Sciencemadness Discussion Board

Perchlorate compositions

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Rosco Bodine - 20-1-2007 at 11:11

Quote:
Originally posted by nitro-genes
Quote:
Originally posted by Boomer
The eutectics mentioned above, using only AN plus an (earth)alkali metal nitrate, all have melting points around 115-120C. To make it pourable without having it solidify instantly when it touches the container wall, you have to go approx. 20C above the mp, which gives 135-140C as the working temp.

Apart from having to use a stinky/messy oil bath instead of a water bath, these temps are too high for my taste to add any RDX, let alone a nitrate ester


Yes, you are absolutely right, in order to make HE additions we should aim for melting temperatures of around 100 deg. C. at the maximum. For RDX this could possibly be 10 degrees higher...

In terms of the most easily prepared eutectic liquid base the following seems pretty interesting, as it melts around 100 deg C, probably even lower:

77% AN
15.5% KN
7.5% H2O

About 7% of emulsifier could be added as the fuel along with 20-60% finely powdered RDX or PETN to make the composition det sensitive...

The water could possibly be elimitated from the mixture using ethylene glycol or glycerol as the fuel, to form a composition something like this:

72% AN
14% KN or SN
14% glycerol or ethylene glycol fuel



[Edited on 20-1-2007 by nitro-genes]


When you include water , eutectic is not the right term
for how the lowering of the " melting point " has been
accomplished . Solutions exhibiting a salting effect
to form supersaturated mixed solutions is what you are talking about . The ratios of salts is generally different
for the same salts to be liquid , mutually dissolved , with water added to the system .

Indeed water can disrupt a eutectic and cause
the separation by melting of one salt which forms a hydrate or a solution preferentially from remaining
eutectic as a liquid with the other . That is for some
clear melt anhydrous eutectics .....adding water could
actually break the eutectic and cause crystallization
to occur at the same temperature where the anhydrous
mixture was liquid before the water was added .

One scheme which should be considered is the "formite"
aqueous reaction mixture which produces the methylamine nitrates from reaction of formaldehyde or paraformaldehyde with ammonium nitrate in the presence of urea . That mixture can be evaporated down to a low water content
or solid .

A second reaction mixture , could be done using hydrated
dolomitic lime and ammonium nitrate to produce mixed
magnesium and calcium nitrates .

Then these two mixtures could be blended with additional
ammonium nitrate and urea , and concentrated to a low water composition . Even at a low water level before crystallization .....in the right proportions such a mixture
with an added gelation agent like guar , forms a water gel
that is *cap sensitive* and strong as about 65%NG dynamite .

Attached is a patent related to the Basic nitrates possible usefulness , particularly as an intermediate in my estimation ,
and examples 2 and 3 are particularly interesting .

While the interest seems to focus here on one pot castable mixtures , there are other useful ways that these anhydrous eutectics may be useful to obtain materials which otherwise can't be gotten alone in an anhydrous state by any simple or economical means . For purposes of production of a combination of nitrates in a granular form which would have
dehydrating properties applicable to nitration schemes ,
it would be convenient if two separate anhydrous eutectics
could be found which when mixed together in the liquid state
would mutually disrupt the eutectics and cause crystallization
of the system containing a large proportion of dehydrating salts in a nearly anhydrous granular condition . The melts
could be simultaneously fed in separate streams as liquids into a mixer grinder where they would combine , flash crystallize and be torn into a free flowing anhydrous particulate . And the composition of such a mixture would
possibly not be obtainable by any other means .

[Edited on 20-1-2007 by Rosco Bodine]

Attachment: US1840229 Basic Nitrate Double Salts.pdf (156kB)
This file has been downloaded 1008 times

nitro-genes - 20-1-2007 at 13:57

Yes I know it's not an eutectic, in which all components have a higher melting point than the resulting mixture. Though I'm quite sure the difference between these supersaturated solutions and an eutectic are not very distinct anyway, since both make use of a series of individual compounds to lower the energy of crystallization of the higher temperature melting compounds. Water is very effective at doing this for the AN/KN and AN/SN mixtures lowering the melting temperature from 130-140 to less than 100 deg. C. with only 7.5% present. These less than 10% watergels are also common for aminenitrates indeed...

Still, I really think such double salts that consist for more than 50% of Ca(NO3)2 or Mg(NO3)2 wouldn't come close to the performance of AN/amine nitrates eutectics concerning bricance. Unfortunately these patents don't give any information whatsover about VoD, or brisancy tests...

Rosco Bodine - 20-1-2007 at 14:38

There is a big difference between an anhydrous eutectic and a hygroscopic hydrate forming salt in a water containing melt ....from a chemical standpoint anyway .

There are things you can do in separate pots and then
combining the products , that can't be done by mixing everything together in one pot with some water .

Those double salts are not meant to define a complete
formulation in and of themselves , but merely a low or no water content form for those components as might be added into a mixture which is more largely ammonium nitrate .....as a way of getting those materials added
in anhydrous form .

