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Rosco Bodine
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| Quote: | Originally posted by nitro-genes
The initiating ability of HMTD is phenominal though, equal or even better than lead azide or DDNP. |
Maybe that is what the books say .....however ....
The literature would have you believe some things which
your own real world experiments will never seem to bear out as being true , and in my experience this is sure one of those
occasions where an unreenforced detonator is the
loading arrangement , lead azide is at least three times more efficient an initiator than HMTD . There is simply no favorable comparison .
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nitro-genes
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In a reenforced detonator I've seen 0.02 grams min. for PETN and 0.03 grams for tetryl, so that is the about the same for dext. LA...
You're talking about an unreenforced detonator. I think that is no comparison since lead azide or silveracetylide/nitrate will make DDT in much
smaller amounts unconfined than HMTD. If you would want to compare HMTD against azides in an unreenforced detonator you should prime the HMTD with the
tiniest amount of a fast accelerating primary like LA or SA to get them going at full speed right away. It is like comparing a runner with a car, the
runner will accelerate much faster than the car in the beginning, even though the potential of the car is much higher. IIRC, MF primed with a little
LA will actually outperform LA alone, while fuse initiated MF will perform much less than LA in small quantities. MF in larger quantities will also
perform better than LA in the same quantaties because it has the time to fully accelerate, that is why LA is no good for initiating insensitive
secondary explosives. HMTD is very good at this though, with its only limitations beeing too sensitive to be safe and impossible to press to higher
densities. Amateurs that use large amounts of HMTD alone in their blasting caps and have no rescources to other basecharges would be better off with
the double salt as a base charge, which could be possibly pressed to higher densities and be more energetic at the same time. Since HMTD alone doesn't
make DDT easily it is more than likely the double salt would require a small amount of
[Edited on 9-2-2007 by nitro-genes]
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Rosco Bodine
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Following that same convoluted logic ,
then Lead Styphnate is a wonderful initiator even better than mercury fulminate , since lead styphnate accellerated by lead azide will do the same
thing even better than mercury fulminate .
The point of practical comparison is what the initiator material does when acting alone . If it is to be commended for its value in a mixture , then
qualify its
usefulness in proper context when describing how great it supposedly is in its performance , and how it is only useful in that qualified sense .
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Sickman
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Yep! Once again we're back to the reality that the literature of explosives doesn't usually represent reality in a fair and accurate way.
Alot of literature will point out several primary explosives such as DDNP, lead styphnate and HMTD and say they have outstanding properties as
initiators and puts them on the same level as the azides, but it's just not so.
I have been trying to understand how all this incorrect, puffed up information has gotten into the literature. My present theory is that many books we
may read on explosives are just compiliations by authors who have no real experiance or first hand knowledge of the explosives they are writing about.
I'm not saying the authors don't ever get anything right. I'm just saying for example that an author who doesn't know anything about DDNP and has no
first hand experiance with it will go to other literature references such as patents. Now the problem with patents is almost every one I've ever read
sounds like a sales pitch and that's exactly what they are most of the time. Trying to present new explosive compositions and new primaries that can
"replace lead azide and mercury fulminate in detonators."
So they flower it up and make their "invention" sound like the best thing to ever happen and that it is the ultimate cure to all the previous
problems. Well it often times isn't true. Like Rosco said, the information contained in patents and other literature must be tested and found accurate
that way before we allow ourselves to accept it as true.
Let me make it clear that in my own experiance, TATP does not compare favorably to lead azide, particulary the azo-clathrate of lead azide with lead
nitrate and lead picrate. They are a total mismatch for power, sensitivity in the dry material, initiatory effeciancy, reaction to elevated
temperatures, and storage stability.
The reason I think peroxides, mostly TATP and HMTD get any attention at all is because their main precursors are cheap and OTC, and the process of
preparing those peroxide explosives is extremely simple compared to the preparation of other primaries or other precursors to other primaries.
For example azides and particulary IMO the azo-clathrates, which Rosco was good enough to bring to the table, will probably look further from reach to
the average member here, because unlike hydrogen peroxide, sodium azide is not readily available OTC. In fact I think the only source of it that can
be purchased OTC is auto airbags.
In my opinion the peroxides and their preparation should be completely abandoned and more research, and posting that research in detail, should be
done for the OTC production of sodium azide in order to give everyone a fair alternative to the peroxides.
Rosco has begun this work by posting a detailed process for the production of hydrazine sulfate, which he came accross in The Hive and also added in
many of his own refinements to the process determined by a series of experiments done by him in order to optimize the process.
