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Author: Subject: Melting whistle mix
papaya
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[*] posted on 8-3-2014 at 11:49


Dornier, don't you want to try the same with KClO4 instead of KClO3, maybe even more powerful?
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[*] posted on 8-3-2014 at 13:09


I would, but I don't own any perchlorates at all. I also doubt it would be more powerful, as its melting point is higher than most fuels' autoignition temperatures. Anyone here who is able to test this with KClO4?
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DubaiAmateurRocketry
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[*] posted on 9-3-2014 at 01:41


I have some perchloate. However I dont own any benzoate. Have you tried nano hexamine mixtures? problem is that they dont melt, however I can try dissolving hexamine and ammonium perchlorate in water and recrystallizing them, it should be very well mixed then. Potassium perchlorate is too insoluable, sodium and lithium perchlorate forms hydrates.
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[*] posted on 9-3-2014 at 07:06


Do you have any fuel normally used in whistle mixtures? Hexamine will not work here, it should be an aromatic salt.

Bert, I tried copper benzoate with KClO3 in a 20/80 ratio by weight. It's a beautiful light blue mixture, which deflagrates quickly with a blueish flame. It ignites before melting, but strong heating and confinement caused detonation.


Have you tested Ba(ClO3)2 and potassium benzoate yet?

EDIT:
I pressed the remaining 0.1 g in a thin walled aluminium foil tube, again with a few mg KClO3/K3[Fe(CN)6] as primer. It went of with an amazingly loud and sharp bang and shattered the aluminium plate it was placed on. So yet another mixture with potential as primary.

[Edited on 9-3-2014 by Dornier 335A]
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[*] posted on 9-3-2014 at 07:10


Outside of high pressure (rocket engine) use, NH3ClO4 often isn't the oxidizer of choice for speed.

NH3ClO4 fireworks star mixtures are generally harder to ignite, slower burning and have lower critical speeds than similar mixes made with KClO4.

For uses where the solid reaction products left by KClO4 detract from flame color & transparency, NH3ClO4 is often substitutes- But almost always with a few % of the Potassium salt to enhance ignition and burn speed.

KClO4 and hexamine mixture burns slowly compared to benzoate or salicylate fuels. We sometimes substitute a few % hexamine for other hot, fast burning fuels in fireworks star mixes to slow & cool the burn, as in blue mixes that would turn to green at too high temperatures.

Usually if you melt the perchlorate in a mix, the stuff is on fire...

(edit)
No, I have not yet tried to melt any whistle fuel analogues. Kind of busy with the work that pays the bills-

[Edited on 9-3-2014 by Bert]




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[*] posted on 10-3-2014 at 01:38


The use of aromatic salts compounds is needed:
-1°) to make the salt resist the heating without sublimation or volatilisation
-2°) because of the high % of charing when heated so the mix is a kind of chlorate/C mix (with atomic or molecular C).
-3°) the oxydation/burning set free some organic acids that participates to the unstability of the chlorate and lower the activation energy during the combustion process.

For this reasons also reaction with perchlorates or with hexamine will behave very differently and not go D2D in tiny amounts.

Maybe hexamine salt and chlorate will provide a different result, but this is another story because in the mix you would have an acidic moeity (hexamine salts are mildly acidic) and so some HClO3 would form and fix to the hexamine to make hexamine di-chlorate salt... Most organic amine chlorate salts are sensitive HE (choc, friction and heat) even more than the perchlorate ones. So this would be like a gun-powder composition with a detonating stuff dispersed into it (between detonation and deflagration).

Edit:
-Copper doesn't stand well chlorate...I had some CuCl2 and CuOCl used to get some green shade decomposing into NaClO3 composition there was a Cl2 smell.

-For the stupid ones don't forget the rule no ammonium salt mixed with chlorates...so no ammonium benzoate mixing with KClO3 or NaClO3! Spontaneous ignition might occure at any time.

[Edited on 10-3-2014 by PHILOU Zrealone]




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[*] posted on 10-3-2014 at 08:55


As P. Zrealone mentions, the use of copper salts mixed with chlorates is in general a bad idea, copper contamination of chlorates is generally percieved as a pretty awful safety risk... Cannot imagine doing it deliberately! It is probably for this reason - copper sensitizes chlorate quite a bit, and the benzoate is easily enough going to act as a fuel...

