Sciencemadness Discussion Board - Picric acid: different instructions

Picric acid: different instructions

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Hennig Brand - 25-6-2009 at 17:37

Could Picric Acid and an oxidizer be used in some way in a cap, to increase sensitivety, such as KNO3 or dare I say KClO3. It would' t have the full power of the pure TNP, but in an improvised fashion it could be made to work possibly with lesser primaries. I have seen figures in an old book, can' t remember exactly where but I have covered over the material a couple times in the last little while so I could probably find it. They mostly focused on gas volume and the heat of explosion of the different TNP and oxidizer mixes and compared the results and the products of the results to the pure TNP figures. I remember for the KNO3 and TNP the gas volume and heat where substantially lower than pure TNP, but with KClO3 the heat was much greater to the extent that the product of the gas volume and heat was about the same as it would be for pure TNP(pretty cool if reliable). I know , I know it says everywhere that TNP and oxidizers are incompatible, and while they probably make a valid point a lot of stuff we play with by way of mixtures are deemed "death mixes" by some. The book did say that it was abandoned because the sensitivity was too high. Well that sounds kind of relative to me, so I mixed a little up(finely powdered each beforehand). I made a small amount and did not store. I have to say it still took a pretty good clout to effect detonation, kind of like a drop of nitro on a moderately warm day, and made about as much noise to with about a match heads amount in tin foil. I know this came from a book that was published either just before the 1900' s or just after, and a lot of stuff in those times was alittle less about safety. A lot of stuff still hadn' t been figured out about the dangers, but in small quantities, in some fashion(even if possibly not storage stable), could it be used as an initiator? Could the risks be managable? Is it any more dangerous than a lot of the more excepted things(or commonly used things) people put in blasting caps? I know its not the purists way but it could easily be set off by even AP I bet, and less primary would help contribute to less danger. For the military it was unexceptable at the time but a lot of useful stuff is. If it couldn 't be fired more than 8 miles from a rifled cannon and make it to the target before exploding, or fulfill some initiating need better than something already in use it was discarded. Probably other reasons to, specific to the military. Even if ignoring the possible dangers, do these oxidizer/ TNP mixes have initiating ability that would make them useful in some way? If you type up TNP and Chlorate, a lot of hazard warnings come up, but none of the stuff I saw gave me much more explanation than "incompatible" . Of course these sites say the same thing about kerosene and NH4NO3(I am not trying to trivialize the possible danger though). If someone has some info on these mixes it would be interesting, if only for curiosity purposes. This may border on the rediculous to an experienced chemist, it is just a curiosity mostly.
note:I used 70/30, TNP/chlorate, I think it was more like 50/50 in the book example.

[Edited on 26-6-2009 by Hennig Brand]

quicksilver - 26-6-2009 at 07:30

In a word, yes. See the actual "formula" for the material "Melaniite"; it's not simply TNP!
In the commercial development of all the energetics industrial materials back about 80-100yrs there were "standards". For temperature, the methodology was to add powdered metals, for OB, the technique was to add an oxidizer, etc. An enormous amount of material is reviewed in the study of that period. See - "EXPLOSIVES - 100yr More or Less" - Hopler. In it, various advertisements are explored as well as information regarding material development in the dawn of the Industrial Age.

Rosco Bodine - 26-6-2009 at 08:26

The most promising idea that is not something which I did followup experimentation to investigate, involved the use of the easily fusible and probably much more easily initiated melt cast base charge of the binary composition
of DDNP and TNP, with an initiating cover charge of DDNP,
perhaps having an intermediate compressed charge and/or involving basic lead picrate or the basic lead picrate / lead nitrate / lead chlorate tertiary clathrate as a component. This seemed to be a logical experiment
towards producing a practical detonator having decent
performance and storage stability, based upon picric acid
derivatives, yet requiring no azide component.

Personally I have favored the technical predictability involved with using compositions which are chemical
compounds or fused "alloyed" mixtures, as distinguished from ordinary physical mixtures, even while knowing that physical mixture compositions indeed do have their usefulness. Ordinary mixtures can certainly produce
good results, I just haven't focused much of my interest
on such mixtures, for being preoccupied and more intrigued by the chemistry of compounds. Therefore I can't really speak well to the specifics of mixtures and
a pyrotechnics related source would be better consulted on that. There is an inherent variability about mixtures for
reason of the physical nature of the reactants, particulate size, homogeneity and uniformity, which makes mixtures
less predictable and probably more dangerous to handle,
even though such disadvantages may not necessarily rule out their use.

We momentarily interrupt this regularly scheduled Rosco broadcast to bring you the following chain reaction

Get 'em while they last

http://www.youtube.com/watch?v=H9YKPx2tFKQ&fmt=18

http://www.youtube.com/watch?v=BvM1JIRi65k&fmt=18

http://www.youtube.com/watch?v=D3CJOyBHPwI&fmt=18

http://www.youtube.com/watch?v=tyiEO6CO1x4&fmt=18

http://www.youtube.com/watch?v=o2d2llB4oIQ&fmt=18

http://www.youtube.com/watch?v=Lmsxr4pj0aQ&fmt=18

http://www.youtube.com/watch?v=1pDBtULvB7A&fmt=18

http://www.youtube.com/watch?v=gKtdlZQIRYc&fmt=18

Attachment: US1428011 DDNP and Picric Acid eutectic.pdf (242kB)
This file has been downloaded 897 times

[Edited on 27-6-2009 by Rosco Bodine]

grndpndr - 26-6-2009 at 19:14

IIRC a turn of the century paper "metallic picrates" compares the use of fulminate of mercury and pottassium chlorate as well as lead picrate/pottassium chlorate physical mixes i would imagine to increase OB balance and thus power in use simultaneously and with some competition.

As far as a melt/ cast TNP, Trimonite is another of the family again dating around the turn of the century and which ive mentioned before used mononitronapthalene to lower casting temp. although it also decreased det velocity to slightly better than 7000MPS.Strangely enough I still see it listed in what I assumed to be relatively current lead block/vod listings .

Rosco Bodine - 26-6-2009 at 21:35

compounding of mixtures is an old art unto itself even older than chemistry which is a derivative art

http://www.youtube.com/watch?v=2B6WtP66gQo&fmt=18

http://www.youtube.com/watch?v=wacyMhxIOd0&feature=relat...

[Edited on 27-6-2009 by Rosco Bodine]

grndpndr - 27-6-2009 at 01:19

Interesting patent.I could see where a far more sensitive
castable TNP/DNP could be useful in an initiator but never hearing of difficulty with using TNP as a booster in a composite cap I wonder about its utility/safety when mercury fulminate,HMTD,or many others will easily det. pressed TNP
without the risk of melting TNP/DNP.

DNP looks to be quite useful in AN.

Correct me if Im wrong but wasnt a reason for using mononitronapthalene/TNP the lower melt temp of the mononotronapthalene and increased safety?
As far as being useful in an arty shell... or really any military munition where a sensitive secondary is very undesirable,TNP/DNP seems unfit from that standpoint.
Might make a good rifle target

Regards

[Edited on 27-6-2009 by grndpndr]

[Edited on 27-6-2009 by grndpndr]

Hennig Brand - 30-6-2009 at 18:18

Interesting, I have never seen anything before on melt, cast charge made of DDNP and TNP. Just got back from a short work trip out of province and I found a chemical company which deals mainly in industial cleaning supplies, but they did have huge quantities of NaOH(so I got 5Kg, even though 40Kg would have been much cheaper per Kg). They also had lots of 28% NH4OH solution so I got a few gallons. The slippery characters that they were though, one of the gallons was all swelled and weakoned on the bottom(maybe was frozen or something before). To make a long story short on the way home it started leaking(nasty stuff!). I was right beside a gas station so I pulled in, removed the offending gallon then bought some windsheild washing fluid, put fluid in car and used poly ethylene jug to hold the ammonia solution from the busted jug. It took a couple hours with the windows down to fully air out the car, even after soking up the bit spilled. The amount spilled was probably less than an ounce, but man was it stinky, and irritating. I guess they saw a way to get rid of a bad container, I think I will be able to get a free gallon of ammonia out of this though, probably

.
This place can order a lot of other stuff as well, but they wanted cash up front,andI wasn' t feeling all that flush. I priced sodium sulfide, which was $150 for 500g, and phenol(crystaline/pure, technical) for $140 for 500g. This seemed kind of pricey, and the guy I talked to admitted that he had to order stuff from a lab supply place a high price(probably with hazard charges to boot).
I wanted to say that KClO3 is a very powerful oxidizer, but it is also a very powerful sensitizer. Mixtures that use this compound generally have much lower reaction initiation energy requirments. Oxygen balance effects may be interrelated, but with KClO3 I think it is much more to do with the chemical nature of this compound(it actually gives of heat when it decomposes for one) and tends to greatly sensitize most pyrotechnique mixtures(TNP and KClO3 for example). I am not sure of the proper way to mix the TNP and the oxidizer, since it didn' t say in the book I saw I believe. I think they said mixture though.
How much easier would it be for a charge of primary explosive to initiate TNP, if the primary was completely imbeded in a charge of the TNP(normal charge with blasting cap), versus the same primary charge pressed on top of the TNP in a compound cap configuration? I guess I am just curious how easy it would be comparably to set off a small charge of TNP(maybe 20-30g for instance) with a cap placed in the material. Anyone try setting off a few decagrams as a test or anything?
I think tomorrow I will make a couple pounds of hexamine(it is so nice to not have to make ammonia when one wants hexamine)

http://www.filestube.com/6d8906f8c8eb7d0a03e9/go.html
This is an active link for free download of the book Propellants and explosives. Thermochemistry and combustion
It is a zipped file. I downloaded it and it seems like one of the better books that I have seen on the subject, in the sense that it wasn' t too advanced and/or convoluted and it has lots of good info and charts on most common explosives. It also spends a lot of time explaining the science of explosives with some math, but in a way that is easily understood by someone who is not an expert. Probably a good reference for anyone, even the advanced.

[Edited on 2-7-2009 by Hennig Brand]

Hennig Brand - 1-7-2009 at 08:34

Propellants and Explosives By Naminosuke Kubota, this book has a chart for some critical diameters for some common explosives, and Picric Acid is included.

TNT=8-10mm
Picric Acid=6mm
RDX=1-1.5mm
PETN=1-1.5mm
AN=100mm

Now it would seem that a lot of folks(including me), have been using tubes that are not much larger in diameter than the critical diameter. Very strong tubes will make up for a small diameter to some extent but still. Even if it does detonate the detonation velocity and hence power will be greatly reduced probably. A 5/16" tube is only about 30% larger than the critical diameter for TNP( of probably a perfect pure sample). This is all assuming that their numbers are correct of course.

How It Works By Marshall Cavendish Corporation, in this book it talks about the sensitivity values of some commonly used explosives. Picric Acid was used as the standard with a sensitivity value of 100, and was not descibed as an intermediate charge at all, but as a definate secondary. It described intermediates(for compound caps, etc) to normally practically have sensitivety values of 60 or less. Primaries had sensitiveties around 20, on average(rough figure).

Sensitiveties of some common explosives from book-
Picric Acid=100
Gun Cotton(dry)=as low as 23 sometimes
Gun Cotton wet=120
TNT=110
PETN=40
RDX=55
Tetryl=70

I know that this book is not a chemistry text book, and is probably more of a book for the laymen to get a feel for explosives technology a bit, but it seemed like a good book taken for what it is. The sensitivity figure is a little confusing to since different types of initiation stimuli and conditions under which it is performed can make results differ greatly between different explosives. It does give a useful, albeit general picture I would say. Picric Acid and TNT are both much more insensitive and with greater critical diameters than what would be considered suitable as an intermediary charge say in a compound cap(if info is correct). I guess anything is possible if one is obstinate enough and has very good primaries, and has good skill in detonator fabrication, and has a need to use TNP because of the inavailability of something easier to use, or more suitable.
Without careful fabrication, and/or very good "hot" primaries how suitable is Picric Acid in this application as an intermediate, used in caps in small quantities, and in small diameter sizes?