In that posting Rosco said the following:
"Full details for the synthesis of sodium azide will be provided in a later communication. This digression simply describes why the improved synthesis
of the hydrazine sulfate is of special interest for producing the hydrazine sulfate in better crystalline form by a method which improves its
usefulness particularly as a precursor material for OTC sodium azide, or when the purpose will be to freebase the hydrazine and extract it with
methanol for any other use."
I'm looking forward to Rosco keeping his word and posting the "Full details for the synthesis of sodium azide."
Now that we know from Rosco how to produce Sodium sulfate from completly OTC materials the next step is to learn how to produce Methanolic Hydrazine
Hydrate (hydrazine hydrate dissolved in methanol) and also how to produce Isopropyl nitrite. These are the two main precursors for a method of
producing a very pure sodium azide.
Rosco,
You have recently expressed to me that:
"It seems strange to me that after posting the information about the clathrates that nobody other than microtek has even mentioned anything about
experiments even being done towards learning anything further about those materials."
I think that many members are interested in the azo-clathrates that you described to us, but I think that they feel they are out of reach because the
"full details" for the OTC production of sodium azide have not come out in a user friendly form.
Also there is perhaps, a fear of the toxicity of the materials and a feeling like proper lab equiptment for the production may not be available?
If you feel like the process is dangerous, please explain which points of the process are dangerous and what is the source of that danger and
obviously how it can be handled and avoided.
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nitro-genes
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| Quote: | Originally posted by Rosco Bodine
Following that same convoluted logic ,
then Lead Styphnate is a wonderful initiator even better than mercury fulminate , since lead styphnate accellerated by lead azide will do the same
thing even better than mercury fulminate . |
Yup!  You're absolutely right!
Cited from a copy of an army technical manual about military explosives:
"When subjected to the sand test with ignition by
a black powder fuse, the brisance of normal lead
styphnate (10.5 grams of sand crushed) is much less
than that of lead azide (16.7 grams of sand crushed).
However, when initiated with a small charge of mercury
fulminate or lead azide, the brisance (24 grams of sand
crushed) is greater than that of lead azide or mercury
fulminate"
Lead styphnate can probably LVD easily or become deadpressed (densities as used for lead styphnate are rarely beyond 2.5 g/cc while it's crystal
density was something like 4.something) and may not be able to sustain high order detonation from a fuse or a small enough amount of LA to be used in
a detonator instead of LA. VoD's of about 5200 m/s are found for lead styphnate though this was found by detonating it with a blasting cap, quite
different from lighting it with a fuse!
I wasn't talking about vague patents btw, but scientific literature in which *tests* were conducted to see the initiating ability of HMTD at only 1000
psi towards several secondary HE's. Real tests in the real world (just like the small critical diameter PBX tests  ). These tests concluded that there is little difference between the initiating
ability on a weight basis compared to dextrinated LA, and furthermore, that there is only a 20% decrease in initiating ability for an unreenforced
detonator compared to an reenforced detonator. My HMTD needed slightly more confinement than TATP, but compressed in a thin cardboard tubing it made
DDT reliably from the slightest spit of a fuse. Still despite it's very good initating ability, the dangers of working with this material still stand
and I advice everyone still using HMTD to search for an other primary to use...
There are two types of initiating explosives, for sensitive basecharge material, like PETN, tetryl RDX, etc, and for insensitive HE's like TNT or AN
based. A good performance with the first group will not garantee a good performance for the others. A good example is the AgNO3*HNO3 double salt. 0.05
grams suffices for PETN in a reenforced detonator, almost as good as dextrinated lead azide, though you can cram as much as you want of it in a steel
pipe, I doubt it will be able to set of ANFO. From my own experience, 400-500 mg of pressed HMTD however can reliably initiate kinepack and ammonal
types of explosives (!) something that TATP or MF couldn't do, so in this sense it really is a very powerfull initiator. Since all modern blasting
caps contain basecharges like PETN or RDX, LA is the primary of choice because of it's combination of low pressure force to achieve high density,very
rapid accelleration and high order VoD even when fully compressed. This was the main flaw with DDNP IIRC, it needed much larger pressing force to
obtain maximum density and could become deadpressed as well, just as lead styphnate can...
[Edited on 9-2-2007 by nitro-genes]
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Rosco Bodine
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| Quote: | Originally posted by Sickman
The reason I think peroxides, mostly TATP and HMTD get any attention at all is because their main precursors are cheap and OTC, and the process of
preparing those peroxide explosives is extremely simple compared to the preparation of other primaries or other precursors to other primaries.
For example azides and particulary IMO the azo-clathrates, which Rosco was good enough to bring to the table, will probably look further from reach to
the average member here, because unlike hydrogen peroxide, sodium azide is not readily available OTC. In fact I think the only source of it that can
be purchased OTC is auto airbags.