As Bert mentioned, Ammonium Perchlorate is a not-so-great oxidizer for use in stuff outside of rocket propellants as it is fairly slow stuff. it would actually be interesting though to test Ammonium Perchlorate recrystallized with hexamine as a rocket propellant though, I imagine said mix would evolve a fair amount of gas and be a decent propellant, though it would likely need a bit of aluminium added to get it going fast enough to get stuff off the ground. Using a deep core would be advised as opposed to an end-burning design.

These mixtures, while interesting, do not strike me as particularly suitable as replacements for primaries, mostly because all of them seem to suffer some inherent instability (f.ex: copper and chlorate...). The chlorate and sodium benzoate mix does look interesting though, I would love to give it a shot sometime if it seems to be able to self confine in such small amounts. Melting a small quantity of it onto a bridgewire might make a decent electrically fired squib.
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[*] posted on 7-6-2014 at 05:28


I ran a series of tests with sodium chlorate and sodium benzoate. At first the mixture seemed to behave identically with the potassium chlorate version, with the exception that now the chlorate melted before the benzoate.
What became apparent after a few tests was that the mixture was more difficult to detonate properly than with KClO3. It did not always go high order when confined in aluminium foil and heated. The aluminium fragments were also larger which indicates less brisance. I had expected the opposite. The somewhat disappointing results are likely due to the melting point and decomposition point of NaClO3 not being matched very well by those of the fuel.
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[*] posted on 9-6-2014 at 05:22


Perhaps this mixture offers a more convenient and reliable way of thermal initiation without the undue sensitivity that plagues most primaries. Although the fact that it needs a rather controlled gradual heating to first melt and then detonate, will most probably complicate things. A bulky metal or perhaps a ceramic interface that transfers the heat gradually from a pyrotechnical mixture to the KClO3-bezoate charge might work in this case, but it will not be convenient and tends to become bulky, cumbersome and unpredictably delayed as most thermo-shock based initiators. Though as a proof of concept test, it might be worth investigating....



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[*] posted on 13-6-2014 at 09:56


Quote: Originally posted by Dornier 335A  
I ran a series of tests with sodium chlorate and sodium benzoate. At first the mixture seemed to behave identically with the potassium chlorate version, with the exception that now the chlorate melted before the benzoate.
What became apparent after a few tests was that the mixture was more difficult to detonate properly than with KClO3. It did not always go high order when confined in aluminium foil and heated. The aluminium fragments were also larger which indicates less brisance. I had expected the opposite. The somewhat disappointing results are likely due to the melting point and decomposition point of NaClO3 not being matched very well by those of the fuel.

Maybe NaClO3 cristallises with water or catch water from the air more than KClO3 does...are you sure the NaClO3 was anhydrous and kept away from moist air?




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[*] posted on 13-6-2014 at 18:37


Hello everyone, been absent here awhile. This topic sparks my interest. As PHILOU Zrealone and Dornier 335A concur, double replacement is forming a double salt. Co-crystallized salts containing oxidizer and fuel , ordinarily tend to be sensitive. Chlorate with organic fuel always react to some extent. What is really remarkable is that this mixture is able to melt without immediately exploding , has high explosion temperature and high impact insensitivity. The expected properties of the resultant double salt will exhibit more susceptibility to shock given the intimate composition of anions, as Dornier 335A has already observed www.sciencemadness.org/talk/viewthread.php?tid=29259#pid3218...

Elsewhere I had proposed :

" Tricyanomethane and Trinitromethane form ionic metal salts. A way in which the two
moieties might be compounded is by a solution of equal parts of Magnesium Tricyano -
methanide and Magnesium Trinitromethanide co-crystallized as a double salt , thus
Mg{C(CN)3}2 + Mg{C(NO2)3}2 => 2 Mg{C(CN)3C(NO2)3} => 2 MgO + 10 CO + 6 N2

In the same way , Benzoate and Chlorate salts , both of either Calcium or Magnesium should result in a double salt. Of course this would be a compound with a one Chlorate anion per Benzoate anion. Performance would be much reduced. A melt of Benzoate in excess Chlorate , of course yields better oxygen balance. The wavering quality of the product produced must be attributable to inconsistent inhomogeneous crystallization. www.sciencemadness.org/talk/viewthread.php?tid=29259&pag...
A way to obtain a well uniform product is to first obtain the stoichiometric double salt and then subsequently to blend that in with a greater amount of Chlorate salt.