[Edited on 1-7-2009 by Hennig Brand]

[Edited on 1-7-2009 by Hennig Brand]

[Edited on 1-7-2009 by Hennig Brand]

Rosco Bodine - 1-7-2009 at 14:10

For a base charge of TNP a 5/16" bore is okay but
a 3/8" bore is better. And yeah it takes a geometrically increased initiator charge to initiate it appropriately.
Those small diameter and small initiator weights which
are given in the literature for "test data" simply do not translate to real world practical application performance in my experience. If you want to use a 1/4" column diameter base charge, and fairly small initiating charges then use compressed particulate PETN as the base charge. If you want to use TNP at that diameter, or any diameter really, be prepared to substantially overdrive it with a hefty initiating charge or it will quench and not demonstrate the kind of output needed.

Hennig Brand - 1-7-2009 at 17:10

I' d say you have been there once or twice Rosco

The more I play with this compound the more your posts make sense. I know you have said it all at least a couple times with this topic, but I appreciate it. Sometimes I need to hear something at the right time or in the right context, makes me less than an ideal student, but probably not that far removed from average forum folks in that way.
I think a lot of folks are simply trying to make their TNP do things it is just not going to do, or at least not well. This stuff is technically challenging, in comparison to a lot of the other explosives I have dealt with. The synthesis has little pit falls, and the use of the explosive also has little pit falls. I am sure there are other things much more difficult, but I have to say that this compound forced me to learn more than most other things I have done. The lessons learned are also applicable in many ways to other similar chemicals I think.

Rosco Bodine - 1-7-2009 at 18:35

Yeah TNP is energetic materials 101. TNP has much to teach you if you want to learn. One thing you will notice as the column diameter is increased comfortably beyond the critical diameter, then the difficulty of initiation based
upon the unequivocality of the initiating material is reduced, meaning the base charge requirement for the more efficient initiators is greatly lessened, and more
mundane initiator materials may be usable similarly as
is the case for when a reenforcing cap is used. Those
two factors can be combined in order to facilitate the use
of less technically advanced initiator schemes to successfully detonate a TNP base charge, and a configuration may be found which has excellent reliability and performance, even for it of course being a device
which is substantially larger in dimension than a compound detonator having something like a PETN base charge. The press loading requirement is also greatly reduced for the column diameters comfortably larger than the critical diameter. Even though the economy of materials required on a "per unit" basis suffers for having to use larger quantities of energetic materials in the device as compared to a device optimized for economic manufacture, the technical demands for the
improvised device are greatly lessened. It is good to know what you need to do in the way of materials and design parameters in order to make efficient use of what resources are available, dependant upon the capabilities
of your tooling and workshop. The applicable principles are the same whether you are in the most advanced research setting having all the exotic tooling and materials, or are limited to primitive and minimal resources. Knowing what you are doing you can then make the best use of what you have.

Bluegrass
http://www.youtube.com/watch?v=2P7J1_hZ7iM&feature=relat...

http://www.youtube.com/watch?v=EvKtxTsVoMo

[Edited on 2-7-2009 by Rosco Bodine]

Hennig Brand - 2-7-2009 at 10:56

Well said, and it rings true Rosco. I appreciate it.
I have read a couple places that stainless steel is fine for Picric Acid casings as well as aluminum(which has been stated lots).
Back in the early part of the last century, I think(even though both available), aluminum and stainless were more uncommon and expensive. I don' t remember hearing about either in the old books,(I have read from) where Picric Acid was discussed.
I live close to a scrap yard and if one is patient and drops in from time to time, a lot of stainless tubing could be collected for $1-2 a pound. In my little book of shop materials it shows tensile strengths for different metals and their alloys(can' t find the book right now though). From what I remember steel can have huge variations in strengths, with the softer and weaker ones being not much stronger than the stronger alloys of aluminum. However, the better steels, and better stainless steels can have 4-5 times more strength for the alloys in common usage(than strongest aluminum). I wonder if stainless steel would be OK for HMTD or if the chromium or possibly nickel, or maybe still the iron would be a problem. Good stainless is pretty unreactive stuff, and a strong alloy would make a proportionately strong casing I would guess. Although the relation between between tensile strength and strength under blast conditions is still a bit of a mystery to me, but it should give a good idea. The strength is measured per unit volume to by the way(by thickness of tube in our case), not by mass.
A composite cap in strong stainless, which could allow for the cap wall thickness to be proportionately thinner( or thinner anyway) and still provide great confinement for insensitive TNP, and be safe(chemically) for both the TNP and HMTD would be nice. Is this workable?

[Edited on 2-7-2009 by Hennig Brand]

Rosco Bodine - 2-7-2009 at 11:07

I wouldn't use HMTD in contact with any metal period.
HMTD is something I wouldn't use at all except for a very near term usage where convenience or necessity was
governing, as it is least desirable among the possible
alternatives. HMTD is basically a quick and dirty short term solution. And that is all it is.

Hennig Brand - 2-7-2009 at 12:16

I think it is time for me to try a bit harder, and develop a little more sophistication, and options in the primary explosive department. Thanks.

Rosco Bodine - 2-7-2009 at 12:39

You will be happier with the result in most cases to come up with a storage stable device you can tuck away for that special occasion when it is needed instead of having to press into service something needed on the spur of the moment when you may have a lot else on your mind.

Hennig Brand - 3-7-2009 at 07:02

That is probably what I should strive for, for sure. There is an appeal to the more easily improvised compounds, and are good to have in ones skill set, but they are inferior usually and should be used as you have said as a quick and dirty solution only if something better can not be made/obtained.
I would like to thank Quicksilver for pointing out Practical Organic Chemistry, looks like a very good book indeed. I downloaded it last night from www.archive.org(the other links didn' t seem to work well for me). I have only looked through it a little yet but it looks like the perfect thing for my level of functioning. A lot of practical stuff(preparation, etc) on useful common chemicals is in the book, and basic laboritory techniques.
This is a little embarrassing, and scary, but is kind of neat as well, as well as being a good lesson. Last night I made some HMTD with 5g Hexamine,22mL 35% H2O2, and 15g citric acid. I know it seems like a lot of acid but it seems to take that much or nothing much happpens, even after sitting for hours. I let it form overnight, and when I woke up this morning (still half asleep) I decided to filter and rinse my product. I grabbed the first funnel I had close which was poly ethylene, but it had a brass screen in it(I use it for my homemade vaccum filtering setup, it is an automotive filter). Anyway still in a sleepy stupor I put a damp filter paper in the filter and poured the HMTD and waste liquid on it, then left it for couple minutes to gravity filter. In less than a minute I started hearing this hissing sound which was quickly getting louder and louder(like a big fuse burning down, with the threat of an explosion soon to follow). When I took a look in the filter there were blue spots bubbling through(from the copper in the brass, I would say?). I quickly got the filter paper off the filter, rinsed the HMTD into a beaker, then drowned it in some water. I rinsed and filtered a couple more times, and all the blue seemed to rinse away fairly easily right away, and it seems to have completely stopped decomposing. I quess it still could be sensitized, so this stuff would be best avoided, I quess. It is only a few grams, and I am drying it now, but I will be very careful with this stuff! Definately not the brightest thing to do! The incompatability issues are worse than I thought. Better to witness it this way then have it happen in a cap!

quicksilver - 3-7-2009 at 07:54

When looking at a lab that didn't turn out as expected (speaking just for myself) I look at what I could improve upon in such a synthesis. Did I pay attention to temperature & weight of precursor materials? Did I look at the lab in terms of what is being accomplished overall? Did I pay attention to time within the synthesis?
Stephnic Acid had many folks stifled due to the need for more exacting techniques that TNP. Once I got to the point that I understood what was actually happening within the synthesis, my TNR was just as simple as TNP.
The areas often tripped up by many are timing, temperature, weight, & technique. I try to avoid "recipes" & stick to molar weights at first.

HOWEVER scaling up or down may NOT maintain the same levels of acids (in nitrations) or reagents & this is where knowledge of the final material can help. Generally you just need to read up on the synthesis a hell of a lot & not blow off "plant-level" synthesis as often a lot has been worked out when scaling up is in place that helps in smaller level labs (strange but true).

[Edited on 3-7-2009 by quicksilver]

grndpndr - 3-7-2009 at 09:32

It had been at least a year since I last did a lab.But before i puy everything away for a move i prepackaged the amounts normally used for the lab.I also used some left over H2SO4 drain cleaner left at the rental.To rid it of a slight discoloration I tried the H2O2 method. A sure thing Synthesis was a Complete failure! could have been any one of the mentioned preps.The H2O2
cleaning,neglecting to be sure the Rooto was concentrated.
Or even ensuring the dry precursors that were hygroscopic hadnt absorbed excessive moisture.I payed the price for the rush, a waste of time and materials but a lesson learned.

Its no waste of time to ensure the suitability of your precursors even if its seems a routinely successful synthesis.
Safety being paramout and i got careless.Thankfully the failure was harmless but on the other hand it could have been catastrophic.It goes to show me at least no matter the # of times ive successfully done the same lab it can turn to shiy in a heartbeat.

[Edited on 3-7-2009 by grndpndr]

[Edited on 3-7-2009 by grndpndr]

Hennig Brand - 4-7-2009 at 09:43

I just got my first full positive result with Picric Acid in a compound cap, and there was no doubt about it. Even from one gram there was a pretty big cloud of black smoke, and much more noise and violence than from the HMTD alone. I used one gram, made from ASA and recrystalized twice, and one gram of HMTD. I know it was maybe a bit dangerous, but I use the stuff all the time to play tricks on people, kids and adults love the little torpedoes and other novelties made with it(Silver fulminate). I made a little pocket with thin waxy tissue and a pinch(probably less than 0.05g), then put this around end of fuse to protect and provide separation from HMTD. Just the gram of HMTD probably would have done it(my last failure only used 0.5g HMTD), but I wanted to get the most out of my 1g and get the HMTD up to velocity quickly. In the future I will use Silver acetylide nitrate instead, but this was what I had on hand. I have been using the same batch of Silver Fulminate for over a year now(less than 1g) and it is still good and doesn' t seem that sensitive(every batch is different). Both TNP and HMTD were pressed to around 1.5g/cc, or there abouts. It was truly awesome, and gratifying. This has been in the back of my mind for the last couple of years, with experiments off and on. I would get discouraged, but always go back to it again eventually. I used stightly smaller than 3/8" diameter semi-soft aluminum tubing from old heating radiator or something, with wooden plugs epoxied in, making sure end with the TNP was good and solid(thick). I pressed so hard that the tubing was doing a lot of swelling(should have some kind of support I quess for best pressing). So instead of a yellow cloud, and yellow on the ground, I got a big black cloud, and great report

The large piece of shale rock I had it sitting on was cracked in several places, which AP or HMTD alone failed to do in those quantities. The nearby rocks had little gouges out of them as well(aluminum shrapnel?). There was no yellow residue or powder from unreacted TNP, only black soot on the broken pieces of shale. I also didn' t find any metal fragments from the cap this time, and every other time I did after the failed attempts.

[Edited on 4-7-2009 by Hennig Brand]

Rosco Bodine - 5-7-2009 at 05:43

A handy method for making detonator capsules from tubing is to use one of those tubing cutter tools which
has a cutting wheel bearing against the tubing which rests upon rollers within a C-clamp sort of frame where
the cutting wheel depth is advanced incrementally by
turning a knob which has a threaded shaft operating
to move the cutter wheel, like a micrometer. If the
pressure on the cutter wheel is kind of median and time
is extended to maybe a dozen revolutions for completing the cut, the tubing will be deformed at the
cut, crimped slightly as well as cut so that a ledge is
formed towards the inside, leaving a circular bur on the
inner wall of the tubing at the cut. Generally the most
convenient approach is to start with a piece of tubing that is twice the length of the desired capsule and having clean cut ends which have been saw cut, and then use the wheel cutter in the middle to produce
two pieces, each having a clean opening as the top
and a chamfered cut end which will be the bottom closure end, closed by a disc which has been punched from sheet stock using a hollow punch and a hardwood
cutting block for the punchings. Very thin aluminum capsules can be made having the end closure discs
epoxied to seal the disc against the inner chamfer, using a dowel inside to tap the disc securely into place. The disc will be actually a slight dome shape, and the slight flattening of that dome as it is tapped will expand and
secure it mechanically at the end. These aluminum capsules may be used as liners placed within stronger
outer capsules of brass or stainless steel made in a
similar manner but having their end closure discs silver
soldered. The laminated capsule liner within an outer capsule can be made secure and permanent by using a thin liquid epoxy such as is used for coating tabletops,
placing one or two drops inside the outer capsule at the bottom, inserting the liner capsule and slowly and firmly
pushing it to the bottom, the liquid epoxy will ooze upward to force the air from the slight gap between the capsule liner and the outer capsule. The liner capsule
should be a few millimeters longer than the outer capsule, and the excess epoxy extruding from the
gap during assembly can be wiped away with a rag.
It is worth the effort to make up a batch of these capsules of maybe a dozen at a time, using materials
whose diameters are found convenient and will match up with whatever igniter squibs or fuse holders or closures are intended to be used later for actuating the device.