In my opinion the peroxides and their preparation should be completely abandoned and more research, and posting that research in detail, should be
done for the OTC production of sodium azide in order to give everyone a fair alternative to the peroxides. |
Been there , done that .
Getting a bit off topic here ....but here goes anyway ,
| Quote: |
Rosco has begun this work by posting a detailed process for the production of hydrazine sulfate, which he came accross in The Hive and also added in
many of his own refinements to the process determined by a series of experiments done by him in order to optimize the process. |
Actually it was Polverone who posted at the hive what
I had written up as a preliminary effort in response to his request for the information . I wrote the synthesis adapted from the Merck patent which
was posted at the hive and Rhodium . Then I went beyond that with an improved
method based on a series of experiments aimed at optimizing the synthesis .
| Quote: |
In that posting Rosco said the following:
"Full details for the synthesis of sodium azide will be provided in a later communication. This digression simply describes why the improved synthesis
of the hydrazine sulfate is of special interest for producing the hydrazine sulfate in better crystalline form by a method which improves its
usefulness particularly as a precursor material for OTC sodium azide, or when the purpose will be to freebase the hydrazine and extract it with
methanol for any other use."
I'm looking forward to Rosco keeping his word and posting the "Full details for the synthesis of sodium azide."
Now that we know from Rosco how to produce Sodium sulfate from completly OTC materials the next step is to learn how to produce Methanolic Hydrazine
Hydrate (hydrazine hydrate dissolved in methanol) and also how to produce Isopropyl nitrite. These are the two main precursors for a method of
producing a very pure sodium azide.
Rosco,
You have recently expressed to me that:
"It seems strange to me that after posting the information about the clathrates that nobody other than microtek has even mentioned anything about
experiments even being done towards learning anything further about those materials."
I think that many members are interested in the azo-clathrates that you described to us, but I think that they feel they are out of reach because the
"full details" for the OTC production of sodium azide have not come out in a user friendly form.
Also there is perhaps, a fear of the toxicity of the materials and a feeling like proper lab equiptment for the production may not be available?
If you feel like the process is dangerous, please explain which points of the process are dangerous and what is the source of that danger and
obviously how it can be handled and avoided. |
The freebasing of hydrazine has already been discussed in great detail in the sticky hydrazine thread and the sodium azide thread . I don't
understand how that falls short of "full details" being disclosed ..except that I did not personally write up a formal step by step . The information
is already there in portions in different threads .
Search and you will find .
There is also a going beyond the methods I described , with the hydrogen peroxide oxidation of hydrazine sulfate .....which although less efficient is
certainly simple .
So there is a way of using hydrogen peroxide to
get to sodium azide although it is much more technically
complicated than making AP .
And also there is microteks work on
freebasing hydrazine hydrate into isopropanol .
Certainly anyone wanting to synthesize sodium azide is not being kept from it by my not writing a 123 step by step .
And there already being available at least three good lab synthetic routes to sodium azide , aside from airbag salvage and the ordered chemical
sources as well .....
I simply don't see that any lack of interest in different
azo-clathrates is due to some unavailability of sodium azide .
As for the dangers , that's been covered also .
Maybe I changed my mind about writing a 123 step by step
just because of what is going on here right now ,
and what the cause of that need for clarification speaks to
is a lack of study and skills and knowledge that makes me uncomfortable as handing the keys to the car to a 12 year old .....and saying " now be
careful " .
If that reserve has discredited me ...well fine , sue me 
But I am still going to leave the unwritten " recipe "
where it is . A variation on microteks method is more
technically simple and attainable anyway ....and this is old news .
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nitro-genes
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One of the things that made me hesitant in making the azoclathrates was the incorporation of a fair amount of lead picrate. Lead picrate alone is
pretty sensitive to static, friction and shock, more so in any case than LA alone and is described in literature as a dangerous and unpredicatble
compound. Although I must admit this is from literature only since I've no experience with it myself.
Never seen any good sensitivity test concerning the clathrates, so for many people it may be a fair choice to stay with the well documented and
thoroughly described LA instead of a relatively new and undescribed product from a patent. (From which you say yourself can contain a lot of bogus
information. )
[Edited on 9-2-2007 by nitro-genes]
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Rosco Bodine
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| Quote: | Originally posted by nitro-genes
One of the things that made me hesitant in making the azoclathrates was the incorporation of a fair amount of lead picrate. Lead picrate alone is
pretty sensitive to static, friction and shock, more so in any case than LA alone and is described in literature as a dangerous and unpredicatble
compound. Although I must admit this is from literature only since I've no experience with it myself. |
I do have some experience with it and the literature from
where you got that information is wrong .
| Quote: |
Never seen any good sensitivity test concerning the clathrates, so for many people it may be a fair choice to stay with the well documented and
thoroughly described LA instead of a relatively new and undescribed product from a patent. (From which you say yourself can contain a lot of bogus
information. )
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Having good information directly from experiments
is better than unconfirmed information from literature references .
