ball park " generalization ,
and you may discover a variation on such figures from your own tests .

[2,4,6-TNP]

Thanks for your reply Rosco,

You must have replied just before I had a chance to edit my
last post. Please check the changes and my comments on the
possibilities of the patent that we looked at!

I know that either there are real possibilities there or it won't
work at all. However the detonator setup you have described
seems flawless and I have enjoyed discussing it with you.

Thank you!

[2,4,6-TNP]

Thanks for your reply Rosco,

You must have replied just before I had a chance to edit my
last post. Please check the changes and my comments on the
possibilities of the patent that we looked at!

I know that either there are real possibilities there or it won't
work at all. However the detonator setup you have described
seems flawless and I have enjoyed discussing it with you.

Thank you!

[2,4,6-TNP]

Thanks for your reply Rosco,

You must have replied just before I had a chance to edit my
last post. Please check the changes and my comments on the
possibilities of the patent that we looked at!

I know that either there are real possibilities there or it won't
work at all. However the detonator setup you have described
seems flawless and I have enjoyed discussing it with you.

Thank you!

[Rosco Bodine]

Various types of safety detonators have been described before
and the in situ compression effect occurs to some extent in all
of them . The new idea of the patent seems to be the use of
a movable piston which acts as a carrier for the deflagrating
material functioning as the initiator , to enhance compression
of the base charge . I am not sure how much advantage this
provides over the effect where the charge pellet itself behaves
as a piston , even without any additional " sliding sleeve " ,
the benefit of which is likely greater in simply providing a stronger
confinement . Pressure would likely expand and lock the sleeve
in the housing and the pellet would extrude through the carrier
shearing from the pressure anyway . I place greater confidence
in detonators which do still rely on a primary explosive initiator ,
having materials which are capable of redundant paths to detonation
inherent in the design . I would disagree with the premise of the
design of safety detonators that primary explosives are somehow
unsafe by their nature . Every primer in every cartridge of ammunition
contains a primary explosve , and crates of millions of rounds of
firearms ammunition sit in storage for decades , without ever just
" going off " . The same applies to blasting caps containing initiators .
They function as they are intended , and some of the initiating explosives
which the detonators contain are actually more stable and predictable
than the base charges . So how much validity is the premise that a
detonator is safer somehow if it is designed to remedy a danger which
does not really exist ?

As for the application of the compression effect to larger devices , well
that sems unlikely to be of any interest since cast loadings are already
used to achieve highest density .

[Rosco Bodine]

Various types of safety detonators have been described before
and the in situ compression effect occurs to some extent in all
of them . The new idea of the patent seems to be the use of
a movable piston which acts as a carrier for the deflagrating
material functioning as the initiator , to enhance compression
of the base charge . I am not sure how much advantage this
provides over the effect where the charge pellet itself behaves
as a piston , even without any additional " sliding sleeve " ,
the benefit of which is likely greater in simply providing a stronger
confinement . Pressure would likely expand and lock the sleeve
in the housing and the pellet would extrude through the carrier
shearing from the pressure anyway . I place greater confidence
in detonators which do still rely on a primary explosive initiator ,
having materials which are capable of redundant paths to detonation
inherent in the design . I would disagree with the premise of the
design of safety detonators that primary explosives are somehow
unsafe by their nature . Every primer in every cartridge of ammunition
contains a primary explosve , and crates of millions of rounds of
firearms ammunition sit in storage for decades , without ever just
" going off " . The same applies to blasting caps containing initiators .
They function as they are intended , and some of the initiating explosives
which the detonators contain are actually more stable and predictable
than the base charges . So how much validity is the premise that a
detonator is safer somehow if it is designed to remedy a danger which
does not really exist ?

As for the application of the compression effect to larger devices , well
that sems unlikely to be of any interest since cast loadings are already
used to achieve highest density .

[Rosco Bodine]

Various types of safety detonators have been described before
and the in situ compression effect occurs to some extent in all
of them . The new idea of the patent seems to be the use of
a movable piston which acts as a carrier for the deflagrating
material functioning as the initiator , to enhance compression
of the base charge . I am not sure how much advantage this
provides over the effect where the charge pellet itself behaves
as a piston , even without any additional " sliding sleeve " ,
the benefit of which is likely greater in simply providing a stronger
confinement . Pressure would likely expand and lock the sleeve
in the housing and the pellet would extrude through the carrier
shearing from the pressure anyway . I place greater confidence
in detonators which do still rely on a primary explosive initiator ,
having materials which are capable of redundant paths to detonation
inherent in the design . I would disagree with the premise of the
design of safety detonators that primary explosives are somehow
unsafe by their nature . Every primer in every cartridge of ammunition
contains a primary explosve , and crates of millions of rounds of
firearms ammunition sit in storage for decades , without ever just
" going off " . The same applies to blasting caps containing initiators .
They function as they are intended , and some of the initiating explosives
which the detonators contain are actually more stable and predictable
than the base charges . So how much validity is the premise that a
detonator is safer somehow if it is designed to remedy a danger which
does not really exist ?