The base charge range for TNP which will be most useful
will be from 1.5 grams to 2.5 or even 3 grams, the heavier
loadings (of course) being my own preference as these
will directly initiate even relatively insensitive main charges
like urea nitrate, without the need for using a booster,
since the cap is big enough to do the job reliably. I would
much prefer to have confident certainty at the expense
of doubling a loading, than to have to use less reliable and more troublesome "extra steps" to get the job done.

If you are press loading at high enough pressure that capsule expansion is occurring, this may make it difficult or impossible to remove the loaded capsule from the holder block if it is a one piece bored holder. A laminated block
holder which is held together with bolts and has the cavity
then drilled and centered of the seam where the halves
bolt together can be used to remedy that problem of an expanded capsule which has gotten stuck in a one piece holder. After loading expands the capsule, the bolts can be
loosened which secure the halves of the holder block together, and the halves separate easily, allowing the loaded capsule to be removed.

[Edited on 5-7-2009 by Rosco Bodine]

Hennig Brand - 5-7-2009 at 07:38

Nice ideas! I think a good dense piece of hardwood, cut down the middle first, then made to be held together with bolts and wing nuts or something might work for me. The bore holes could be carefully drilled, perfectly centered on the join between the two halves of hardwood(starting with small drill bits and working up to size of the cap you wish, for better control of accuracy). When starting with smaller bits first, their is room for corrections, when right, larger bit will easily follow smaller bore mostly(depending on bit and material) . The two block halves should of course be held tight together, in the right position before drilling. Drill press would be ideal, but can be done without. Good idea, do you think hardwood would be ok? I think I saw you refer to phenolic resin at least once before, but hardwood should work right?

I guess it is pretty important, though I don' t know much about it, to have thin endcaps when using TNP as an initiator. My big thick epoxy and wood endcaps, give good confinement, but how much less effective is my weight of charge at initiating in this arrangement? How much inferior is it to use wooden endcaps, normaly? I tried soldering an aluminum plug in my aluminum tubing, but had no luck getting the solder to stick. I found with a little research that choice of aluminum and solder and process control are all very important with aluminum soldering. Brass solders very easy usually though. I have never had much luck soldering steel either. There are many techniques and specialty solders, and I have only tried a few common ones. I think the chamfered ends and disks looks like a good solution, thanks. The idea is to have the initiator as close to the secondary as possible, while still having a strong enough cap to fulfill the needs of the primary and/or intermediate, right?
Lots of good ideas thanks. I will try to do some of them justice.

Rosco Bodine - 5-7-2009 at 08:53

A 96/4 Sn/Ag soft silver solder using a liquid flux like
alpha metals or "ruby fluid" will stick to stainless steel
or plain steel or to brass even better. There are supposedly some aluminum brazes / quasi soft solders
but I haven't tried them.....more trouble than it's worth
when epoxy works fine as basically a seam sealer.

If a thick end cap is used then I would position the cap laterally in the insertion into the main charge since there
is a "projectile" having a disruptive effect coming off the end of the det.

Hardwood is okay for the blocks, or structural plastic, or aluminum, or fabric reenforced phenolic, or you could even probably cast the blocks with chopped fiberglass reenforced resin. A drill press should be used for the
boring of the mated blocks, unless you work out some sort of casting scheme for making a shell holder which
can be separated.

For a TNP base charge it is probably essential that the
initiator be in actual physical contact compressed directly onto the column of TNP so you want something chemically compatable. With more sensitive base charges like PETN, actual physical contact is not required
with the initiator, where sympathetic detonation or
flyer fragment impact initiation by flying particles of a granulated partition material can be exploited. But TNP isn't that sensitive so it would require a pretty huge scaleup to exploit that sort of scenario, which really would not be practical for TNP except in a large ordnance.

Polypropylene culture tubes actually make decent capsules,
but off course it is probably an unauthorized off label use
if you really worry about such polite manners and all, not
wishing to so rudely and abruptly end the existence of labware

It's definitely a short goodbye for that culture
tube being so horribly abused in such an uncultured way

However, when must needs be, the time may come when some sacrifices are just plain necessary.

Luminosa ( Full of light )
http://www.youtube.com/watch?v=djw1Oa8yg70&fmt=18

[Edited on 5-7-2009 by Rosco Bodine]

Hennig Brand - 5-7-2009 at 13:50

You know another score for TNP in the teaching department. I find you can get away with just about anything with the more sensitive and easier made explosives (esp nitric esters), and still get a descent initiation. The TNP really forces one to hone their skills, especially when used in small quantities, because if off by very little from what is best there is a very good chance it will not work at all. Most of these lessons might never be learned at all, with say the dynamites, because (I believe) the differences are usually not perceived in those cases, whereas with Picric Acid if one plays with it long enough, the best practices will be made apparent. These leasons could have great value when trying to get the most out of other energetic compounds(I would think).
Thanks for the advice on the support blocks and stuff. What is your preference Syphnic Acid or Picric Acid? Or what do you usually prefer using? Not to be a bother, but you seem to have quite a bit of experience working with both.
I know they are too small for TNP really, but have you seen the plastic tubing that is used for airbreaks sometimes. It must be tuff stuff for sure.
It would probably take one hell of a slapper or exploding bridgewire detonation system for Picric Acid alright. Haven' t really heard of that particular flying fragment detonator you mentioned. I do have some really big capacitors, 25uF @ 2000V, that should make a bridge wire explode! I find I am a bit reluctant to play with them, as capacitors like that make me more nervous than primaries in some ways. A good charging/discharging and safety system could make it very foolproof if care was taken. I have quite a few of these capacitors, as I took them out of electrical assemblies that were going to be tossed by salvage place. They were part of a military vehicle, but I don' t know what for. Are these suitable as an exploding bridgewire capacitor?

Rosco Bodine - 5-7-2009 at 15:58

Picric Acid is generally what I have used because it is cheaper and completely OTC, and its derivatives are also very useful. However, as a base charge Styphnic Acid appears that it would perform nearly as well and would be more easily initiated for being a bit more sensitive. The crystals of styphnic acid are distinctly harder material
than picric acid, forming from boiling water crystallization
more easily a precipitation of uniform sized hexagonal plates about the same mesh of table salt, giving a free pouring material which press loads beautifully. Styphnic acid is IIRC a higher density loose poured and it compresses to a pellet smoothly. I haven't really done
tests of the styphnic acid dets for comparison of the
performance against picric acid, but the witness plate
evidence indicates that styphnic acid would do the job almost as well on a weight basis as would TNP, and
perhaps on a volume basis for the combined base and initiator column may even do better. So styphnic acid is no slouch either as a base charge, but is of course more
expensive and the precursor is less convenient. In certain configurations however it is possible that styphnic acid could be technically superior. That is a
range of experiments which I haven't really investigated.
But it appears that styphnic acid being more sensitive to initiation would perhaps not require an initiator to be press loaded, but could probably be topped with an aqueous dextrine solution dampened putty made of microparticulate lead azide and lead styphnate, allowed
to slowly air dry to a hard pellet in a firing squib later
inserted against the base charge, or perhaps simply
depositing the damp putty directly directly onto the
the compressed base charge and letting it air dry in place. Styphnic acid is distinctly more sensitive to initiation and indicates having a smaller critical diameter
would be probable although I haven't checked this.

grndpndr - 5-7-2009 at 22:10

Im sure you have far more experience here but are you sure a reinforced cap is really nescessary?I havent heard of any complaints from plain AL hobby tubing cut with the obligatory tubing cutter and epoxied wood dowels.As for pressing a small 4in vice(to small!) and dowel seemed perfectly adequate except in the case of max density for mercury fulminate which apparently didnt matter nor did a bit of tissue/etc seperating the primarys and TNP.A test similar to davis chem of powder and explosives IIRC revealed a textbook result,Hole punch in the bottom of the witness plate and no bulging of the detonator with the TNP pressed to near max density and apparently very brisant compared to commercial #6-#8 and more akin to a military engineer detonator.I made dozens without failure electric and fused.The tubing was both 5/16 and 3/8 for the larger caps 2-3 gramsTNP .I also subscribe to the more is better approach for inexpensive materials when detonating a potentially expensive labor intensive energetic.Regards,no disrespect intended .Though ive made more than I can recall I certainly realize Im no expert(as my failed lab reveals)and Appreciate
your input.Regards.
Safetys sake a large sandbag was always placed over the pressing op and detonator.
My apologys for all the edits but it occurs to me condenser coils/tubing is nescessarily much softer than the hobby tubing.

[Edited on 6-7-2009 by grndpndr]

[Edited on 6-7-2009 by grndpndr]

[Edited on 6-7-2009 by grndpndr]

[Edited on 6-7-2009 by grndpndr]

[Edited on 6-7-2009 by grndpndr]

Rosco Bodine - 6-7-2009 at 05:52

Quote: Originally posted by grndpndr

Im sure you have far more experience here but are you sure a reinforced cap is really nescessary?

What I said about the need of reenforcing caps was qualified with regards to the quantity and properties of the initiator and base charge, and the geometry of the
device, ect. which are factors having bearing on whether or not a reenforcing cap is required or not.
You must have misunderstood or maybe I wasn't clear.
My own preference is to not use a reenforcing cap design. The quantities and materials which I report may then be presumed applicable to an unreenforced
configuration. I have tried to be specific about the
differences and how one configuration may be useful compared to another, without going so far into the
topic as would change this into a complete instructional step by step which would get this thread locked. When
you edit more than once, you can also edit out all your previous "edited notices" so that only one will appear.

You may be confusing the reenforcing cap configuration
with the laminated capsule design which I have described
having an aluminum liner. They are two entirely different things. A reenforced detonator can be made in any capsule
type laminated or not, where the reenforcement means
simply that the the initiating charge is itself mechanically
contained and retained in a pressed confinement against the base charge. The idea of a reenforced detonator is confinement of the initiator to intensify its impulse directed upon the base charge, and has nothing to do with the outer capsule which contains all of the inner elements assembled
in whatever sequence. Usually the reenforcing cap which
contains the initiator is a miniature capsule having a perforated closure disc, and the thimble like capsule is
filled with the initiator. Its diameter is a sliding telescoping
fit within the outer capsule, and when it is pressed against
the base charge in final loading, the expansion of the inner
walls of that thimble locks it into place holding the initiator
securely against the base charge. The perforations allow
for an igniter charge above the partition to commute fire to the initiator within the reenforcing cap. A laminated capsule is just a "stronger capsule" but a reenforced detonator references a specific configuration of containment for the
initiator itself being mechanically confined against the base charge, to greatly enhance the impulse of the initiator.

[Edited on 6-7-2009 by Rosco Bodine]

Reinforced detonators

grndpndr - 7-7-2009 at 05:29

Thank you sir for taking the time to clarify that for me.I believe I have the
basic idea now.I at first thought the reinforced cap was similar to a strongly confined hard to detonate energetic
in principle which didnt seem to make sense.If i understand the idea of the composite cap is to avoid the use of a metallic tubing avoiding its decomposition problems the metall tubing supplying the strenghth to withstand the pressing?