And when the process or the product are not an exact duplicate of what is somewhere already described in the
literature , then it is all purely experimental anyway ,
and you become the authoritative source for your own information .
What you know for sure beats the hell out of what you have heard , thought , or read .
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quicksilver
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| Quote: | Originally posted by Sickman
The reason I think peroxides, mostly TATP and HMTD get any attention at all is because their main precursors are cheap and OTC, and the process of
preparing those peroxide explosives is extremely simple compared to the preparation of other primaries or other precursors to other primaries.
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That's right on the money IMO. I also think it's a shame because the precursors needed for interesting experiments are available if people would make
a damn effort instead of just wanting to make a noise, etc.
"And the Kewls went unto the temple and stood before the priest as he sayeth unto them: Renounce the peroxides; turn your head from Satan and be
healed! And they saw the uncleanness all around them: their beekers and flasks were befouled! And as they saw, they wept for they knew they were
shamed in the eyes of those who went before them."
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nitro-genes
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| Quote: | | Quote: | Originally posted by Rosco Bodine
Following that same convoluted logic ,
then Lead Styphnate is a wonderful initiator even better than mercury fulminate , since lead styphnate accellerated by lead azide will do the same
thing even better than mercury fulminate . |
Yup! You're absolutely right!
Cited from a copy of an army technical manual about military explosives:
"When subjected to the sand test with ignition by
a black powder fuse, the brisance of normal lead
styphnate (10.5 grams of sand crushed) is much less
than that of lead azide (16.7 grams of sand crushed).
However, when initiated with a small charge of mercury
fulminate or lead azide, the brisance (24 grams of sand
crushed) is greater than that of lead azide or mercury
fulminate"
Lead styphnate can probably LVD easily or become deadpressed (densities as used for lead styphnate are rarely beyond 2.5 g/cc while it's crystal
density was something like 4.something) and may not be able to sustain high order detonation from a fuse or a small enough amount of LA to be used in
a detonator instead of LA. VoD's of about 5200 m/s are found for lead styphnate though this was found by detonating it with a blasting cap, quite
different from lighting it with a fuse. |
This is probably also the reason that the clathrate truely is more brisant than the components apart. Lead picrate becomes insensitive to fuse
ignition when pressed to higher densities just like lead styphnate so it's full potential (more brisant then LA alone at full density) can never be
realized in a small amount by fuse only. Putting a tiny layer of LA over an amount of lead picrate will probably give the same results as the
clathrate itself although this isn't as practical as an intimate mix though...
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Rosco Bodine
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So here's more off topic information ...but relevant to
reply to what you are saying .
Actually I have tried many composite mixes including
that one , and the only lead salt mixture which I found showing that synergistic increase was the mixture of
lead styphnate and lead azide , a mixture which is well known and has been documented and published by several sources as well as being used
commercially .
The only composition of lead salts which I found among the *few* I tested which would high order detonate from the use of a small layer of azide as a
shock initiator ,
was a nitrocellulose bindered and hardened putty which
was filled with the triple salt clathrate ( basic lead picrate - lead nitrate - lead chlorate ) . Observing this
led me to attempt the quadruple clathrate complex
having included lead azide based upon that particular
substrate ......an experiment which was successful ,
although I have not yet given the details for that
synthesis . The chlorate variant did prove to be a
more powerful , perhaps 25% more powerful initiator
than the non-chlorate variant and seemed to have
a saturation limit of azide well beyond the non-chlorate variant . I expect that a perchlorate variant would
likely also form according to the same scheme , but
I have not tried this . The yield was above 90% but was not quantitative , so I was uncertain about the exact
composition of the clathrate produced and I have not repeated the experiment . But it appeared likely to me
that the crystalline variant was likely :
4 [ Pb(C6H2N3O7)2 - Pb(OH)2 - Pb(NO3)2 - Pb(CLO3)2 - Pb(N3)2 ] - 16 Pb(N3)2
This is an exception to what is declared in the Kenney patent with regards to saturation limit for occluded
Pb(N3)2 being at 13 , soooo I was a bit uncertain of my own preliminary estimate and observations , especially without repeating the experiment . But
anyway , that's what I found .
The next experiment contemplated was to try the perchlorate variant and see what resulted .
Anyway , this is a good example of the purely experimental scenarios I mentioned earlier . So
where exactly in the literature do you go for information
concerning a compound which just made its earthly
debut five minutes ago in your beaker ?