[Edited on 20-1-2007 by Rosco Bodine]

nitro-genes - 20-1-2007 at 15:48

In solutions, the crystal latice of the component to be dissolved has a higher energy than the breakdown of these crystals to form a solution. So, the slight favorable enthalpy that drives the formation of a crystal latice is overcome by the more favorable electrostatic interactions with the solvent, breaking the crystals down, into solution...

This is the same for an eutectic I think...:)

Rosco Bodine - 20-1-2007 at 16:47

The properties of magnesium nitrate is a peculiar one which especially interests me .

The dihydrate melts at 129C , converts to the monohydrate gradually from there , or above a temperature unknown as yet
( if anyone finds it let me know ) , but the monohydrate
persists even when heated to the decomposition point of 330C where the monohydrate decomposes directly to
magnesium oxide and nitrogen oxides and water vapor .

Perhaps vacuum conditions at a bit less than the 330C decomposition temperature would dehydrate the monohydrate , and provide the anhydrous salt , but I have found nothing concerning this . ( dittos concerning this possible vacuum dehydration if anyone finds any reference , let me know )

Anyway , a similar "persistent , tenacious hydration" is also reportedly the case for KOH and some other things ,
where once the water is there ....there simply is no getting rid of the residual water by heating alone .

So I looked at the mixed salts where this tenacity for
water is overcome . And an anhydrous basic magnesium nitrate also has its appeal after recognizing that on neutralization with acid it would only require half the acid to convert to the normal nitrate as would the magnesium oxide , and produce the same one equivalent of water ,
as is the lowest stable hydration state attainable from
ordinary heating all the way up to the decomposition point . There is a curiosity on my part as to the possibility of a binary anhydrous eutectic of basic magnesium nitrate and normal magnesium nitrate ,
as well as the tertiary eutectic of those two with
ammonium nitrate from which they may be formed by double decomposition . Also of interest are the binary
anhydrous eutectics of normal magnesium nitrate and normal zinc nitrate , as well as their possible tertiary eutectics with ammonium nitrate .

The reason for my interest relates to the dehydrating property of such nitrates in nitrations , as well as in concentration of nitric acid , and also in the original distillation of nitric acid .....
where nitrates which do not form acid sulfates as
a niter cake byproduct would double the yield of
HNO3 obtainable by using both of the hydrogens
provided by the sulfuric acid . There is significant
potential value in any of these uses , if a convenient
manufacture of a dehydrated form of these alkaline earth
nitrates could be devised .

Actually the patent ( US3173756 ) anhydrous double salt
of claim 11 , NH4Mg(NO3)3 mp. 167C is about as promising a candidate as I have found for those applications mentioned , although it is not perfect , and something
of a modification on this may be more easily attainable
as a lab scale preparation of a granular material .

Obviously the property of melting point is not the principal concern here , but the priority is the anhydrous nature
of the Magnesium Nitrate " donor " composition , and its
convenient manufacture . Even so it is possible for this
to have further usefulness in more complex mixtures having
much lower melting points as desired for fusible explosives ,
with or without added water , as may be the need there .

This general discussion of the mixed nitrates is absolutely parallel to what was being discused in the use of salts added to the nitrolysis mixture being described in the RDX thread , and also has implications related to three or four
other threads . Certain ratios of specific combinations are
going to be more useful in certain applications of interest
where the properties of that particular mixture are desired .

The blending of these salt mixtures into melt in fuel emulsions , slurries , or casts , or water gels is something
like an artful blending of the different "colors" of compositions
available on the artists palette , or in the chemists databases as is the case here . And the more complex the mixtures get the more complicated this whole business becomes .

[Edited on 21-1-2007 by Rosco Bodine]

grndpndr - 21-7-2009 at 05:31

Im not sure if this is pertinentv to the discussion but us patent532276for a vegetable oil modified eutectic/emulsion
using AN/HnO3.suitable melt point depressants include urea nitrate.a variety of oils paraffin oil seemingly the best organic
fuel

Mr. Wizard - 21-7-2009 at 15:44

Quote: Originally posted by Boomer  
Weight plates from the gym? No those holes were *not* there before! ;)

BTW I can go look up the mix, even though it was leftover stuff, all components were weighed. Oh and the liner was hand-rolled around a metal cone, using four layers of 0.2mm copper sheet and super glue.[/rquote


The holes on the sides are made as the plasma cutter on a computer controlled cutter pierces the sheet of steel to cut a hole. If it started at the edge, it would leave a ragged edge. They start inside the hole to make a clean cut. Then the cutter is guided to cut out the hole.