The pelletized detinators fascinate despite the drawbacks of I would suppose fragility,possible hygroscopic.Still i can evvision some great uses for such a devise,I suppose some rather exotic primarys are used.C an you recccomend some reading resourcesRosco, regarding primary sensitivities as wekk as pelletized detonator primaries/construction Regards. grndpndr

Rosco Bodine - 7-7-2009 at 11:26

Basically a reenforced detonator has extra confinement around the initiator so that the impulse of the initiator is focused more in the direction of the target base charge as opposed to three quarters of the energy of the initiator going off into space in different directions where
that energy is lost and never delivered to the base charge. Even in an unreenforced detonator you will find that the geometry of the initiator is important and the portion of the initiator having accelerated to maximum velocity should conform to the geometry of a ribbon charge , a platter charge which directs more efficiently
the impulse from that disc into the columnar section of base charge. When you get that effect then you are
getting what you need for maximum output. I'll have to get back on the rest later.

grndpndr - 9-7-2009 at 00:26

This must be the reasoning behind the concave end of a commercial cap.Focusing the energy very much like a SC.
The concave end like a platter charge or old fashioned monroe effect AP design.That effect would be simple to duplicate using hollow tubing
and copper/al end cap dimpled with a hammer and a properly sized ball bearing.Soldering the IMP sc end plate to the tubing of a composite cap and grinding the excess

I missed the primary reinforcement used to concentrate its shock helping detonate the composite caps secondary.It would be great to be able to buy a sized end cap to fit.Possibly in the copper fittings of a plumbing supply. To fabricate the reinforced primary cap/help initiate the secondary with a SC end cap?

Have thier been attempts to create detonators that are in fact minature CSCs? I have heard of military SCs maybe prior to piezoelectric CSCs that use a nose fused minature CSC to detonate the main CSCs detonator.Complex for sure but superior to some ideas ive seen floated elsewhere.

[Edited on 9-7-2009 by grndpndr]

[Edited on 9-7-2009 by grndpndr]

Rosco Bodine - 9-7-2009 at 05:47

Yes the shaped charge effect is exploited in some detonator designs for the initiator, the base charge, or both, but it is an added variable factor and a complexity which is not good to make an included aspect of an improvised cap except as an enhancement of redundant capability. For an improvised device you will likely be using components which were actually designed and manufactured for another purpose, instead of being precisely optimized for what they are being adapted.
That alone introduces enough complication and will generally increase the size of the device you are cobbling together. It is easier and better to put together
something basic and functional than it is to get elaborate when that isn't necessary.

[Edited on 9-7-2009 by Rosco Bodine]

grndpndr - 10-7-2009 at 04:32

KISS principle.

[Edited on 10-7-2009 by grndpndr]

Rosco Bodine - 18-7-2009 at 16:52

Something worth experimentation with regards to the lead salt of picric acid and the lead salt of styphnic acid
is making a determination if there is possible the formation of a double salt which is anhydrous, and could have improved properties as an initiator if it does exist. Ordinarily the normal picrate and the normal styphnate of lead are each monohydrate salts. However there is a double salt Lead Acetate Styphnate
which is anhydrous, I think

, and a parallel circumstance may occur for the double salt which I hypothesize may exist similarly as Lead Picrate Styphnate. If it exists as anhydrous double salt,
by virtue of having less water and more nitrogen,
and being made from two parent compounds having
interesting properties, it could be worthwhile.

Formula for the hypothesized salt would be
Pb2[(C6H2(NO2)3O]2(C6HN3O8)
This may be novel and therefore unreported.

http://www.youtube.com/watch?v=1lleBP7Ai7Q&fmt=18

[Edited on 19-7-2009 by Rosco Bodine]

grndpndr - 19-7-2009 at 11:21

Thanks for the lead Roscoe,I never cease to be suprised by how accomodating you are with those of us with lesser understanding /skills.Regards,grndpndr

In redards to the double salts/complex salts a quick check revealed several patents that may be useful though I havent
had time to look at them.
US patents 3293091 complex salts of basic lead picrates
2226391 man of basic lead trinitro-m-cresolate

2295104man of lead trinitroresorcinol and double salts
I havent seen the entire patents they may not apply at all to what you had in mind but in any event something learned isnt a waste.

[Edited on 19-7-2009 by grndpndr]

Rosco Bodine - 19-7-2009 at 11:57

No problem. My time for experiments has been non-existent, but I keep thinking about things and come up with virtual experiments in my mind. I share the ideas with anyone else who may have the time and the inclination to check out any of these possibilities where
the literature has nothing to say, but it would seem possible. It just leaves a head scratcher there for
not knowing. While I am speculating, if such a double salt does exist, it may also be a clathrate former if
the basic salt holds together as the double or multiple salt. There could be a synergistic multiple salt clathrate variant maybe with a chlorate or perchlorate component,
and possibly the azo-clathrate series as well. But the most immediate interest would be the formation of
the possible normal double salt to see what properties it might have and if it is a synergistic compound where
each enhances the other. Such things do happen sometimes, so it is definitely worth a look. If the normal double salt does exist and have a synergistic enhancement between the picrate and styphnate components, it would perhaps have enough initiating
ability that in a reenforced configuration it might be
usable for initiation of a styphnic acid base charge of
very fine mesh crystals, in a 5/16 to 3/8 in column
diameter base charge. A lot of unknowns there, but
that is what I was thinking.

grndpndr - 19-7-2009 at 12:15

I most often do nothing with what ive learned or think ive learned actual experimentation the only way I would be assured what I had done was successful.Being of practical mind due to nescessity: skills not up to the task of interests
in many cases.Sometimes the 'simple' successful practical applications
require a suprising amount of effort which can be very satisfying.Attempting to improve ones understanding given limitations a slow process but quite engaging.Your help here is always appreciated.

Rosco Bodine - 19-7-2009 at 18:21

The method I was contemplating was to use a mixed hot solution containing sodium picrate 2 moles and sodium styphnate 1 mole, added dropwise at equal rate and simultaneously with an equal volume solution of lead nitrate 2 moles, slightly acidic with nitric or acetic acid, going into a starting lump of hot distilled water also acidified slightly with acetic acid. The presence of a slight acidity is useful to prevent the formation of the basic salts which lead is prone to do if the pH is too high.

http://www.youtube.com/watch?v=860HwEgSRhY&fmt=18 True Nature

Something with regards to improvising compound detonators of the reenforced type which I have seen described but have never tried, involves the use of cartridge brass of the straight wall variety or the blanks for what would later be
necked down using dies. Two different brasses are selected which are a close but easy telescoping slide fit for one inside the other and the intiating charge is placed in the smaller diameter and press loaded. The smaller shell casing is decapped and a fired primer or a drop of epoxy or solder closes the primer hole on the larger shell casing. A small increment of base charge is pressed loaded more lightly onto it. The main base charge is pressed in increments to nearly fill the larger shell and the shell filled the remaining way with a lightly pressed increment. Then the two shells are pressed firmly together, at a slightly maybe 10% reduced pressure as was originally used on the initiator. The soft brass of the inner casing expanded by the loading pressure locks everything into place. I forget which brasses are convenient for this. There are several which can be used this way.
.444 Marlin was one if I remember right. Just a little info
there for the scrounging around the gunsmiths shop sort of
thing. Coating the outside of the smaller casing with some epoxy just before final assembly would possibly help make sure there is no creep after pressing. Probably all gunsmiths know about this one and have known for a long, long time.

[Edited on 20-7-2009 by Rosco Bodine]

grndpndr - 19-7-2009 at 21:56

Done a fair amount of reloading besides what youve mentioned a live primer in the primary side would make a fine stab or FP detonator.One would still want the interior to be of 5/16-3/8 if TNP were involved as a booster leaving pistol cartridge brass or carbine straight walled brass possibly .30carbine for the interior brass5/16 some .31hundreths actually .308 to accomodate the projectile if the brass were resized otherwise the projectile a drop in fit
likely near 2in long.The brass of course would be heavier at the primer end advantageous if ive been following the reinforced detonator posts correctly.

Rosco Bodine - 19-7-2009 at 22:44

You got it, the thickened brass at the base of the shell
acts as a reenforcing collar and confinement for the initiator and the extra mass there probably causes a
reflected wave additive to the main wave through the initiator in the direction of the base charge, so it is the
double whammy there which makes whatever initiator
is used have an amplified effect. It is similar to the situation if you were trying to crack a boulder with a stick of dynamite just laying against it, and it didn't work.
And then you put a five gallon bucket full of wet mud on top of another stick and tried it again and yep that'll
do it better. Pushing back against seventy five pounds
of mud gives the detonation wave a bit more traction
at the start, and it's the same deal with the reenforcing cap.
Anyway, I wouldn't do this or at least wouldn't make any habit of it using a regular press and dies. You need something where you can regulate the loading pressure
pretty well and know exactly what sort of pressure you are
delivering. And you need to use separable dies and have some sort of provision in safeguard for the what if one of
the things goes off during pressing....which can happen.
These things are not a trifling matter in terms of what they can do to press, dies, and operator if they should misbehave
and go unexpectedly. Think ahead, and be safe.

[Edited on 20-7-2009 by Rosco Bodine]

grndpndr - 20-7-2009 at 05:48

Of course safety first,I would never confine a cap like that in a steel die!Basically,reinforced det. just tamping/stemming the primary charge not with mud/sandbags but metal.
The cap material ive seen used never required additional support to possibly create addittional shrapnel and careful is the word in measuring wgt/density for pressing to the correct gr/cc3 w/correct wood dowel and screw press.As well as sandbags covering the pressing op.and personal protection.In any event my interest is theoretical rather than practical application.Just as much fun, well....almost,but much safer in many respects.:

[Edited on 20-7-2009 by grndpndr]

grndpndr - 16-8-2009 at 00:55

Another problem withn the HG fulminate/picric acid compund detonator would be the reactivity of the HG fulminate with the AL tubing or copper tubing.As well as storage stability of HG fulminate.
Given purified HG fuminate from powerlabs acetic acid ammonium hydroxide IIRC will give very good quality HG Fulminate with very good crystal shapes and density by itself increasing possible shelf life.
However im unaware of any material coating/tubing which is nonreactive with HG fulminate and TNP.SS possibly or a simple coating of the AL, steel,copper tubing?The basic Idea is successful in the extreme with just 1gr/2gr+ HG fulminate/TNPbut a storage stable cap with the material mentioned is out of the question.Ive yet to investigate the lead picrate /pottassium chlorate-TNP compound cap
90/10. AL would be suitable/nonreactive with this metal I assume but the safe storage life is still in question.

Rosco Bodine - 16-8-2009 at 21:43

Nobody but me that I know about ever reported it, but mercury fulminate can be purified quite easily from boiling water, so long as the process is carried out over a reasonably short time of exposure to the elevated temperature, the stability of mercury fulminate allows it.
Exactly how safe the process is I cannot guarantee, other than I did it and it went smoothly without any incident. I started a beaker of water boiling on a stirring hotplate and with rapid stirring sprinkled in
the amount of crude mercury fulminate to achieve about a 90% saturated solution at the b.p. of H2O, and then rapidly cooled or quenched the solution and out dropped snow white and pure mercury fulminate, pretty as you please. But truly this was just a curiosity and
mercury fulminate is not really a superior initiator.

Hennig Brand - 28-8-2009 at 07:58

I have just tried to purify MF from water. I did get partial success, in the sense that I got a feel for it. I used 4.6g of MF from a batch I made two weeks ago, from 5g of mercury, and a 600mL beaker. I used a magnetic stirrer as you suggested, but mine is homemade and doesn' t have a heating function. I used a hotwater bath which I keep near boiling by replacing the water with water from a kettle kept at a boil nearby. I added 50mL of boiling water to the beaker then added the 4.6g of MF (your way is better I know as it keeps less MF crystals, undissolved floating around at one time), but I was trying to be quick. I soon found that I had filled my 600mL beaker with water from the kettle, and that the temp was only around 85C despite my best efforts, and I still hadn' t made all the MF go into solution. From a link that I have found this morning, if correct, it states that MF solubility in boiling water to be 1g to 130g of the water. So if 600mL of water was at the boil (100C), it should be about what was needed to put the 4.6g of MF in solution. I wish I had found this link before, oh well, live and learn. It sure takes a hell of a lot of water!
Link for wikianswers-MF solubility
http://wiki.answers.com/Q/Is_Mercury-II_Fulminate_Soluble_in...