As for the application of the compression effect to larger devices , well
that sems unlikely to be of any interest since cast loadings are already
used to achieve highest density .

[Child-of-Bodom]

Ok, I tried again.... I dissolved 0.75gr NaNO2 in 5ml H2SO4 in an ice-EtOH bath, heated it after 15 min to rt, (12°C brrr), and after 20min, the erlenmeyer was transferred to a watherbath of 55°C, 10 minutes later everything was dissolved.

1.5gr 2,4DNA was added in small portions, the slurrie was poured to a beaker, (next time I'll start in a beaker...) and 21grams of ice was added. A yellow, but ice-cold solutiuon was the result, this was filtered, and 1 ml HClO4 dissolved in 25ml dH2O was added at one, and the solution was stirred vigoriously.
In less then a minute, a yellow precipitate was seen, stirring was continued for 1 more minute, the solution was filtered, and washed later with dH2O acidified with a little HClO4.

No color change of the precipitate has occured, even after 12 hours. Tests are not perfomed yet, hopefully to come in the next week.
The strange thing is although that I have a sore throught, and it feels like I've sniffing a lot of NO2, while there was hardly any present in the reaction...

[Child-of-Bodom]

Ok, I tried again.... I dissolved 0.75gr NaNO2 in 5ml H2SO4 in an ice-EtOH bath, heated it after 15 min to rt, (12°C brrr), and after 20min, the erlenmeyer was transferred to a watherbath of 55°C, 10 minutes later everything was dissolved.

1.5gr 2,4DNA was added in small portions, the slurrie was poured to a beaker, (next time I'll start in a beaker...) and 21grams of ice was added. A yellow, but ice-cold solutiuon was the result, this was filtered, and 1 ml HClO4 dissolved in 25ml dH2O was added at one, and the solution was stirred vigoriously.
In less then a minute, a yellow precipitate was seen, stirring was continued for 1 more minute, the solution was filtered, and washed later with dH2O acidified with a little HClO4.

No color change of the precipitate has occured, even after 12 hours. Tests are not perfomed yet, hopefully to come in the next week.
The strange thing is although that I have a sore throught, and it feels like I've sniffing a lot of NO2, while there was hardly any present in the reaction...

[Child-of-Bodom]

Ok, I tried again.... I dissolved 0.75gr NaNO2 in 5ml H2SO4 in an ice-EtOH bath, heated it after 15 min to rt, (12°C brrr), and after 20min, the erlenmeyer was transferred to a watherbath of 55°C, 10 minutes later everything was dissolved.

1.5gr 2,4DNA was added in small portions, the slurrie was poured to a beaker, (next time I'll start in a beaker...) and 21grams of ice was added. A yellow, but ice-cold solutiuon was the result, this was filtered, and 1 ml HClO4 dissolved in 25ml dH2O was added at one, and the solution was stirred vigoriously.
In less then a minute, a yellow precipitate was seen, stirring was continued for 1 more minute, the solution was filtered, and washed later with dH2O acidified with a little HClO4.

No color change of the precipitate has occured, even after 12 hours. Tests are not perfomed yet, hopefully to come in the next week.
The strange thing is although that I have a sore throught, and it feels like I've sniffing a lot of NO2, while there was hardly any present in the reaction...

[pdb]

Microtek :

The movie posted by Axt (http://geocities.com/roguemovies8/) shows clearly that this salt deflagrates in small amounts, when DPNA detonates in same quantity. This is concurring with my own observations and contradictory to yours. I am thus wondering which alternate salt you may have synthesized or under wich differrent conditions you performed your DDT test.

[pdb]

Microtek :

The movie posted by Axt (http://geocities.com/roguemovies8/) shows clearly that this salt deflagrates in small amounts, when DPNA detonates in same quantity. This is concurring with my own observations and contradictory to yours. I am thus wondering which alternate salt you may have synthesized or under wich differrent conditions you performed your DDT test.

[pdb]

Microtek :

The movie posted by Axt (http://geocities.com/roguemovies8/) shows clearly that this salt deflagrates in small amounts, when DPNA detonates in same quantity. This is concurring with my own observations and contradictory to yours. I am thus wondering which alternate salt you may have synthesized or under wich differrent conditions you performed your DDT test.

[209]

I would really like to make some Lead Styphnate and I have all the required materials except for this acid: Styphnic acid.

Through research I have found that styphnic acid is quite similar to picric acid. Would Picric work to make Lead Styphnate?

[The_Duke]

The short answer is no… :rolleyes:

You will be hard pressed to find styphnic acid as it is explosive. You will have better luck searching for resorcinol.

Don't resurrect old threads to ask questions that are irrelevant to the topic at hand, and in the future, UTFSE!