Answer : You don't go anywhere except your own notes
and understanding , trying to keep some rational perspective about what you are doing , consider the
possibilities and make an educated *guess*
[Edited on 10-2-2007 by Rosco Bodine]
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Boomer
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How true. But there lies a danger in it, just like in you saying:
"Having good information from experiments is better than unconfirmed information from literature references".
I know you did not mean it that way, but the danger I see is people - especially young beginners - conclude a compound is safe, and dangers are
exaggerated, because 'nothing happened' the last few times. I have read many claims by noobs stating "You are stoopid, my AP is safe, I made 3 pounds
and nothing happened!"
Don't get me wrong, I know you for a serious scientist, but reading
"Lead picrate alone is ... described in literature as a dangerous and unpredictable compound" (nitro-genes)
"I do have some experience with it and the literature from where you got that information is wrong" (Rosco)
at least makes me doubtfull whether SOME (your words) experience by ONE person, even through real-world experiments, is enough to disclaim the dangers
of a compound cited again and again in the literature. After all, it *is* one of the most sensitive primaries. And reading "unpredictable" raises more
flags for me than "extremely sensitive". In the latter case, at least you know what to expect.
BTW my personal opinion is that of a person who has little time for experiments, and whose main interest is not in making the perfect primary:
How much I would like to make the clathrates etc. I still go with TATP how sad it may be, for the following reasons (apart from little time):
- A compound cap with the sensitive MHN needs far under 100mg even of this, and say 50mg is an amount I am willing to handle. A remote press is needed
anyway, *whatever* you press on top of 2g MHN or PETN.
- My caps are either electric and fully moulded, or the fuse is secured in place first. This way, the primary is safe from mechanical forces and
static once finished.
- The non-electric ones tend to be self-defusing once the TATP sublimates, in case you forget one or have to store for longer that planned. I
disassembled several caps after 1-2 years which only had an empty space above the MHN, meaning they were safe.
- There is still the EBW
Oh and about TATP *being so much weaker* than HMTD, my real world testing showed both are more than sufficient if directly on top of a nitric ester.
Needless to say I prefer the chemically stable TATP then. From fragmentation tests, I would rate HMTD 30-40% above TATP.
Whatever primary you use, a compound cap is the way to go - Let a secondary do the job of kick-starting the main charge - They are more brisant than
any primary anyway. Why discuss the difference between 4800 m/s and 5300 m/s when there are enough compounds going 8000+ m/s with 50mg of just about
anything on top going first?
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Rosco Bodine
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I am not generalizing to the point of saying that all the literature is wrong about everything , on the contrary it is pretty reliable about almost
everything , and should be presumed reliable in the absence of any good evidence to the contrary , which are exceptions .
But neither am I going to dismiss the significance of experimental data , when experiments show me directly
that something described in the literature is wrong .
COPAE has errors in it , and so does PATR , Urbanski ,
and other literature , patents included , and professional journals .....nothing in human endeavor is error free ,
and when you do some in depth fact checking and verification experiments ......you absolutely will find
errors in the literature , often simple typos , but also
more than that .....stating of information , usually conclusions or generalizations made by the writer but
stated for fact instead of qualified as opinion , which
are things that are simply not so Also there is a
common mistake of stating things which may be true
in an exceptional circumstance , without making it clear
that the statement is only true in a highly qualified and
restricted sense and should not be taken as a sweeping generalization . The dangers concerning picrates have been mischaracterized in that way .
Lead picrate has been used commercially in cartridge primers , and it is fit for such use . If it was unduly sensitive and dangerous , then it would
never have been
used as an improvement over fulminate , which it is .
Basic lead picrate is better still , and its double salt with lead nitrate . Lead styphnate is better yet and has become the standard primer .
This is *not* the experience of *one* person ....
which makes me conclude that some of the literature
is in error . There are errors in the literature which I have pointed out as they appear to me , so that others can take a look and see that this is
so .....and any careful reader will find and can confirm these errors themselves .
Frankly , if your knowledge of explosives is based only on unverified information which you have accumulated from
reading ......it is something like having read volumes about fishing without ever wetting a line , and then claiming to be a master angler .
Anyway , I hesitate to even post anymore in peroxide
discussions because they always without fail make a descent into arguments which are meaningless and
unscientific . That seems to be where this discussion
is going . I have followed carefully the online discussions
of energetic materials for years and have tried to make my contributions , and to clear the air of the smell of way too much bullshit being stated by
" experts " for fact .
I have tried to provide *verifiable* , *repeatable* ,
detailed and accurate information to substantiate what I say . If I haven't got credibility ....then please ...
send in someone who does .