[Edited on 28-8-2009 by Hennig Brand]

User - 28-8-2009 at 16:03

Wtf has this 2 do with PA?

[Edited on 29-8-2009 by User]

grndpndr - 29-8-2009 at 11:45

Quote: Originally posted by User

Wtf has this 2 do with PA?

[Edited on 29-8-2009 by User]

If youd have bothered to keep up with the thread it might be
it has to do with det PA ,picric salts etc..WTF does your post have to do with anything but whining?

[Edited on 30-8-2009 by grndpndr]

uchiacon - 13-11-2009 at 03:13

Hey guys,

I just managed to purity about 56g of ASA, but it appears that it has saccharine traces in it.

My question is, will this effect the TNP synthesis, and would it be best to do my first TNP reaction with nitric acid and sulfuric? I've had bad experiences with solid nitrate and sulfuric acid, and nitric acid makes the stirring much easier.

Also been having trouble finding phenol(wow, that stuff is a bitch to find!) no industrial suppliers will give me any samples, even though I easily bought 99% sulfuric acid from a chemical company which is much worse. Do you guys buy it from lab suppliers? If so, at what price? Or do you find an industrial user and buy off them and what do they use it for? The cheapest I found from a supplier was 90USD for 500g, or 200L drums lol for god knows how much.

Any help is appreciated.

Cheers

Uchi

[Edited on 04-07-09 by uchiacon]

entropy51 - 13-11-2009 at 11:27

Quote: Originally posted by uchiacon

Also been having trouble finding phenol(wow, that stuff is a bitch to find!) no industrial suppliers will give me any samples, even though I easily bought 99% sulfuric acid from a chemical company which is much worse. Do you guys buy it from lab suppliers? If so, at what price? Or do you find an industrial user and buy off them and what do they use it for? The cheapest I found from a supplier was 90USD for 500g, or 200L drums lol for god knows how much.

I think 90 USD for 500 g is not a ripoff IMO, but others may know of cheaper suppliers. I paid just about that much to have a pharmacist in a mom & pop pharmacy order it for me. Don't try this at a chain pharmacy.

Several of the many chem suppliers that have been named on this very forum sell phenol. I don't know why you're having such a hard time, or are you not located in the US? Our overseas members have also mentioned a lot of suppliers as well. Go through the threads here and make a list of the companies that are mentioned. If they are discussed here, they will probably sell to individuals.

I sort of doubt that many of us are buying from industrial users, but I could be wrong. That would be my last resort, if that.

Finally, chemistry is just not a cheap hobby. I wish it were so.

uchiacon - 13-11-2009 at 20:53

Well I live in New Zealand, which is why I can't order this stuff as easily as others...

Correction, the phenol is actually $100US/500g, which is a fucking ripoff. I know that when you buy these chemicals you're paying for A. the company name thats screwing you, and B. because they've taken a bit more time to refine it. I would also assume theres a HUGE markup on that, and they try to cover this by saying it's analytical reagent grade. Sure, but how much did that refinement actually cost?

Funny though, I might just skip DDNP and try to synthesise sodium azide from scratch with the hydrazine and nitrite method. In fact, it's probably actually the best route from here, and the best primary to date.

$100 US would easily cover all the chemicals (the apparatus I already have) for maufacturing sodium azide.

uchiacon - 21-11-2009 at 02:32

Well, I managed to find a replacement for phenol; I'm fairly sure that sailicylic acid gives a higher yield of TNP than phenol too. I have a beaker full of yellow crystals, they stain like heck, and the volume is several times greater in TNP than what I had of salicylic acid. Now lets hope theres no crap in there. I'm buying my salicylic at $30 (21USD) for 500g, which is pretty crazy. And it's ridiculously fine.

When I figure out how to resize images I'll post some.

I'm looking into lead styphnate and lead azide, I'm sure I can track down some resorcinol to make the styphnic acid with. I don't think its particularly hazardous and it's widely used in parts of the industry that I phoned around looking for phenol.

Hydrazine hydrate will be a bit harder though, but if I can find a source of it then the lead azide manufacture should be quite straightforward from then on.

Is it used in narcotics manufacture at all?

uchiacon - 23-11-2009 at 01:24

Ok, so I've been making TNP (or attempting to) using salicylic acid. I'm following the powerlabs procedure, but the four times I've done it (15g salicylic, 25ml sulf and 37.5mls of nitric) the salicylic acid has ALWAYS hardened into some crusty semi liquid brown reddish crap in the beaker. I heat the 99% sulfuric acid to about 60 degrees C, dissolve in the salicylic and turn up the heat to 100 degrees.

It then progressively turns into a dark brown/reddish solution. Then I take it off, give it a stir, and suddenly it just completely hardens into this crusty goop. Then I cool it in an ice bath, add the nitric at -20 and everything goes fine from there. Chuck it into cold water, precipates out the TNP and then I wash it and dry it.

But today as I was filtering out my first batches, I thought it was unnecessary to wash the crystals with about 1L of ice cold water as suggested by powerlabs. I used abotu half that, and when the TNP was sufficiently dry, I attempted to try and ignite it with hardly any success.

The pale yellow material stains my hands, is relatively insoluable in water but doesnt burn well at all. I did manage to get a large chunk to burn, but it only burned when I held the blowtorch on it for a while.

It also won't detonate from a hard hammer blow, what's wrong???

User - 23-11-2009 at 04:30

What is the source for your salicylic acid?
Did you just buy it or is it purified/modified from aspirin?

It sounds like there is a percentage of TNP in your product.

[Edited on 23-11-2009 by User]

Rosco Bodine - 23-11-2009 at 05:07

Probably the use of salicylic acid as the precursor would be better adaptable to the synthesis which has been described by myself and confirmed by ordenblitz as being useful for the acetylsalicylic acid precursor. You could use a bit more, maybe 20% more H2SO4 than the minimum proportion which has been described, in order to have a thinner reaction mixture which is easier to stir. Anyway picric acid is not a deflagrating material like smokeless powder but it should definitely give a good snap from a sharp impact of steel on steel, and it should be capable of initiation, although with some difficulty because it is not a very sensitive material at all, requiring a persuasive initiator which generally knocks the doggie doo out of it in order to achieve its effective initiation.

Have a fairy nice day

franklyn - 29-12-2009 at 00:53

The following two papers could be useful in a two stage process for TNP

Highly Accelerated Microwave Assisted Aromatic Nitration with Dilute Nitric Acid
http://www.envirofacs.org/Pre-prints/Vol%2039%20No%201/Paper...

Salicylic Acid Nitration by Means of Nitric Acid/Acetic Acid System
http://pubs.acs.org/doi/abs/10.1021/op060148o
Direct download here _
http://www.aseanbiotechnology.info/Abstract/21020685.pdf

Someone may want to request these two in the references section _

Batch salicylic acid nitration by nitric acid/acetic acid mixture
under isothermal, isoperibolic and adiabatic conditions
http://linkinghub.elsevier.com/retrieve/pii/S030438940600623...

Solubilities of Salicylic Acid in Pure Solvents and Binary Mixtures Containing Cosolvent
http://pubs.acs.org/doi/abs/10.1021/je800475d
May have use in processing aspirin to rid it of binders.

.

Rosco Bodine - 29-12-2009 at 02:22

I sure as hell wouldn't subject precursor aromatics beyond the dinitration stage
to microwave radiation under nitration conditions, because it smacks of a fools errand. What's cooking in the microwave is a sprengel explosive.

franklyn - 29-12-2009 at 10:45

Quote: Originally posted by Rosco Bodine

I sure as hell wouldn't subject precursor aromatics beyond the dinitration stage
to microwave radiation under nitration conditions, because it smacks of a fools errand.
What's cooking in the microwave is a sprengel explosive.

Did I imply that ? or are you stating the obvious to the foolhardy.
Rapid exotherm is a problem as it is , no need to go to afterburners.

The second paper outlines a conventional process yielding mononitro
product using 70 % HNO3 in AcOH - which I can add is potentially
detonable, there is also serious risk of ignition that is overlooked.

The first paper outlines initial nitration by microwave in water containing
15 % HNO3 yielding mainly dinitro products even a small amount of trinitro
product in less than three minutes !
Most details are in the middle two pages , it's only four pages.
Or is it true you can't teach old dogs new tricks

Rosco Bodine - 29-12-2009 at 16:25

If nitrosalicylic acid was the desired end product, or use of a dilute nitric acid for preliminary nitration was a goal, maybe the microwave process could have value there. But for picric acid as a desired product it would seem that involving a sulfonated intermediate, a sulfosalicylic acid, and thermally driven nitration
would be safer and more predictable. My opinion about the inherent danger is based upon a prediction and expectation that it will take a lot more HNO3 concentration than 15% to achieve the trinitration, and that seems like a
dangerous mixture of (oxidizer) which is also the nitration agent to be in mixture with a material which is already explosive at the dinitration stage, being heated
in a way that could generate hot spots within the mass.....which is precisely the thing wished to be avoided for the safe and smooth nitration of anything.

franklyn - 30-12-2009 at 16:12

" If nitrosalicylic acid was the desired end product, or use of a dilute nitric acid for
preliminary nitration was a goal, maybe the microwave process could have value there."

This is the point I expressed in the opening line of my initial post
" could be useful in a two stage process for TNP ".
The inherent problem with mixed acid nitration is that as the process proceeds ,
the HNO3 if it is not fortified becomes less concentrated as it is consumed ,
precisely opposite to what is desired to obtain the trinitro end product. Indeed
according to COPAE benzene without an activating group attached requires
fuming HNO3 to obtain Trinitrobenzene. A reason why industrially aromatic
nitration as for toluene is done in stages.

" My opinion about the inherent danger is based upon a prediction and expectation
that it will take a lot more HNO3 concentration than 15% to achieve the trinitration,"

Initial mono or dinitro products can be made in a facile manner by this microwave
procedure and those in turn subjected to the conventional approach more
efficaciously it would seem , with better use of HNO3 and less wasted. As HNO3
is consumed in the microwave process and the concentration is reduced , the risk
you apprehend is self restrained. Which is very likely the reason so little trinitro
product is seen - no more HNO3. Timing here matters of course since allowing this
to go on would doubtlessly decompose the end product. Such application for the
disposal of energetics has been considered.

All this said , I absolutely concur with your discourse here _
http://www.sciencemadness.org/talk/viewthread.php?tid=13187&...

.

[Edited on 31-12-2009 by franklyn]

Rosco Bodine - 30-12-2009 at 16:33

Ironically the depleted acid has a higher oxidizing effect so that
presents something of a dilemma with regards to the safety
when introducing the third nitro. It may be workable but it
isn't a process which on first look fills me with enthusiasm.

Hennig Brand - 2-1-2010 at 13:26

Sorry for interrupting, I have a quick question.
Rosco, how much better is Na nitrate than K, or NH4 nitrate in an ASA nitration? I ask because I have never used sodium nitrate, and also because I just recently discovered that NaNO3 can easily be made from NH4NO3 and plain old baking soda. I didn' t realize this before, I think because I was only considering the solubilities of the two nitrates in a double displacement reaction. The trick is apparently to boil off and decompose the Ammonium bicarbonate, leaving you with pure sodium nitrate in solution. From a youtube video about this it shows two processes, one with the baking soda, and one with soda lye. For the NaHCO3 one, it says to take 80g of An and add it to 150mL of water. After everything that will dissolve has, filter onto 84g of NaHCO3. In a well ventilated area boil down to less than 100mL in a well ventilated area as a lot of ammonia is given off. Dehydrating what is left should yeild very pure sodium nitrate.
I thought maybe some weren' t aware of this either. Maybe this summer I will get a chance to try "Rosco' s good old country recipe".

I have a feeling that it will be far better than Potassium nitrate. What has been your observation Rosco?

