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Author: Subject: Some old English patents appertaining to mixtures intended to substitute primary explosives
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[*] posted on 6-4-2010 at 14:02


Quote: Originally posted by Blasty  
In the section about explosives in Thorpe's A dictionary of applied chemistry, there is mention of several patents regarding mixtures that are intended as replacements for primary explosives, like mercury fulminate, in blasting caps/detonators, an interesting but relatively little known or talked about subject:

[snip]

You may find Richard Escales und Alfred Stettbacher's
Die Explosivstoffe
Intitialexplosivstoffe
Verlag von Veit & Comp.
1917

Useful. It has been reprinted.

And —

Explosiv- und Züdstoffe in the yearly editions of —

Technicsh-Chemisches Jahrbuch
(1904 is volume 27.)
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[*] posted on 7-4-2010 at 07:55


Quote: Originally posted by Blasty  
In the section about explosives in Thorpe's A dictionary of applied chemistry, there is mention of several patents regarding mixtures that are intended as replacements for primary explosives, like mercury fulminate, in blasting caps/detonators, an interesting but relatively little known or talked about subject:


-------
You could check :—

JP Cundill
Dictionary of Explosives
2nd Edition London 1895

It has been reprinted, or you can DL it from Google.com/books

JD Daniel
Dictionnaire Matiéres Explosives
Paris 1902
Google books again.

Patents for Inventions
Abridgments of Specifications
Class 9
Ammunition, Torpedoes, Explosives and Pyrotechnics
HMSO
Reprinted by Museum Restoration Service
Canada 1981

Various volumes.

I own
1855-1866
1867-1876
1877-1883
1884-1888
1889-1892
1893-1896
1897-1900

I do not know if there are earlier/latter volumes.




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[*] posted on 23-6-2010 at 15:51


I found some interesting old passages about the intricacies of detonating nitrocellulose using both primary explosives as well as non-primary explosives:

http://books.google.com/books?id=Y449AAAAYAAJ&pg=PA499&a...

"These effects are less marked in the case of loose gun-cotton, on account of the large quantity of air interspersed through its bulk. As compressed gun-cotton is less compact than nitroglycerin, it should follow that it is less easily detonated than nitroglyeerin ; and this is found to be the case. Nitroglycerin may be detonated by the fall of a weight from a moderate height, by a gun-cotton fuse, or by a mixture of potassium chlorate and fulminate of mercury. Gun-cotton detonates only with pure fulminate of mercury, and the best results are not obtained unless the fulminate be enclosed in a rather thick case of sheet-tin, and placed in contact with the gun-cotton, conditions which realise the greatest initial pressure. The quantity of force thus converted depends on the suddenness of the shock, and on the amount of work which it is capable of doing. These elements vary with the detonator, and Abel has found that chloride of nitrogen is not very efficacious, and that iodide of nitrogen, which explodes by the slightest friction, is incapable of exploding gun-cotton. But chloride of nitrogen develops lens heat than any other compound here treated of (see table), therefore a larger quantity of it must be employed, and judging by analogies drawn from other iodine substitution-substances, iodide of nitrogen should develop less heat and work than the same weight of chloride of nitrogen : hence its inactivity in this respect."

http://books.google.com/books?id=G1cmAQAAIAAJ&pg=PA725&a...

"The difference in the behaviour of such explosive substances as nitro-glycerine and its compounds, and gun-cotton when exposed to the influence of a source of heat, has been made the subject of careful investigation by many distinguished chemists in this and other countries. M. Nobel has shown that crude nitroglycerine can be detonated by contact with a small charge of confined gunpowder or by a large percussion cap.