__________________________________________


First we obtain the stoichiometric Calcium Benzoate Chlorate double salt

Ca(C7H5O2)2 + Ca(ClO3)2 => Ca2(C7H5O2)2(ClO3)2
Having a molar weight ratio of 282 : 207

Next we compound this with Sodium Chlorate

Ca2(C7H5O2)2(ClO3)2 + 3 Na(ClO3)
Having a molar weight ratio of 489 : 320

which will detonate into
=> CaO + CaCl2 + 3 NaCl + 14 CO + 4 H2O + H2


.

[Edited on 14-6-2014 by franklyn]
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[*] posted on 14-6-2014 at 20:51


The question of what are the optimal ratios of Benzoate to Chlorate confirms that zero oxygen balance yields the highest heat value per weight of material.
Ignoring everything to the left of NaCl in the balanced equations seen below , and just summing the heat of formation of CO2 , CO , and H2O , in ratio to the total weight of the ingredients , the higher the number , the higher the heat value , an additional 192 kilocal for every mol of NaClO3.

This does not automatically confer higher brisance. The number of gas mols is constant while the number of mols of solid products increases , and as a result the gas proportion is reduced with better oxygen balance. ( High velocity explosives in composition with Aluminum trade some brisance for enhanced blast. The optimal amount is around 18 to 20 percent which yields a third of detonation products as solid alumina.) This also occurs for the stoichiometric mixture , with 8 mols NaClO3 , where best performance will likely be seen.

The following values in kilocalories per mol are applied for thermodynamic calculations
- 94 for CO2 , - 26.4 for CO , - 57.8 for H2O

Ca2(C7H5O2)2(ClO3)2 = mol wt. 489 , NaClO3 = mol wt. 106.5 . . . . . . . . . . . . . . . . . . . . . . .∆H / mol wt. . . . . . . .solid mols / total of mols


Ca2(C7H5O2)2(ClO3)2 + 3 NaClO3 => CaO + CaCl2 + 3 NaCl + 14 CO + 4 H2O + H2 . . . . . . 601 / 809 . .~ 0.74 , . . . . % solids . .~ 21

Ca2(C7H5O2)2(ClO3)2 + 4 NaClO3 => CaO + CaCl2 + 4 NaCl + 2 CO2 + 12 CO + 5 H2O . . . 794 / 915 . . ~ 0.87 , . . . . % solids . .~ 24

Ca2(C7H5O2)2(ClO3)2 + 5 NaClO3 => CaO + CaCl2 + 5 NaCl + 5 CO2 + 9 CO + 5 H2O . . . 986 / 1022 . . ~ 0.96 , . . . . % solids . .~ 27

Ca2(C7H5O2)2(ClO3)2 + 6 NaClO3 => CaO + CaCl2 + 6 NaCl + 8 CO2 + 6 CO + 5 H2O . . .1199/ 1128 . . ~ 1.06 , . . . . % solids . .~ 30

Ca2(C7H5O2)2(ClO3)2 + 8 NaClO3 => CaO + CaCl2 + 8 NaCl + 14 CO2 + 5 H2O . . . . . . . 1605 / 1341 . . ~ 1.2 , . . . . . % solids . .~ 34

12 : 21 parts by weight

Dividing the mol weight of the stoichiometric mixture 1341 by the mol weight of each of the preceding mixtures individually , you obtain a factor by which to multiply it's ∆H value , thus normalizing the shown values for an equal weight of material ( 1341 ) in every case. This works out to 996 ∆H for 3 mols NaClO3 , 1164 ∆H for 4 mols , 1293 ∆H for 5 mols , 1425 ∆H for 6 mols.


.

[Edited on 15-6-2014 by franklyn]
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[*] posted on 15-6-2014 at 09:46
new use for tetraphenylborates!


Naively I think the stability of the molten stuff is repulsion between fuel anion and oxydizer anion. In order to get a neutral intermediate, MO(-) breaks off leaving either PhC=O (+) or the chloryl cation, or some radical. If that's true, perhaps the properties and stability could be fine tuned, deliberately and science like. Patents cost and if it's obvious to me it's obvious.

Phthalate and terphthalate with two carboxylates: dead weight, but maybe less reactive?

Gallates used to be used in whistle composition, and salicylates. I'd guess those are worth investigating in the molten MClO3 or 4 mixture, and common too.

If we want to get baroque there are the anisic acids, aminobenzoic, etc.

I doubt the arylsulfonates have [had any reason to] been tried in pyrotechnic compositions before. And if we want to be absurd, tetraphenylborate salts are known.