Rosco Bodine - 2-1-2010 at 14:39

There hasn't really been any charted comparison study done by me to compare the efficiency of the different nitrates. I haven't tried all of the possible combinations to really optimize the process in terms of economy of acid or
other goals, but mainly was trying to a achieve a pure end product with
reasonable economy and safety, which proved to be predictable using
sodium nitrate. The lower solubility of the byproduct bisulfate when using
the potassium nitrate requires a greater proportion of acid to maintain a stirrable reaction mixture, so it is less economical and therefore no effort was made
to really optimize a procedure using the potassium nitrate, although it did
seem that it can be substituted in a similar procedure where it may work as well with adjusted proportions and other reaction parameters adjusted for tuning the reaction to accommodate whatever differences are encountered. The same is possibly true for a nitration using ammonium nitrate, but this is not certain, and it is also possible that use of a nitrates mixture or a two stage process may be workable, but such schemes add complexity. There are different behaviors about the nitration which are observed depending upon the temperatures, and the
water content and the particular nitrate used. The most common mistake that people make in approaching the nitration is being fearful of the heating which
is required to maintain the reaction system at a point where it is responsive to
reaction rate control achieved by rate of addition of the nitrate, compounded
by impatience about the time required to observe the delayed effect of each
addition and pace the process of additions accordingly. There is a responsiveness to additions which is not linear but changes as the nitration proceeds. What most people have described as "runaways" are actually delayed inductions of an avalanche rate increase, due to too low a starting temperature and too rapid addition of nitrate which causes accumulation of unreacted material in a reaction mixture which becomes self heating and then avalanches on the rate increase consuming the unreacted material, as if it were putting a match to kindling. This is why keeping the temperature elevated but within limits and going slowly with additions of nitrate is essential to control the nitration rate.

Attached is the picric acid pages from Thorpe in which there is described a nitrate process involving water dilutions, Kohler, DRP 67074, which I am not certain is accurate for not having tested this. But there are different processes and variations which could be the basis for experiments, as there are many different ways of making picric acid.

One interesting experiment I would suggest involves the drying of picric acid by use of a dessicant, in order to see the pronounced color fading that occurs on the moisture loss.
I have suggested the use of amalgamated aluminum as a dessicant in posts in other threads, and this would seem to be an ideal dessicant for use in an exhaustive drying of a sample of picric acid.

Attachment: Picric Acid, Thorpe 1911, dictionary_of_applied_chemistry.pdf (687kB)
This file has been downloaded 1097 times

[Edited on 2-1-2010 by Rosco Bodine]

Hennig Brand - 2-1-2010 at 16:03

I had the sense that sodium nitrate made life much easier, if just from the TNP purification stage after nitration(the sulphate being much easier to deal with). I think there was also a sense that ammonium nitrate for some reason did not work well, which seemed counter intuitive(something to do with the ammonia or something?). I was going to try NANO3 long before now by making it from HNO3, but once I had the acid I figured I might as well use it. If making NANO3 is as easy as it looks from NH4NO3 with just a beaker, it is looking better and better. Thanks for the input. I don' t quite understand how amalgamated aluminum is going to be a good dessicant, but then I don' t know much about it really.
Rosco, you wouldn' t happen to have a good old country recipe for Pentaerythritol? That would be nifty.

Rosco Bodine - 2-1-2010 at 16:21

PETN is best made by the DuPont process and it has been posted before. Here's Rosco's "good ole country recipe"

http://www.sciencemadness.org/talk/viewthread.php?goto=lastp...

Here is the patent DRP67074 I referenced earlier and it may be perfectly applicable to nitration of other precursors than phenol, or illustrates that there are nitrations possible which
can be done with acceptable efficiency in reaction mixtures where substantial water is present. I am not fluent in German but can only pick through it enough to get the general idea. Any insight others who know the language better may offer about this process is welcome.

Attachment: Picric Acid Process, Kohler, DE67074C.pdf (99kB)
This file has been downloaded 798 times

[Edited on 3-1-2010 by Rosco Bodine]

Hennig Brand - 2-1-2010 at 16:59

I won' t stray any more from the main topic after this. While I am interested in PETN, I was actually asking about PE. I was hoping there was an easy to follow method that could help me make this valuable precursor.
I regards to that other thread about Picric acid sensitivety, I think you are right. One of the main reasons I had such a hard time detonating my TNP samples for so long was that my perception was skewed by all the claims about TNP' s extreme sensitivety. I probably had a lot more success in the synthesis earlier on than I realized, since I was using the sensitivety as kind of an indicator of purity, etc. Picric Acid is very insensitive stuff, and unless there exists some very special conditions for which I am not aware, it is always relatively insensitive. I agree.
Thanks for the good links in the last post as well.

[Edited on 3-1-2010 by Hennig Brand]

Rosco Bodine - 2-1-2010 at 17:34

Sorry for my digression there about PETN, I saw you wrote PE and I'm not really sure what is the best method there. There is the classic method which presumes availability of acetaldehyde and formaldehyde as precursors, which are both actually less conveniently available due to storage and shipping issues, than is the more mundane PE itself which is cheap and nonhazardous. The classic synthesis for PE is in Organic Syntheses, Wiley. It is online unrestricted.

Taoiseach - 3-1-2010 at 05:54

I can confirm that salicylic acid as precursor works very well.

Experimental

80g of dry SA were put in a 2L round bottom flask. 250ml conc. H2SO4 were gradually added with stirring. Heat was applied until the thermometer read 95°C; the mixture was then stirred for about 15min at this temperature and gradually turned into a vicsous yellow syrup.

The flask was then put outside and left to cool to about 45°C. At this temperature, 300ml conc. HNO3 were added in small portions. After acid addition was complete, the mixture was observed for about 30minutes. Not much happened, there was slight evolution of NOx fumes and little bubbling. Heat was then applied until the reaction became more vigorous. Unfortunately I was unable to read the thermometer as the whole flask was suddenly filled with thick red fumes and I was forced to leave the area

Basically I applied heat for a short time, then observed if the reaction would self-accelerate. If bubbling would subside, more heat was applied and so on. There's a fine line between adequate heating to get the reaction started and turning it into a runaway nitration. The fact that the flask was placed outside where it was freezing cold might have been a lucky coincidence that prevented runaway. Heating it to a certain temperature until the reaction gets going and then slightly cooling it might be the trick. At the point where the reaction suddenly became violent the thermometer was reading about 70°C if I remember correctly. I forgot to properly stir the solution while heating it, and that was definetly a mistake. It makes the reaction somewhat unprecitable because the solid cake of phenolsulfonic acid at some point gets crumbled by the gas evolution which further accelerates the reaction.

Anyways, after the reaction had subsided the flask was filled with glittering yellow crystals. No red goo or brown crap, just nice clean yellow picric acid

The flask was heated to 120°C for about 30 minutes, then left to cool. The picric acid was seperated by dumping the crystal mass in 3000ml cold water, stirring and filtering. The filter cake was pressed as dry as possible on filter paper and then recrystallized from a 1:2 water/EtOH mixture. A nice crop of potassium picrate was recovered by bringing the filtrate to boil and adding K2CO3 until no more gas evolved. The picrate started to precipate in beautiful hair-like needles almost instantly after the beaker was removed from the flame.

Yield is yet to be determined as the PA is drying over NaOH now. A small portion was thoroughly dried with a hair dryer, placed on concrete floor and given a good smack with a hammer, and Boom it went

[Edited on 3-1-2010 by Taoiseach]

entropy51 - 3-1-2010 at 08:43

Quote:

No red goo or brown crap, just nice clean yellow picric acid

Any idea how much of it is 5-nitrosalicylic acid, also nice yellow crystals?

DE67074

Formatik - 6-1-2010 at 04:06

First they change phenol into dinitrophenolic acid, this being done by: heating 100parts phenol with 1000 parts conc. H2SO4 at 80 deg. to convert it to phenolsulfonic acid. Then it's changed into nitro- and dinitrophenolsulfonic acid by adding 192 parts (2 Mol.) of dry powdered NaNO3 in small portions to the cool sulfonic acid. Then the temperature is let rise to 100 deg. After all is solubilized, it's slowly heated to 140 deg. Then it's diluted with water and to the hot solution, milk of lime is added until alkaline reaction. Filtering the gypsum, to obtain the calcium salt in the filtrate. Which is evaporated, and acidified with hydrochloric acid, dinitrophenolsulfonic acid precipitates.

One of the examples then puts this above obtained dinitrosulfonic acid directly into procedure where it's diluted with 320 parts water, and then in the still hot 80-90 deg. solution, 148 parts NaNO3 are added. Then it's heated for 2 hours at 140 deg. After cooling, the picric acid is separated from the sulfuric acid and precipitated sodium bisulfate, extracting the latter with water.

Rosco Bodine - 6-1-2010 at 05:23

From what I am reading ( more or less

) and trying to understand,

It looks like the better approach involves examples 2 and 4, where the initial sulfonation carried out at 160-170. That higher temperature of sulfonation
produces a phenol disulfonate, then mononitrated by one equivalent of NaNO3.

Then the mononitrophenoldisulfonate is diluted with water and the nitration is completed by use of an additional two and one half equivalents of NaNO3,
with the nitration completed as before by heating two hours at 140 C.

If I am understanding correctly by this approach there is no use of lime nor
isolation of the partially nitrated intermediate, as is done with the alternate
scheme involving examples 1 and 3.

Formatik - 8-1-2010 at 14:56

Quote: Originally posted by Rosco Bodine

If I am understanding correctly by this approach there is no use of lime nor
isolation of the partially nitrated intermediate, as is done with the alternate
scheme involving examples 1 and 3.

No, that's wrong.

Example 2 is using phenol and conc. H2SO4 to get phenoldisulfonic acid, indeed mononitrated to nitrophenoldisulfonic acid. But then they say to precipitate the nitrodisulfonic acid, just like the dinitrosulfonic acid (from example1 which is also used in example3) using the calcium salt.

Example 4 converts phenol into nitrodisulfonic acid just like example 2.

Btw, I'm not sure if I'm right here since I haven't looked at these papers, but I believe nitrosalicylic acids are the result as long as temperature is controlled. Since if salicylic acid is nitrated with mixed acid below 10 deg., yield of 3- and 5-nitrosalicylic acid is near quantitative (Hirsch, Ber. 33, 3239), but heating salicylic acid with strong nitric acid converts it into picric acid (Marchand, J. pr. [1] 26, 397).

[Edited on 8-1-2010 by Formatik]

Rosco Bodine - 8-1-2010 at 19:29

What puzzles me is why they would use lime at all except for possibly a sample analysis where there would be an effort to precipitate and identify intermediate products which are present in a nitration mixture ? It is a one pot nitration
which has no requirement for being separated into two stages, so the generation of waste byproducts like gypsum is no advantage that is at first apparent.

I couldn't agree more.

Formatik - 8-1-2010 at 19:39

Sometimes patent inventors come up with quirky, kooky, hula-hoop methods they hope will be carried over into the industrial setting.

franklyn - 15-1-2010 at 12:25

Continued from this post abaove - Files attached
http://www.sciencemadness.org/talk/viewthread.php?tid=389&am...

.

Attachment: Cold Microwave chemistry synthesis using pre-cooled reagents.pdf (79kB)
This file has been downloaded 1675 times

Attachment: Microwave Nitration of phenols with Ca(NO3)2.pdf (88kB)
This file has been downloaded 1876 times

Vod of bullseye make it a usable base charge?

pjig - 25-5-2010 at 19:13

Is it to far fetched to say bullseye or other fast double based powders could be used for a base charge in a blasting cap? I have only seen one patent where it was posted as a usable base charge. Could this be possible? I would assume that the charge could be cast using a solvent( nitro methane or acetone, etc) to bring up the density. I have found studies showing that bullseye is capable of achieving up to 25,641 fps unconfined with a #8 cap. This would lead me to believe it could useful, assuming that the primary is efficient. ( ddnp, fulminate, or hmtd..etc)

My question is can this be a possible way to manufacture of compound detonator ? Or would the base charge need to be a matrix of another secondary with the double based powder( like picrate acid, r-salt, etn..... and so on) to be strong enough?

franklyn - 30-5-2010 at 13:45

Page 43 Excerpted from
Comprehensive Chemical Kinetics: Vol 13
Reactions of Aromatic Compounds
By C. H. Bamford, Charles Frank Howlett Tipper
http://books.google.com/books?id=YJngAwojNqwC

We see here that constitution and equilibria of acid matters more than
the relative activation of the ortho , para , meta , sites on an Arene ring.