It occurred to Mr. E. O. Brown, assistant-chemist of the War Department, that gun-cotton might also be ignited and exploded by detonation. Experiment proved this to be the case when the particles of the cotton were in a finely-divided state, and when its mass had been subjected to powerful pressure. Further trials, however, showed that gun-cotton is not nearly so sensitive or so susceptible to detonation as nitro-glycerine. The detonation of compressed guncotton cannot be accomplished by the explosion of ordinary fulminates. Nitro-glycerine can be detonated in contact with compressed gun-cotton without exploding the latter. An electric fuse, charged with 100 grains of a mixture of sulphide of antimony and chlorate of potash, has been fired on a disc of compressed guncotton without causing any explosion. The gun-cotton merely ignited and burnt away. A bottle, containing three-quarters of an ounce of pure nitro-glycerine has been detonated on the top of a disc of compressed guncotton without exploding the latter. The gun-cotton in this case was scattered by the violence of the explosion, and fragments of it inflamed. A detonating fuze containing ten grains of mercuric fulminate failed to explode a hank of gun-cotton thread, while half that amount of fulminate was sufficient to cause compressed gun-cotton to detonate violently.

These experiments support the views held by Mr. Abel:—

1. That gun-cotton, freely exposed, cannot be detonated by any explosive agent less sudden and violent in its action than mercuric fulminate.

2. That nitro-glycerine, which is more readily exploded by a blow than gun-cotton, may be detonated through the agency of explosive mixtures far less violent and sudden in their action than fulminate of mercury.

3. That the mechanical condition of the gun-cotton most materially influences the result, and that a considerable compactness or density, and a consequently great resistance to motion of the particles, is essential for the detonation of gun-cotton.

To what, then, is this remarkable action due? How comes it that the same substance is susceptible of a totally different metamorphosis into its gaseous products according to the manner in which fire is applied? Is it that the violence of explosion is proportionate to the amount of heat evolved in the disturbance of the chemical equilibrium of the particular substance used as a detonator? Is it due to the facility offered for the passage of heat throughout the material acted on? Is it owing to the suddenness or sharpness with which the detonating substance acts? Experiment does not support any one of these views. There is far more heat evolved in the combustion of 100 grains of sulphide of antimony and chlorate of potash than in the explosion of ten grains of mercuric fulminate; the latter, however, invariably detonates compressed gun-cotton, while the former fails to do so. It is impossible to detonate loose porous guncotton, so that the action cannot be due to the facility with which heat can permeate the mass. Both iodide and chloride of nitrogen, even in comparatively large charges, fail to detonate gun-cotton; yet the explosion of these substances is certainly far more sudden than mercuric fulminate. We must accordingly look elsewhere for an explanation of this extraordinary phenomenon, and recent experiments appear to favour the theory advanced by Mr. Abel, that the relative power of different explosive agents to accomplish the detonation of gun-cotton appears to be in direct proportion to the mechanical effects of their explosion ; in other words, to the blow they are capable of inflicting on whatever body they may be in contact with.

When iodide and chloride of nitrogen are fired on a thin sheet of copper, the indentation produced by the explosion is not nearly so marked as in the case of the mercury or silver fulminates. The indent produced by the former is not nearly so deep or sharply defined; indeed, a charge of two grains of chloride of nitrogen has been exploded on a watch-glass without fracturing it, whereas half that amount of silver fulminate was sufficient to shatter the glass to atoms. The mechanical effect of mercuric fulminate is much enhanced by confinement in a strong case, such as a tin tube, and under such conditions the violence of its action, as measured by work done, is in excess of either of the nitrogen compounds.

This may probably account for the fact that, although more instantaneous in its action, iodide of nitrogen fails to detonate gun-cotton, even in a charge twenty times greater than the usual charge of mercuric fulminate. Possibly, further investigation may throw more light on this remarkable explosive property. There may yet be some hidden peculiarity in the concussion or powerful vibration produced by some substances distinct from the mechanical force due to their explosion. There appears to be a species of entente cordiale between explosives of a certain class. They have a strange, undefined sympathy with one another. If one goes off, all the others in the immediate neighbourhood seem instantaneously to be en rapport. As the synchronous vibrations of a tuning-fork are taken up by other instruments, so the molecules of various explosives pulsate in unison. Thus, bodies in a state of high chemical tension may prove more susceptible to the operation of mechanical force chemically applied."

http://books.google.com/books?id=t-_mAAAAMAAJ&pg=PA179&a...