Anyway , lead picrate is somewhat irrelevant with regards to discussing the azo-clathrates , because it isn't lead picrate that is the substrate
anyway ....but it is
the basic lead salt that is the clathrate former , and
I don't claim to know more than anybody else about
this particular family of salts , just that I have tried to
share some accurate and useful information about them
and point to references and experiments which are of
interest and which seem to provide reliable information
which should be of value . I'll leave it where it is now ,
and what is so or not so can pass or fail on its own merits .
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quicksilver
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That’s a good illustration of the "safety" problem: personal experience by a mature individual using science and safety to test and quantify
individual characteristics of energetic materials. But we are a public forum and not all readers possess the same abilities.
In a public setting too many individuals generalize results that are specific to individual testing scenarios. Personally, I have had a smattering of
experience with nitrated phenols. I believe them to be overstated in their sensitivity to a greater extent. However that doesn’t mean that some dolt
who sloppily allows material to gather between threads in a container, etc would not experience a hazard. To me it’s common sense to not expose the
material to undue friction but depending upon what someone “wants to hear” – that they may construe the material to be “safe” regardless of
the situation.
Peroxides are easy to make and the attraction is there for someone who has an interest in energetic materials to manufacture them. Hearing that they,
in and of themselves, need some stimulus to pop they forge ahead not realizing that the stimulus occurs on a level much different than that of a
material like PA. Or someone hears that a material like lead styphnate is not an efficient initiator, believes that material will not explode with
violence enough (given a multi gram weight) to lift a finger or three.
From my own experience, I believe that flash powder has caused more accidents among those who have a longer experience with pyrotechnic materials than
most any other. Due simply to the comfort zone that is promoted in those who set up shows for a living and have made so much of the stuff that they
don’t focus on the activity as much as the show.
Therefore I think it’s that comfort zone that is a real danger. And too many diminishing remarks may take those with limited experience there. On
the other hand it’s those same remarks t (“styphnate’s a poor choice for an individual primary for secondary explos” or whatever) that adds to
the knowledge base. I would hate to have to always add an addendum to every remark that it is still a very dangerous material. But it seems that when
reading a thread like this from the beginning a person could get the idea that peroxides, if "manufactured correctly" may be experimented with
impunity. ....Which then appears to demand the mention of weight of "stockpile" and it's relation to accidental initiation (& resultant damage).
I don’t remember the name of that old Clint Eastwood movie where he said “A man has to know his limitations”.
[Edited on 12-2-2007 by quicksilver]
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Rosco Bodine
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One thing I have noticed is that misinformation in the literature often gets repeated by others , over and over again , and becomes a sort of
mythology which takes on a life of its own , gaining credibility by repetition ....obviously by people who never put it to the test ....or else they
would be debunking the misinformation instead of perpetuating the myth .
It is evident the effect of " indoctrination " of those who
are a bit paranoid about materials which they have chosen to avoid actually making and testing themselves ,
and yet will not just come out and say so , but will instead pass along something which they have read as if it was knowledge which was directly
theirs , instead of
being properly attributed to the actual source .....
which generally turns out to be some encyclopedic reference containing a whole lot of error , both known
and unknown .....and never revised , even in later editions . Errata is alive and well and would achieve eternal life without intervention by
proofreaders and
editing of its content . I don't think I have a single textbook where there is not a few lines stricken in highlighter and some footnote commentary
added , or sometimes just a question mark to indicate a
" maybe so / maybe not " sort of dubious or qualified nature concerning that particular " fact " which just got uncarved in stone by yours truly .
Anyway the point is .....the scientific literature is not
the unchallenged gospel truth in its every word ,
and just because " it is written " does not necessarily make it so . I am not saying everyone should throw away the book , but what I am saying is
not to leave your brain at the door for those who are absorbing and
processing the information contained in the pages therein . When you are reading whatever it is written ,
do not mentally add as an invisible prefix any
" thus sayeth the LORD " to the content of a science book or article authored by a man .
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nitro-genes
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| Quote: | Originally posted by Rosco Bodine
Anyway , I hesitate to even post anymore in peroxide
discussions because they always without fail make a descent into arguments which are meaningless and
unscientific . That seems to be where this discussion
is going . I have followed carefully the online discussions
of energetic materials for years and have tried to make my contributions , and to clear the air of the smell of way too much bullshit being stated by
" experts " for fact .
I have tried to provide *verifiable* , *repeatable* ,
detailed and accurate information to substantiate what I say . If I haven't got credibility ....then please ...
send in someone who does . |
From the perspective of NaN3 economy and it's initiating ability these clathrates defenitely seem very interesting and usefull, with a huge amount of
other possible related compounds yet to investigate. I never claimed to be an expert by saying that lead picrate is described as a very sensitive
compound as I said myself that I hadn't got any experience with it myself. It is just that I haven't seen any conclusive data about it's sensitivity,
or I must have missed it completely, in which case I sincerely apologize. Everyone presents it as beeing a worldclass primary (by saying this I don't
mean it isn't) which led me to believe that the sensitivity of this compound was tested to be low or at least not higher than the parental compounds
alone, but apparently noone knows or has tried to find out, which I find strange...