Catalysis of Nitrous acid.gif - 99kB

quicksilver - 31-5-2010 at 06:24

Yes. A dbsp could be utilized as a combination of materials if detonated with an appropriate train would satisfy the speed & brisancy need to get picric acid to shoot.
Picric acid is often compared with TNT but it's "needs" are substantially different.

You can make TNP from so many materials it's quite unique.

Attachment: german-picrci-acid105560920.pdf (88kB)
This file has been downloaded 818 times

pjig - 31-5-2010 at 20:33

Quote: Originally posted by quicksilver

Yes. A dbsp could be utilized as a combination of materials if detonated with an appropriate train would satisfy the speed & brisancy need to get picric acid to shoot.
Picric acid is often compared with TNT but it's "needs" are substantially different.

You can make TNP from so many materials it's quite unique.

dbsp's seem to get overlooked in their ability to be a possibly replacement for tnt , "in a pinch" . It has been said that dbsp is about par in ddt with tnt. ( around 22-23,000fps)

Im wondering if a detonator can be made, by pressing a base charge of dbsp powder into a case and then a strong primary. Would the dbsp have to be combined with a stronger energetic material to be effective and cast as a melt or matrix?

I have successfully initiated kinepak with a cap made of .5g hmtd and a base of dbsp 1g. Im not sure if it was luck or good confinement that led to ddt, but it worked.. It does seem like a very underpowered cap though ,possibly a #6 equivalent.

As far as a good" train" are you saying that tnp, if cast into a dbsp melt should serve as a sensitive base( like pent) ?

quicksilver - 1-6-2010 at 08:22

Air pockets are a problem in respect to efficiency.The polymers (Polyester often enough) utilized in many dbsp are best fused with a solvent that minimizes the air pockets (thereby creating a solid where there once was a compacted group of particulate) - similar to a extremely heavy NC lacquer.

Somewhere there is a list of those DBSP with higher NG content (TiteGroup 37%; BullsEye 40%, Nitro 100 20.5% AA #2 variable @ 20.5-23%, Cordite/Ballisite 49%, Chinese ball copy WW231 43% & so on). This packaging emulates the percentages on many common energetic dynamites, etc. The controlling of the burn rate (& thereby it's use as a propellant) was a duel faced agenda of a heat-oriented primer rather than a detonation - and the design element incorporated in the physical shape of the powder. Burn rate adjustment & DDT in this area is a science w/ a great deal of research behind it.

However the mp of Picric Acid is rather high & that of TNT low: low enough to be the material of choice when a cast material was called for. So the physical shape of the powder can be overcome by the use of a solvent & Picric Acid's high mp can be dealt with by the use of a lower melting addition (ETN, TNT, DNT, etc). Past efforts to melt Picric Acid were fraught with a great deal of danger & uncertainty.

When hot water was used with Picric Acid (water bath / sand bath graduated heating) the material retained bubbles unless the heat was high enough to come close to a danger point. {See Military Explosives, Weaver, 1905, 1917}

[Edited on 1-6-2010 by quicksilver]

The WiZard is In - 1-6-2010 at 12:02

Quote: Originally posted by quicksilver

You can make TNP from so many materials it's quite unique.

No doubt I will be chastised because I had previously posted
this in a different thread, however, I work for free.

The Chemical Gazette
London 1859
Some Observations on the Amount of Picric Acid obtained from Botany Bay Resin. By
Prof. BOLLEY.

The so-called Yellow gum, or Botany Bay resin (the resin of Xanthorrlueahaslilis)
[Xanthrorroea saxtilis] , was indicated by Stenhouse, and subsequently by Warington
and Bottger, as the most abundant source of picric acid. - It was said to furnish 50 per
cent, of picric acid, so that notwithstanding its high price, it was the most economical
substance from which to obtain picric acid.

The author has had numerous experiments made on this subject by his pupils in the
Pharmaceutical Laboratory at Zurich. In these the resin was treated with 10 times its
weight of nitric acid in a retort, and the distillate repeatedly poured back. At the
commencement strong effervescence and evolution of nitrous acid took place
without any application of heat; the action was afterwards assisted by heat, and this
was continued with return of the distillate until the mass in the retort was
completely dissolved to a reddishyellow fluid. This treatment furnished-
Experiment 1. 22-5 per cent, of picric acid (somewhat purified by combination with
potash and reprecipitation by muriatic acid).

Experiment 2. 25-6 per cent, of picric acid (obtained by crystallization from the acid
liquid).

Experiment 3. 15 per cent., and therewith a yellowish powder, consisting principally
of woody fibre, partly converted into pyroxyline.

By treating the resin with alcohol until nothing more dissolved, there was found to
be 16-68 per cent, of insoluble matter, of which 2-5 per cent. was ash. The portion
insoluble in alcohol consisted principally of small fragments of wood. In experiments
1 and 2, but little was to be detected in the residue left undissolved by nitric acid.
The difference in the results of these experiments and those made by others, may
rather be attributed to impurities or differences in the composition of the raw
material, than to differences in the mode of preparation. The statement that 50 per
cent, of picric acid may be obtained from the resin, can only be true in rare cases. -
Schweize- rische Polytechn. Zeitschrift, 1858, p. 125.

pjig - 1-6-2010 at 12:40

@quicksilver ...

Thanks again for your input, it's greatly appreciated...

I wonder if just dbsp powder is used w/o any other energetic material (dissolved in a solvent) would work alone, if cast in to a case as the main base charge. ...
Also knowing that when the mix dries it could shrink. Could this be anything to fear, if the base charge is allowed to fully dry, before the primary is pressed?

Also as a side note,and a bit of curiosity, does fine grade aluminium add to the ddt as it does in tnt? I was pondering the though of making a melt of nm+dbsp+Al to be cast as a plastic in a SC..

quicksilver - 2-6-2010 at 05:32

Albeit this is OT the question re: DBSP gives rise to transportation issues just as water packing Picric Acid does..
The short answer is - yes. DBSP is exactly what people would imagine it is; an explosive. The propellant aspect is a process of "taming" the materials via a combination of physical structure and a specific type of "primer" that does not act like a ignition cap.
Thus DOT can issue a "propellant" label for it's production & sale.
In hand-loading (or reloading) there is a phenomenon called "detonation" where too LITTLE powder is placed within a cartridge and the result is a catastrophic explosion, often resulting in damage to the firearm.

IF the material (dbsp) is altered in shape and form via a solvent, etc and it is initiated by a true primary it will detonate. This has been proven by various laboratories & experimenters. It also exists in some IED's & documented therein by some military services. I don't have notation of source listing at hand, but I do know that it exists from various references.

Addition of Al will generally sensitize & generate more heat in a detonation while slowing the VoD to a degree. Heat in an explosion will alter the overall affect & had been in place for a variety of reasons from anti-personnel to visual observation of an HE round. It's placement in Picric Acid is not common but it's use with TNT is. The addition to something like DBSP in reference to a DDT is something that has not been professionally explored. However the detonation modeling (see Davis & Fickett) often used today would show that more generated heat at the time of ignition would affect detonation in cases where a "borderline ignition exists.
Primers for firearms are often lead stephnate based. in such cases where a primary is "weak" (such as primer composition) powdered aluminum may have a profound effect in pushing ignition to detonation.

gnitseretni - 2-6-2010 at 05:58

Why make a plastic explosive? Why not mix the NM with a sensitizer (like HNO3 or microballoons) and use it in a SC? Being that it's liquid you'll get a better uniform density than you'd get with a plastic explosive.

pjig - 2-6-2010 at 07:59

@ Quicksilver, thanks again for your well informed answer..

(AS far as tnp, I dont think Al would be advisable to mix with)

The reason of making a SC out of the dbsp,Al and NM is one, that is not corrosive to metals and safer to handle, and if some where to get on you in the process. All in All I think it's just the novelty that one can create an OTC explosive ( not that N-acid isn't available ) ,with fairly high bristance and ease of access to materials.

[Edited on 2-6-2010 by pjig]

@ quicksilver

pjig - 9-6-2010 at 19:24

A quick Q. on compadibility....
I noticed that it was claimed that it may be possible to mix ETN and PA, for reasons of lowering the MP. I was just making sure that there are no incompadibilities of these( forming dangerous picrate compounds or spontanious reactions ) when mixed in a melt.
I'd imagine that this base charge would form a great compound det. able to initiate most sleepy explosives.

Now as far as a stabilizer for PA would it be needed for storage of the above mix, or would the cast be fairly thermaly insensitive. I'd imagine that urea may improve the shelf life. It seems both ETN and PA are very sensitive to quite a few different things, I'd hope a melt would stabilize this.( ETN=heat->deteriorates , PA= dangerous picrates)
One of my fears would be that the PA in the base charge would react with any metals ( electric ematch, squib, or priming comp. ..etc. ) forming a dangerous cap. One would have to take great care to seal the end of the ematch with wax paper glued on the business end.
PA and NM are used in one patent and shot in a aluminium can by a cap and booster pellet(6g) wrapped in foil....Isn't PA reactive to Aluminium? Pat. us5140908

I appologise as this is slightly off the main topic...

[Edited on 10-6-2010 by pjig]

[Edited on 10-6-2010 by pjig]

quicksilver - 10-6-2010 at 05:34

Well, all I could add is that patents are not always complete (or totally correct) so take everything you read in a patent w/ a grain of salt.
This is how I would project the issue: you have a nitric ester & a (very) mild acid. Their exposure level to each other would not be for any lengthy period of time. What's more, I believe that one or more of our senior members has experimented with a eutectic with these materials. frankly, I have not.

No "red flags" go off when I think about such a combination (ETN/PA).

[Edited on 10-6-2010 by quicksilver]

Hennig Brand - 10-6-2010 at 13:05

Aluminum is one of the things normally considered safe to use with Picric Acid. IIRC the Picrate formed is much less sensitive than the Picric acid it came from. It will also form very slowly, especially with little moisture and little heat.

I would also like to add that I have been making some Sodium Nitrate from Ammonium nitrate and Baking Soda, and using that in Rosco's TNP synthesis. It works so much better in all respects than Potassium nitrate that it is well worth it to first synthesis the Sodium Nitrate(I think). I see very little reason to bother with the Nitric Acid, the results were that much better than with KNO3. The synthesis(TNP) was much less work, and a superior product.
It takes a while to make the NaNO3 but it is a very simple process, which requires little attention.

Rosco's ratios where I believe 1 g ASA, 4 mL H2SO4, and 1.8 g NaNO3. I found I needed more like 4.5 mL acid to even get all my ASA into solution. I just did a 50 g batch and will get back with a dry yeild. It looks very good after one recrystalization, better than mine looked after two recrystalization when using KNO3 I believe. Nice big pale yellow, well formed, clean looking crystals.

Rosco Bodine - 10-6-2010 at 19:06

The composite of picric acid and ETN offers nothing as it is damned near impossible to completely detonate and probably isn't storage stable because of the acidity of the picric acid adversely affecting the ETN stability. What happens is the matrix of melt cast ETN detonates and vaporizes the particles of picric acid into a dye cloud without the picric acid being detonated. Picric acid is so insensitive to initiation that it requires the adiabatic heating provided by the compression of occluded air between the crystals to augment the detonation wave, and filling the microscopic voids with cast ETN doesn't do the trick. It barely even works with PETN crystals as the filler and is ten times harder to initiate than a compressed particulate composition. Anyway test it if you like and you will have proof positive just how damn hard it is to detonate picric acid under anything but very deliberately specific optimized conditions which would unlikely be encountered just by chance. Picric acid will detonate brisantly in a specifically optimized configuration of loading density and crystalline form. And it will do well in combination with various other materials, but ETN isn't one of them. The testing of a melt cast ETN / picric acid composite is an experiment which caused me to be further convinced of what I already knew from other similar experiments, and that is that picric acid is like TNT, not a sensitive explosive at all and is actually quite difficult to cause to detonate accidentally, and not even all that easily caused to detonate deliberately. That is no impediment however to its practical use, because under very specific conditions it will go high order very reliably.

[Edited on 11-6-2010 by Rosco Bodine]

pjig - 10-6-2010 at 21:13

Quote:

What happens is the matrix of melt cast ETN detonates and vaporizes the particles of picric acid into a dye cloud without the picric acid being detonated

That sucks... Thought I might have been on to something here.