[Edited on 21-7-2009 by Mr. Wizard]

octanitrocubane - 4-12-2009 at 09:49

Heres a patent concerning several perchlorate based compositions some of which are as powerful as TNT and consist of fairly easy to get/make chems

US Patent 5665935 - Cast primer and small diameter explosive composition

From what i have a read of the patent these charges are castable and have good mechanical properties kind of like hard cheese.

hissingnoise - 5-12-2009 at 02:07

They have, IIRC, significantly lower VoDs than TNT. . .

octanitrocubane - 5-12-2009 at 05:40

The majority of the compositions do have low VoDs, however the 12th embodiment has a VoD around 23,000 ft/sec which is pretty much the same as TNT.
Im not entirely sure as to gas output compared with convential H.E`s but from simple calculations it isnt far off.

Rosco Bodine - 11-8-2010 at 22:15

Here's a composition which belongs with this thread.
Haven't tried this so I can't offer any further information.

GB21481 describes ammonium perchlorate compositions
containing aluminum and nitronaphthalene

Attachment: GB21481 nitronaphthalene ammonium perchlorate aluminum.pdf (166kB)
This file has been downloaded 688 times

The WiZard is In - 12-8-2010 at 07:15

Quote: Originally posted by Rosco Bodine  
The properties of magnesium nitrate is a peculiar one which especially interests me.



Noted in passing — magnesium nitrate has been suggested for use
in preparing cellulose nitrate by several US patents.

2 776 -944 - 964 - 966
3 714 143

Google.com/patents works for me.

Rosco Bodine - 12-8-2010 at 10:16

Quote: Originally posted by The WiZard is In  
Quote: Originally posted by Rosco Bodine  
The properties of magnesium nitrate is a peculiar one which especially interests me.



Noted in passing — magnesium nitrate has been suggested for use
in preparing cellulose nitrate by several US patents.

2 776 -944 - 964 - 966
3 714 143

Google.com/patents works for me.


Yeah there has been discussion here in this forum for several years about the potential usefulness of magnesium nitrate alone or in combination with other nitrates as a dehydrating agent in nitration and possibly also in nitrolysis reactions, as well as lowered melting point oxidizer melt compositions, so it is a very interesting potentially valuable material. And it is possible to form the magnesium nitrate in situ from reacting other magnesium salts. There appears actually to be advantage in using magnesium nitrate in combination with other nitrates, in order to break the persistent hydrate via a preferential double salt formation
which can then allow complete dehydration of the magnesium nitrate at relatively low heating. The double salts
are unstable in an acidic environment, so the free magnesium nitrate will split off again in anhydrous form when such double salts and / or salt mixtures containing them are added to nitration acid mixtures. It should be a very slick method for dehydration schemes and oxidizer melt compositions.

When you reference any patents here, if you will type them in a particular format using the country prefix letters and number like for example. This form will bring up worldwide search hits at ESPACENET, and the numeric only portion without any commas will bring up search results at google patents.

US2776965

Use this format and the forum search engine will hit on the result and you can find related other discussions where that patent or an associated patent number string has appeared.
For example, search the above number and you will find:

http://www.sciencemadness.org/talk/viewthread.php?tid=4701&a...

It also helps any parallel word search to hit to inlcude keyword type identifiers along with the number in a separate sentence from the attachment. Patents can be a source of good information as well as reference to other publications.

The WiZard is In - 12-8-2010 at 13:48

Quote: Originally posted by Rosco Bodine  

When you reference any patents here, if you will type them in a particular format using the country prefix letters and number like for example. This form will bring up worldwide search hits at ESPACENET, and the numeric only portion without any commas will bring up search results at google patents.

US2776965

Use this format and the forum search engine will hit on the result and you can find related other discussions where that patent or an associated patent number string has appeared.



A most excellent idea. What we need here is a style
manual for mad scientists. While you are busy writing use a
custom one for use here, we could use the McGraw-Hill Style
Manual : A Concise Guide for Writers and Editors.

An example attached.

Making possession and a knowledge of Fowler's Modern English
Usage and Stunk and White. [Some clam Stunk and White are
word fascists, just ignore them.

I have a really good idea. Page charges that would improve
the signal to noise ratio here by several quantum's leaping.

And all post should be checked for (non native English speakers
will be assigned a secret ID code to exempt them from this
requirement) for :—

Comma split
Periphrasiss
Split infinitives
Fused participles
Ellipsis
Double
Negatives
Case
Passives
Compound
Prepositions
Conjunctions
Inversion
Anacoluthon
Object-shuffling
Walled-up objects
Nominativus pendens

When can we expect your draft?




Style-manual.jpg - 256kB


djh
----
The Bible says that sowers are also reapers. But an exception must be made for
those who sow by implying and those who reap by inferring. The current tendency
to make "infer" synonymous with "imply" would destroy an essential distinction. Let
us continue to use "imply" when a speaker or writer implants allusions or suggestions,
and to use "infer" when a listener or reader harvests from indirect or direct statements
a crop of his own conclusion. Blessings may ensue.

Lewis Jordan Ed.
The New York Times : Manual of Style and Usage
1976
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