Anyway, these homemade PETN PBX sheet explosives with critictal diameter of under a mm turned out to be validated multiple times and caught on video
by an experienced person as well, though I seem to remember someone calling this bullshit because of some unscientific arguments and without any first
hand experience as well.... So let's call it even shall we?
Just kidding, no harm intended! 
[Edited on 13-2-2007 by nitro-genes]
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quicksilver
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When the "Mr. Anonymous clathrate" post went up I reproduced the experiment ASAP. And generally my experience was the same. It took a tiny bit more
clathrate than DLA to initiate a given .8 gr of PETN. I don't remember how much more but it was basicly insignificant except for a military bean
counter. However the second thing I did was get that damn patent in my hot little hands. I tried most of the picrate configurations within and
although it turned out that I couldn't find a magic bullet it was damn fun.
One thing about individual experimentation is that to quanitfy results the experiementor needs a hell of a lot of "back up" / repeatable results, etc.
I suppose that's why software engeneers have shit-loads of beta testers. Example: --- I have seen basic lead styphate used to light up a .8 gr unit of
PETN and the damn thing worked at the .33 gr level. The problem I see with experiments of this type is that I would need to have various samples of
PETN in various crystal shapes in various levels of density to such a degree that one individual couldn't cover all the variables... So it's not
making a fair assumption that such and such does this and that IF I have only a few testing mediums to quanitfy the results, no? And to really cover
some ground the experiment would really need to go on for some time. Covering many areas such as (in this instance) crystal shape, density, temp,
diamieter, type of initiation, humidity, containment issues, etc.
The point about critical diameter you just mentioned is a good example. The only way that could be assessed is to have a hell of a lot of materal at
one's disposal.
On RS they have a tread about "Explosives Falsities" or wantever....and if you check it out - it degenerated into movie make-believe because that's
really the only thing that hobbiests can attack with impunity. The lab & testing facilities nesessary to really go after some serious results
would be beyond the means of most guys. However, moving to some area wherein one could get some outstanding results would be possible IF several
experimentors directed their energies toward a common simple goal. Witness the efforts with ETN.
[Edited on 13-2-2007 by quicksilver]
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Rosco Bodine
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One of the things that I intended to try next and haven't gotten around to doing , is to attempt the azo-clathrate
synthesis at several times the dilution and see what would be the increase in crystal size and perhaps have
a better uniformity of crystal . I was thinking to do
the synthesis at perhaps five or six times the dilution ,
and I also wanted to look at the perchlorate variant
to see if it would show the same increased azide content
capability which had been observed for the chlorate .
P.S. I am still dubious about sheet explosives when the
thickness is down to what is really " film " thickness and there simply isn't ( or shouldn't be ) enough cross section there to sustain a detonation
wave by a secondary explosive . It begs the question in my mind of how much
silver fulminate is included as a dispersed component
and " pigment " in the " explosive paint " in order for it
to function .
[Edited on 13-2-2007 by Rosco Bodine]
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quicksilver
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I was also. It sounded like someone had to come up with some stats for the state to maintain their budget. The only reason I felt it could fly was
that there are some compound detonators that are unique shapes for use in military apps and the secondary was very thin.
On the subject of clathrates I can readily maintain that they are quite stable. I just can't find much written about them other than some of the
original work was done by a nun IIRC. Regarding a perchlorate varient; where would one start? A heavy metal perchlorate?
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Rosco Bodine
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The only written descriptions of which I am aware concerning the azo-clathrates is a brief mention in
PATR , which references the patents ....along with what
I have written myself Actually I believe Von Herz and Friedrich were aware of
some of these multiple salts , but
never fully understood exactly what they were was clathrates nor fully described them .
I seem to have a talent for obscure topics of interest as
curiosities so if anyone finds anything more ....
please share .
Regarding the chlorate , perchlorate , and other variants
it works just the same as when forming the acetate or
aminoacetate , lactate , ......and azide variants ....you
simply add a soluble sodium , potassium , or perhaps ammonium salt of the desired acid , to an equimolar amount of additional lead nitrate being
present in advance in the original reaction mixture , and double
decomposition occurs , with the new lead salt being formed .....complexing itself into the clathrate . This
will occur even in opposition to what the usual solubility
driven double decomposition would provide .
Actually this was described in detail in the earlier patents
which dealt with the non-azide containing clathrates ,
and it works exactly the same way with the azo-clathrates .