Makes sense though, ETN being sensitive to the acidy conditions eventually breaking it down.
The patent posted in my last text was showing the improvement of picric in NM . Seems like a worthy material, probably close to Nitric A and NM. I guess thats why they used a 6g booster pellet to ddt it.
Do you supose any incapability's are in a DBSP/ TNP mix then..?

Rosco Bodine - 10-6-2010 at 22:31

Yes there is incompatability there for the same reason, acidity attacking the ester.

Hennig Brand - 11-6-2010 at 07:18

OK, for my 50g ASA batch I used about 750mL of boiling water to put the crude product into solution. This was all done in a glass whistling kettle (I have about 8 of these kettles now, made in Germany, borosilicate, $6 on sale

).
I put cloth pot holders under it and several layers of towels around it, and covered the top to prevent cooling due to evaporation. I left it to cool all night. I have almost exactly 43g after the first recrystalization, which is not the best I guess but it seems like very nice pure stuff.

Once I retrieve what is in the crystalization water I will probably have about 50g Picric Acid total.

I only kept the temperature at 100-110C for ~45 minutes at the end, and I didn't have magnetic stirring for the last stage of heating(I only have stirrer, not stirrer-hotplate). No doubt there are refinements that I can make to increase yield.

By the way, I have been using 0.4g Lead Azide with my TNP in compound caps. I have been just pressing it right on top of the TNP. Any reason why I shouldn't do this? I think Rosco indicated that this combination is very compatible and storage stable a while back(I think).

[Edited on 11-6-2010 by Hennig Brand]

Rosco Bodine - 11-6-2010 at 14:02

The older members are keenly aware of the inhalation hazards attendant to nitrations, but we are in receipt recently of a lot of postings from a younger crowd who evidently from their postings haven't done a thorough study of earlier writings and are likely to be complacent about the dread and insidious dangers of "oxides of nitrogen", particularly in settings where formal lab equipment and procedure is not being used. For the bold and careless experimenters who dismiss the inhalation hazard, I would recommend putting your affairs in order before experimenting, including of course pre-writing your obituary so that surviving family will be spared the anguish of retrospective biography to publish to those still living on earth, some description of who you were when you formerly lived and breathed in the same world. It would be thoughtful and considerate of others to do these things as advance arrangements, and such kindness may even help you to get your wings and harp while on your way to join the heavenly choir.

http://www.youtube.com/watch?v=3sgD2JXk4XQ&fmt=18 How Shall I Sing That Majesty ?

[Edited on 11-6-2010 by Rosco Bodine]

Hennig Brand - 11-6-2010 at 15:48

Interesting. I didn't have a proper fume hood, but I was outside with a rather large and powerful fan with cowling sucking away fumes as they came out of the top of the beaker. Just being outside is more than half the battle usually I think, especially if you are mindful and use the wind ( if any) to your advantage it can be very effective at limiting your exposure to fumes. I left out most of the details of my experiment, the main reason being anyone following along in this thread knows exactly what the score is. Also I am not as quick to pad all sharp corners, or remove all danger, just to make it completely safe for all the dumb-asses out there. All that said I do agree that with Picric Acid the poison gas is by far the biggest risk factor, and should be always kept in mind when experimenting.

Rosco, do you use any kind of barrier between TNP and Lead Azide in your experimental caps?

Hennig Brand - 11-6-2010 at 16:05

Sorry for the lousy picture, but I am just starting to get the hang of this picture thing. It does kind of show the crystal structure, but the color is off(it is actually very pale yellow).
43g TNP

[Edited on 12-6-2010 by Hennig Brand]

43g Picric Acid best1.jpg - 54kB

Rosco Bodine - 11-6-2010 at 17:16

Quote: Originally posted by Hennig Brand

I do agree that with Picric Acid the poison gas is by far the biggest risk factor, and should be always kept in mind when experimenting.

You are not a novice. My message was more directed to all the energetics hatchling newbees out there, as a serious warning deliberately meant to scare the "bee jeezus" out of them about the "oxides of nitrogen" which can never be dismissed or ignored as a trifling matter.

Quote:

Rosco, do you use any kind of barrier between TNP and Lead Azide in your experimental caps?

No, but I normally do not store any assembled components for any significant length of time.

Truly pure and dry picric acid is very pale colored, and at a low pH may not even significantly stain a paper filter but slightly in spots. That looks like a nice sample. The slightest moisture even from the air causes it to darken and the color to deepen to distinct pastel yellow or canary yellow.

[Edited on 12-6-2010 by Rosco Bodine]

Hennig Brand - 12-6-2010 at 05:17

Sometimes it is hard to tell when someone is giving you the gears a little bit, anyway no harm done. Sometimes I am already "primed" if you no what I mean, especially if 2 or 3 other people already gave me the gears that day.

Thanks for the reply. I also boiled down my crystallization water to between 1/3-1/4 of its original volume and cooled. I wasn't as careful with slow cooling(no insulation), but it still look very good. The crystals are fluffier of course but still look mostly like good, clean, pure crystals. I had absolutely no resinous products, or at least non that collected during the boil-down. After drying well it looks even a little lighter yellow than the main crop, but of course the main crop has much larger, denser crystals. It must be a little less pure, so if I want to purify it more, it should probably go into the next batches recrystallization.
I obtained about 6.7g from this, so I came very close to 50g TNP from 50g ASA.

Using NaNO3 in place of KNO3 just making this synthesis so much more enjoyable, as well as making it much easier to produce a superior product.

Of course I had to test a little. A little in aluminum foil, a large ball peen hammer, and a small anvil. On the third or fourth wack with the hammer I got a good bang out of it.

By the way, during the nitration I kept the temperature around 75-80C, using just the exotherm of the reaction to control the heat. I had very vigorous magnetic stirring for this. After NaNO3 was all added, I gradually heated it up to a final temp of ~115C, with manual stirring for this.

[Edited on 12-6-2010 by Hennig Brand]

quicksilver - 12-6-2010 at 12:48

Notice the collection of crystalline shapes, needles, spires: a whole collection. That would make a pretty nice slide. Fisher Labs had a reagent grade sample that was packed 30% water and as yellow as I'd seen. we dried some and it still maintained a VERY light yellow (dyed most likely) but was SO light as to be clear at 100x. My belief is that at the point of bearing all TNP you'll see the clarity but any DNP (aside from the moisture issue) what-so-ever and you'll never get that transparency.
There's a fantastic book that is available mostly only in the UK called "Fuels, Explosives, & Dyestuffs" - Tooley.
It explained various benzene-ring materials & their idiosyncrasies. A great experiment is to nitrate aniline. The colors, when exposed to other materials can vary to such a degree that it almost seems unnatural.
I would love to save up for a digital camera for a microscope (especially one with a size gradation). - Good job on that TNP!

Rosco Bodine - 12-6-2010 at 15:41

Any leftover solutions can be treated with KNO3 and left standing to evaporate and reduce in volume. You will recover any significant still dissolved picric acid in the wastewater as potassium picrate which slowly crystallizes out.

grndpndr - 13-6-2010 at 19:15

Quote: Originally posted by gnitseretni

Why make a plastic explosive? Why not mix the NM with a sensitizer (like HNO3 or microballoons) and use it in a SC? Being that it's liquid you'll get a better uniform density than you'd get with a plastic explosive.

or a 6/1-6/1.25 IIRC.NM/ 325mesh AL preferably coated w/stearic acid.The patent #US6960267,'05' 'Multi component Liquid exp.comp.+method.Would make a nice
rel high vis liquid high brisance HE w/o the density /brisance lowering microballoons.If more viscositys needed a small amt(few%by wieght)fumed silica IIRC

Hope I havent made a mistake vis a vis silica viscosity enhance.)#8 cap
The AL will stay in suspension for 24 hrs according to the patent
As its a essentially binary HE its easily mixed in the field from basically 2components the stearic acid can always be added to the AL if its uncoated.Seems the AL has more requirements than anything,325 mesh,%stearic acid.Abstract claims a small/ med bore HE suitable for CSC's,EFP's,demolition,breaching,about anything a 7000mps plus high brisance HE can accomplish.

Back on topic this thread keeps getting better as far as Im concerned.Im not sure the DBSP hasnt been discussed before but perhaps that was a mekp/DBSP composition. Stretching TNP/ETN supplys is no new idea as far as the arts concerned or myself.Ive searched for whats been used in the past seems limited.Trimonite or TNP/Mononitronapthalene 80/20.Not an answer to bulking the HE but a useful /safe (i assume) eutectic.
And really IMHO only a primary DNP/TNP for use in a composite cap
Ive seen some mention of TNP/AN recently and in older Books.
ETN/AN also sounds worthwhile as a composite/matrix concerned.But If a person has to do more nitrations for a suitable eutectic for SC/efps I would seriously consider the NM/AL compositions.Particularly where a watertight device suitable for a cast eutectic is used,far simpler possibly superior results over pressed crystaline HE's.If TNP/AN could be used as just a composition assuming the brisance VOD were similar to amatol 80/20-60/40 with a room/fridge temp shelf life of 3-6months.Same for
ETN the hope and search for a suitable energetic material to stretch the few ozs I could concievably make per batch were I so inclined.Cleaned up a 4lb sack of Hi yield 16-0-0 Na of Soda as its been my normal nitrate until I began to experience failures,only change was bonide 15-0-0 used prior w/o problem.Purified HiYield by sedimentation/ decantation followed by several filterings and finally recrystalization to get decently clean Na Nitrate crystals that were soluble w/o clay etc.Strangely enough the prills appeared relatively white and clean?SUPRISE!!
Problem as carefully as I carried out this process out of 4lbs I ended up w/2lb 2oz of useable NaNO3!.Id be better off buying a 25lb pail of tech grade even w /hazmat.Half the (inexpensive)LOL, Na Nitrate I assumed :mad:

Nice batch Hennig! I see Im not alone in using coffee filters.Ive gone a step further at least for me.I bought a ss wire mesh bowl shaped kitchen device w/handle, large enough to handle the largest coffee filter,paper towel or cheesecloth,nice because it supports the filters can be placed on the beaker or jar intended to catch the mother liqour w/ both hands used to pour, also got the next smaller size. Wire Kitchen strainer?!Lots of useful stuff in kitchen ware! FWIW

@ Roscoe,If the TNP were nitrated w/KNO3 would the saved mother liqour also produce some pottassium Picrate from sedimentation? Thanks!!

[Edited on 14-6-2010 by grndpndr]

[Edited on 14-6-2010 by grndpndr]

Rosco Bodine - 14-6-2010 at 02:51

Ummmm, lemme think, okay.... yes it will

pjig - 14-6-2010 at 12:38

Quote: Originally posted by Rosco Bodine

Any leftover solutions can be treated with KNO3 and left standing to evaporate and reduce in volume. You will recover any significant still dissolved picric acid in the wastewater as potassium picrate which slowly crystallizes out.

I like your conservative view, in making the best use out of all the materials. I hate wasting the leftover solutions, as they can usually be re-used in the next batch. It make's a lot of sense to recover the picrate out of the waste, as it has it's uses too..

[Edited on 14-6-2010 by pjig]

grndpndr - 16-6-2010 at 13:00

Is NH4NO3 a suitable bulking material for TNP for the short term (<2wks)
in a composite.Perhaps in similar ratios 80/20-60/40.
I recently tried KNO3 after using NaNO3 almost exclusively
synthesising TNP.There is quite a difference.

[Edited on 16-6-2010 by grndpndr]

Hennig Brand - 23-6-2010 at 13:52

I've been gone for most of the last 2 weeks.

Thanks for the compliments Quicksilver and Grndpndr, and thanks Rosco for the insight.

One quick insight. When using KNO3 in place of NaNO3 in a Picric Acid synthesis, the outcome seems far worse everything else being equal. The thinner nitration solution(with NaNO3) greatly facilitates effective mixing which is crutial to efficient nitration and preventing oxidation. A related issue is the Potassium Bisulphate(?) impurity also being a much more difficult impurity to rid one's self of when purifying. I could be a bit biased now, but with NaNO3 this nitration seemed perfectly smooth by comparison, and gave a much superior product to boot. This may all seem pretty obvious to most, but for me the extent of difference between the two was quite surprising.

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