"Among several other interesting results furnished by an examination into the conditions governing and results attending the transmission of detonation by tubes, a remarkable want of reciprocity was found to exist between mercuric fulminate and gun-cotton. The latter substance is more susceptible to the detonative power of mercuric fulminate than of any other substance, as will presently be further shown. The quality of fulminate required to detonate gun-cotton is regulated by the degree to which the sharpness of its own detonation is increased by the amount of resistance to rupture offered by the envelope in which the fulminate is confined. From 20 to 30 grains are required if the detonative agent is confined in a thin case of wood or in several wrappings of paper; but as small a quantity as 2 grains of the fulminate suffices to effect the detonation of compressed gun-cotton, provided the fulminate be confined in a case of stout metal (sheet tin), and be closely surrounded by being tightly imbedded in the mass of gun-cotton. If there be no close contact between the two, the quantity of fulminate must be very considerably increased to ensure the detonation of the gun-cotton; and, in attempting to transmit detonation from mercuric fulminate to gun-cotton by means of tubes, it was found necessary to employ comparatively very large quantities of fulminate in order to accomplish this, even through short lengths of tubes. But when the quantity of fulminate used reaches certain limits, the detonation may be transmitted from it to gun-cotton through very long lengths of tube. In applying gun-cotton, on the other hand, to accomplish the detonation of mercuric fulminate, it was found that this result could be attained, and through considerable lengths of tube (7 feet and upwards), by means of very much smaller quantities of guncotton than is needed of fulminate to induce the detonation of gun-cotton through the corresponding distances.
This want of reciprocity between two detonating agents corresponds to one even more remarkable, which was observed by the lecturer in his earlier investigations on this subject. In the first place it was found that the detonation of 1/4 oz. of gun-cotton (the smallest quantity that can be thus applied) induced the simultaneous detonation of nitro-glycerin, enclosed in a vessel of sheet-tin, and placed at a distance of 1 inch from the gun-cotton ; while with 1/3 oz of the latter the same effect was produced with an intervening space of 3 inches between the two substances. But on attempting to apply nitro-glycerin to the detonation of gun-cotton, the quantity of the former, which was detonated in close contact with compressed gun-cotton, was gradually increased in the first instance to 3/4 oz., and subsequently even to 2 ozs., without accomplishing the detonation of the latter, which was simply dispersed in a fine state of division, in all instances but one, in a large number of experiments.
The force developed by the detonation of nitro-glycerin was found, by careful comparison of the relative destructive effects of corresponding quantities, to be decidedly greater than that of the fulminate, of which from 2 to 5 grains suffice for developing the detonation of gun-cotton, when it is in close contact with them. The non-susceptibility of gun-cotton to detonation by nitro-glycerin is therefore, it need scarcely be said, not ascribable to any deficiency in mechanical force suddenly applied when the nitro-glycerin is detonated.
That the power possessed by different very highly explosive substances, of inducing the detonation of such bodies as gun-cotton and nitro-glycerin is not solely ascribable to the operation of mechanical force very suddenly developed, is indicated not only by the singular inertness of guncotton to the influence of nitro-glycerin as a detonating agent, but also by a comparison of the behaviour of other detonating substances with that of the mercuric fulminate, when applied to the detonation of gun-cotton. Thus, the detonation of silver fulminate is very decidedly sharper than that of the mercury compound, yet it is in no way superior to the latter in its power as an initiative detonating agent; indeed, a somewhat larger amount of it appeared to be required than of the mercury salt to induce detonation of gun-cotton with certainty. Again, the iodide and chloride of nitrogen are far more susceptible of sudden detonation than the silver fulminate ; yet while 5 grains of the latter, confined in a stout metal envelope, suffice to detonate gun-cotton, 50 grains of chloride of nitrogen confined by water, appeared to be the minimum amount with which the detonation of gun-cotton could be accomplished with certainty, while no success attended the employment of confined iodide of nitrogen in quantities ranging up to 100 grains.
The incompatibility of these results with the general conclusion, based upon numerous and greatly varied experiments, that the facility with which the detonation of gun-cotton and nitro-glycerin, and bodies of a similar character as explosives, is induced by an initiative detonation, is proportionate to the mechanical force aided by the heat developed by the latter, led the lecturer to the conclusion that a synchronism or similarity in character or quality of the vibrations developed by the detonation of particular substances, operates in favouring the detonation of one such substance by the initiative detonation of a small quantity of another, while in the absence of such synchronism, a much more powerful detonation, or the application of much greater force, would be needed to effect the detonation of the material operated upon. This view has received considerable support from results since obtained by other experimenters, especially by MM. Champion and Pellet; but the subject is one which still needs further experimental elucidation.”


http://books.google.com/books?id=4Z08AAAAYAAJ&pg=PA140&a...