[Edited on 15-6-2014 by halogen]




F. de Lalande and M. Prud'homme showed that a mixture of boric oxide and sodium chloride is decomposed in a stream of dry air or oxygen at a red heat with the evolution of chlorine.
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[*] posted on 15-6-2014 at 17:16


Along the same lines I thought of this , mixing Calcium Chlorate and Calcium Picrate
to form a double salt with a much improved oxygen balance. Perchlorate would do
nicely also. Though it's been contemplated by some , melting picrate salts seems
risky , www.sciencemadness.org/talk/viewthread.php?tid=6551
Formation from cold solution seems the proper route.

2 Ca(ClO3)2 + 2 Ca(C6H3N3O7)2 => 2 Ca(ClO3)2 (CaC6H3N3O7)2


Calcium Chlorate Picrate.gif - 2kB

=> 2 CaO + 4 CO2 + 8 CO + 2 H2O + 3 N2 + Cl2

____________________________________________


While on this subject , another possible double salt using Calcium to link Trinitromethane with Trinitrophenol.

Calcium Picrate Trinitromethane.gif - 3kB

=> CaO + 4 CO2 + 3 CO + H2O + 3N2
.

[Edited on 16-6-2014 by franklyn]
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[*] posted on 16-6-2014 at 04:00


PHILOU Zrealone, the mixture ignites at more than 250°C. I'm sure there won't be any water left in the liquid.

I believe the goal is to find the best compromise between homogeneity of the mix, oxygen balance and actual usefulness. The molten mixture is homogeneous and can have perfect oxygen balance (I mixed mine to -10%), although not very useful in practice due to the high melting point.

I was able to detonate melted and quickly solidified flakes of the mixture, but those are likely to be less homogeneous. What about cooling the liquid down faster, like dripping it into liquid nitrogen?

Double salts' complete homogeneity even in the solid state is indeed interesting Franklyn. I think smaller or better oxygen balanced anions are the way to go with chlorate, rather than mixing the double salt with excess chlorate afterwards. Using calcium as the cation might be problematic because the benzoate crystallizes with water and the chlorate is very hygroscopic.

I will try a mixture (preferably molten or cast) of NaClO3 and calcium picrate as soon as possible, hopefully this week. My theoretical calculations say it will have exceptionally high performance (>8000 m/s at max density). KClO3 or NaClO3 and potassium picrate is also on my list.
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[*] posted on 19-6-2014 at 12:19


Okay, I've synthesised three metal picrates now: potassium, calcium and sodium. I tried combinations with sodium and potassium chlorate. Below you can see melting points and ignition points for the ingredients:

Data from Urbanski, Fedoroff and Wikipedia

The criteria for a mixture like KClO3/sodium benzoate seem to be the following:
- At least one of the components have to be molten at the ignition point.
- The fuel and oxidizer have to be compatible in the melt.
- The oxidizer should not decompose first, otherwise bubbles will form.
- And finally the mixture should detonate fairly easily.

Only one of the six mixtures fulfilled all four criteria and gave satisfactory results. It was potassium chlorate and sodium picrate, 50/50 by weight. One milligram confined in aluminium foil and heated briefly in a flame exploded with incredible power, turning the foil into hundreds of fragments. Potassium chlorate and potassium picrate ignited before melting. Sodium chlorate and potassium picrate started to bubble and detonated very seldom. Calcium picrate behaved very strangely. It deflagrated only slowly, even though Fedoroff wrote it "explodes violently at 323-28°". A mixture with potassium chlorate could detonate if confined well enough and heated quickly, but its brisance was not very impressive.

One mixture which could work is sodium chlorate and copper picrate; copper picrate is said to explode violently at 282-287°C. (I know copper/chlorate is generally a bad idea but it's worth a try.)




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[*] posted on 20-6-2014 at 03:06


copper and chlorate? you sure this isnt because it could by accident get near ammonia and form the primary explosive tetraammine? when i get all the acid out of my copper chloride ill attempt to make copper chlorate, i recall it has even been sold in smaller amounts for use in exotic fireworks
and if pyrotechnicians dares to handle it, then there shouldnt be that much worries about it
but again, you cant get smarter by assuming you know it all




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[*] posted on 25-7-2014 at 07:52


This type of composition is very powerful when melted and it does explode but not deflagaration.
I Wonder can I twist the formula in order to make it explode in no time when a fire near to iit.
Currently using this formula :
Potassium Chlorate = 7.11%
Sodium benzoate = 2.99%
.

KClO3 is laboratory grade where sodium benzoate is food grade which is obtain from a bakery shop
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[*] posted on 26-7-2014 at 05:08


What is the other 90%, or did you make a mistake?



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