So ( theoretically ) ....
if you wanted to introduce lead perchlorate ,
you would simply add sodium or potassium or ammonium perchlorate in the amount corresponding to the molar
amount of basic lead picrate - lead nitrate already formed , in a residual solution containing excess lead nitrate which will then further react to
form lead perchlorate , which would complex to form basic lead picrate - lead nitrate - lead perchlorate .
*All* of the sequential lead salts in the clathrate are
derived from lead nitrate alone . All of the other lead salts
in the complex are formed by double decomposition .
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quicksilver
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Some of the luckiest moves I have made were wondering into the chemistry building at the local U and simply asking for old stock. I wound up w/
perchloric acid (which was a whole world of discovery unto itself)..... until that time I was utilizing ammonium perchlorate but I found some
limitations there. But my prize thus far is cupric, nickel & mercuric nitrate (they had a hell of a lot of water in them due to their age but I
dried them out)......the cupric turned out to be much too sensitive to make more than a few Mg of azide (that's a story!) but Hg NO3 might form the
basis for a unique clathrate. From what I read crystal size influences mercuric azide however they only seem to present an issue if one
re-crystalizes, as the initial product is tiny. But in a clathrate the size issue raises it's fearsom head..... Another thing I found fun is a web page that is popped out by a guy who sells used microscopes. I found a 100-300x
that has a measuring element to it and I check the crystals through it (it's a cheapy but it works). One day I am going to find a way to attach a
camera and post some pics.
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Sickman
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I did a little internet search to try and track down Joseph F Kenney, the author of the clathrate patents, in hopes that I could email him and request
more information about the clathrates that he patented.
Unfortunatly, it appears that he already got old and died around ten years ago.
I found this info on a certain Joseph F. Kenney:
JOSEPH F KENNEY, 16 Mar 1927, 18 Mar 1997 
Maybe it's not the same person? Anyway, he must have already been 40 years old (if same person) when he published/applied for the patent on the
"azo-clathrates". Only lived to 70? Too bad for us, as he would likely have extensive information on the properties of those compounds that was simply
too exaustive to include in the patents.
[Edited on 15-2-2007 by Sickman]
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Rosco Bodine
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I would have to go back and review this to be certain ,
but I am pretty sure that the clathrates of the sort
I was experimenting with are all a type of mixed lead salts composition , exclusively containing lead salts only , and the basic lead picrate is the
lattice forming material which wraps itself like a matrix or cage structure surrounding the various other lead salts for which it has peculiar
affinity to absorb ......almost like it was a lead specific molecular sieve ....or a synthetic lead analogue of zeolite perhaps . I have thought that
perhaps the basic lead picrate forms something like an expanded hydrated sol-gel structure which has preferential affinity for lead salts to the water
of hydration or solution ....so it acts something like a
" flocculent " does in in water treatment
scenarios , latching onto those other lead salts and
crystallizing out as an insoluble or nearly so , complex salt . I think you could probably get many different
*lead* based salts to participate in the formation of
clathrate complexes of this sort .....but I am not so sure that anything other than lead based salts would work ,
actually I am doubtful anything other than lead based salts would add into the lattice .
[Edited on 15-2-2007 by Rosco Bodine]
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quicksilver
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If you could give me a leg up of where to start looking....as I would love to attempt it but I don't want to waste stuff (of course). Perhaps that was
in reference to the picrate lattice?
I'm going to search this evening....I'm sure your right in terms of picrate latice clathrate compounds. I am just day-dreaming here: What I was
thinking was something along the "fulminate" concept;of using a metal salt in that case Hg (but in our case Pb) and piggy-backing another on top of
the existing one. This may sound impractable but using the basic lead picrate and a alternative metal (let's say Cu) - the way copper fulminate uses
mercury fulminate as a starting point.
But there's always the perchlorate (Pb) idea.
[Edited on 15-2-2007 by quicksilver]
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Rosco Bodine
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If you mean to ask what other candidate materials might possibly be clathrate formers of this multiple salt type ,
which could follow the mechanism of the lead salts .....
the candidates for experiments would be those metal
salts which readily form a hydrated gel when basified ,
but a gel which dehydrates and collapses on heating
to near boiling .....and this property would need to be
so for the basic picrate salt of that metal also , at least to the extent it would form a hydrated salt which may convert to a lower hydrate or
anhydrous condition upon
further heating and/or changing pH .
Of course lead may be peculiar in its behavior , or I could be wrong about the mechanism so all of this is highly
speculative .
Also I would bet that the pH has to be within a fairly narrow range where this hypothetical sol-gel mechanism occurs , at least with any efficiency
.....and if that window
condition of pH and temperature , perhaps concentration as well , is not present for the complex formation , then it won't appear as a product even
from a mixture of its required precursors .
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