"The explosives such as the dynamites, nitroglycerin, dry gun-cotton, and the picrates detonate with extreme violence when a relatively small quantity of fulminate of mercury or chlorate of potash is detonated in close contact with them. These small primers are generally of 0.4 gramme to each 50 gr. of charge. In practice 1.5 gr. of fulminate will explode any ordinary charge.
Dry gun-cotton will not explode by the use of iodid or chlorid of nitrogen: fulminate of silver as violent as that of mercury fails also unless a large quantity is used; whilst chlorate of potash and sulphuret of antimony accomplish it easily ."


It is interesting to notice the contradiction between the last statement above (viz. that gun-cotton can be set off by a charge composed of a mixture of potassium chlorate and antimony sulfide) and the one given in the second source (viz. that 100 grains of such a mixture failed to explode gun-cotton.)

One of the Von Dahmen patents specifically mentions that one of his mixtures can detonate gun-cotton:

http://www.google.com/patents?id=5B1QAAAAEBAJ&printsec=a...

[Edited on 23-6-2010 by Blasty]
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[*] posted on 16-9-2010 at 00:05


Quote: Originally posted by Blasty  
Quote: Originally posted by Rosco Bodine  
(by weight) KClO3 5 parts and potassium ferricyanide 3 parts is a fulminating mixture.


Yes, a similar mixture, but with potassium picrate added in (invented earlier by Designoble and Casthelaz, but who apparently had not fully realized its potential use as an initiator) was already used by Prudencio Castellanos in the 1870s to detonate dynamites:

http://www.google.com/patents?id=2C9tAAAAEBAJ&printsec=a...

He called his devices "percussive petards". He made them both out of metal capsules as well as of cardboard tubes. The percussive mixtures he used do not require pressure after being loaded in the containers, and seem to work best granulated.

Something that Castellanos says in his patent also struck me as curious: even black powder charges were apparently being used to attempt to detonate dynamites. It doesn't seem that the fulminate blasting cap was as universally accepted as one would think from reading most history books on the subject.


Attached is the Designoble and Casthelaz patent US76173 which lists potassium ferrocyanide (not ferricyanide) in mixture with potassium chlorate and potassium picrate, describing the mixture as being "three times as powerful as mercury fulminate", probably an exaggeration, but such an anomaly could I suppose be possible. I wonder also about the energy difference which may be manifested dependant upon whether the ferrocyanide or the ferricyanide is used, or what difference may be realized by use of different metal ferricyanide salts or double salts. It may be possible to improve such mixtures.

Attachment: US76173 chlorate - picrate detonating mixture.pdf (174kB)
This file has been downloaded 614 times

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[*] posted on 18-9-2010 at 22:13


Quote: Originally posted by Rosco Bodine  


Attached is the Designoble and Casthelaz patent US76173 which lists potassium ferrocyanide (not ferricyanide) in mixture with potassium chlorate and potassium picrate, describing the mixture as being "three times as powerful as mercury fulminate", probably an exaggeration, but such an anomaly could I suppose be possible. I wonder also about the energy difference which may be manifested dependant upon whether the ferrocyanide or the ferricyanide is used, or what difference may be realized by use of different metal ferricyanide salts or double salts. It may be possible to improve such mixtures.


Those are good questions, which I wish I had better conditions to investigate myself. Unfortunately, my ability to perform such experiments is pretty limited (only during two seasons a year can I make any "loud" experiments, when everyone around here is discharging all sorts of fireworks.) If we could count with the cooperation of someone who is located in a more suitable environment to test such things many of these interesting questions could be settled once and for all.
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[*] posted on 23-10-2010 at 21:13
Here is an obscure composition


Here is a mixture which I found in PATR, a chlorate mixture which is reportedly brisant.

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[*] posted on 25-10-2010 at 21:20


Quote: Originally posted by Rosco Bodine  
Here is a mixture which I found in PATR, a chlorate mixture which is reportedly brisant.



Thanks for the info on this yet another mixture intended to substitute primary explosives. I don't suppose you have been able to find information on how it was intended to be deployed (strong containment required or not?, pressed or loosely packed?, granular or powder form?, etc.)

My concern with this mixture, as with all mixtures that contain ammonium and chlorate compounds, would be the possibility of ammonium chlorate being formed, which is well known to be a very unstable compound capable of exploding spontaneously. If I ever prepared such a mixture, I would try to use it as soon as possible and not store it for long periods of time, which would increase the chances of that dangerous compound being formed.

[Edited on 26-10-2010 by Blasty]
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[*] posted on 13-4-2011 at 22:20


I found this passage in Tenney L. Davis' Sugars in Fireworks and Explosives (The Sugar Research Foundation, 1948, page 152) appertaining to the general topic of this thread:


Quote:

Nitrolactose has been recommended for use in detonators and blasting explosives. Large describes primary charges for compound detonators consisting of mixtures produced by the concurrent precipitation of nitromannite or nitrodulcite with PETN or nitrocellulose and/or with tetryl or other nitro-compound. In particular he recommends a concurrently precipitated mixture of nitromannite 50 parts, nitrolactose 35, and tetryl 15. These mixtures when lighted by a flame burn in the open with a flash, but when confined in a blasting cap shell, they detonate and are capable of initiating the high explosive secondary or main charge of the detonator. Lange finds that nitrocellulose alone is satisfactory for this purpose, and reports that 0.2 g. detonates nitromannite and that 0.5 g. causes the satisfactory detonation of tetryl.



I am not sure if there was a typo here and the "Lange" reported as finding that nitrocellulose by itself can detonate nitromannite and tetryl is actually the same person as the "Large" referred to earlier in the passage. The Large patents Davis refers to are U. S. Patents 1,928,204 to 1,928,207:

http://www.google.com/patents/about?id=aB5FAAAAEBAJ&dq=1...

http://www.google.com/patents/about?id=aR5FAAAAEBAJ&dq=1...

http://www.google.com/patents/about?id=ah5FAAAAEBAJ&dq=1...

http://www.google.com/patents/about?id=ax5FAAAAEBAJ&dq=1...


[Edited on 14-4-2011 by Blasty]
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[*] posted on 14-4-2011 at 07:55


I am familiar with the [written] material, & it is a typo TTBoMK. Apparently Davis had either worked for or consulted with the Sugar Research Foundation in expounding the boundaries of their sales (explosives). There is more to this via additional papers published by Davis. There was some interest in using MHN as it filled a gap between primary and secondary and it's use in detonators. A nitrated sugar could present a substantial sales agenda, etc.
Pyrotechnia has a free download entitled "Essential Tenny Davis" which has SOME of the material. Davis published long before the classic 1940's work and some of this material is still available now that he has become so popular. Unlike many other polyols mannitol & lactose were fairly common and less expensive. However they needed a higher level of nitration to become appropriate for explosive use. Even Schonbein had worked with nitrated polyols back in the mid-19th century.




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[*] posted on 18-5-2011 at 15:41


Quote: Originally posted by Blasty  
Something that Castellanos says in his patent also struck me as curious: even black powder charges were apparently being used to attempt to detonate dynamites. It doesn't seem that the fulminate blasting cap was as universally accepted as one would think from reading most history books on the subject.


I found this passage regarding this subject in the Proceedings of the National Safety Council, 1918, page 1122:

"It is a common practice in some sections to place a dynamite cartridge in the bottom of a bore hole and the main charge of black powder on top of that, firing the black powder with fuse or squib. The dynamite explodes from the shock of the black powder but it does not explode as completely as when detonated by blasting cap, so that it is doubtful if any real benefit is obtained by this method. Different explosives have such different rates of detonation that it is not only wasteful but frequently dangerous to use this method of blasting."

It seems that as late as the 1910s there still were miners using black powder to set off dynamite.
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