History
   
 
 
Historic survey of the chemical-technical development of detonators and primers:

Definition of terms:

Primary explosive (initiating explosive):

Primary explosives can be caused to detonate by relatively weak mechanical impact or by sparks. Primary explosives are required to have a high shattering power and trigger rate as well as a sufficiently high chemical and thermal stability. The most important representatives are fulminating mercury, lead and silver azide, lead trinitroresorcinate (trizinate), diazodinitrophenol and, as additive in primers, tetrazene. The production and processing of primary explosives is one of the most dangerous activities in the chemical industry and require a high technical safety effort.

Primers:
These are articles (such as percussion caps) containing explosives or consisting of explosives which are intended to trigger a conflagration or deflagration of other explosives.

Detonators:
These are articles containing explosives or consisting of explosive which are intended to trigger a detonation of other explosives.

We should like to point the interested reader to two books entitled EXPLOSIVSTOFFE and EXPLOSIVES (publisher: Verlag WLEY-VCH GmbH) on which the owner of our company has been working as co-author for more than 10 years.

1608

In his “Basilica chimica” Oswald Croll mentions fulminating gold ammonia which was give the name “Aurum
fulminans“. Its composition is outlined by Kunckel in 1700, confirmed by Bergmann (1769) and Scheele (1777) and its constitution determined by Dumas (1830).

 

1609

Fulminating gold is mentioned in the writings on alchemy by Johann Thölde of Frankenhausen.

 

1621

Proof is apparently provided in “Tractatus de quinta Essentia” first taken by Joachim Morsius from England in 1621 and printed in Hamburg that the Dutchman Cornelius van Drebbel was familiar with fulminic acid salts, in particular fulminating mercury. Similarly, van Drebbel probably discovered fulminating gold.

 

1690

Kunckel provides the first reliable information on the formation of fulminating mercury (Kunckel: Laboratorium chymicum, page 213).

 

1799

Howard (England) discovers that fulminating mercury is formed when pouring nitric acid on a mixture of red mercury oxide and aqueous ethyl alcohol and described for the first time in detail the explosive properties of this compound.

 

About 1800

First industrial-scale preparation of fulminating mercury by Lulien Leroi in France; he and his brother-in-law lose their lives in an explosion.

 

1815

The British gunsmith Josef Egg of London invents the percussion caps made of copper and filled with black blasting powder and potassium chlorate. Other sources attribute the invention of the percussion cap to the Scotsman Alexander Forsyth (1807).

 

1816

Fulminating mercury mixed with wax or alcoholic benzoic tincture is used as ignition material.

 

1817

Deboubert in Paris produces the first weapon in which a percussion cap is ignited by the thrust of the cock.

 

1821

The Englishman Wright produces the first percussion caps filled with fulminating mercury.

 

1836

In France, 800 million percussion caps are produced from 15-16 tonnes of fulminating mercury in the course of one year.

 

1858

Peter Gries discovers the aromatic diazo compounds (-> diazodinitrophenol).

 

1864

Alfred Nobel builds the “patented Nobel fuse” named after him. An inner tube of glass or tinplate holds gunpowder which is caused to explode by a fuse being inserted and which triggers nitroglycerine held in an outer cartridge to explode.


1867

In British patent no. 1345 of 7th May, A. Nobel describes the first fulminating mercury blasting cap with a sheath of copper and brass.

 

1888

In the course of his investigations into guanidine derivatives, Thiele obtains a yellow explosive substance which 40 years later is recognised as being tetrazene.

 

1890

Curtius discovers hydrazoic acid.

 

1891

Wislicensus produces sodium azide from a nitrous oxide and sodium amide, thus laying the foundation for its industrial synthesis.

 

1893

Tests by Will-Lenze with silver azide, lead azide and mercury azide as initiating detonator. A number of serious accidents occurred which, as later shown by L. Wöhler’s investigations were caused mainly by crystal fractures. Following a fatal accident during the manufacture of lead azide in the Chemisch-technische Reichsanstalt in Berlin, these experiments which were subject to secrecy were abandoned for the time being.

 

1900

Tests for the production of non-rusting, i.e. potassium chlorate-free priming compositions. The Swiss major Ziegler succeeded in creating the first “non-rusting percussion cap” by using barium nitrate as oxidising agent.

 

1900

Wöhler and Bielefeldt simultaneously replaced part of the fulminating mercury in blasting caps by a nitro body. Two-part design of a blasting cap (“safety blasting caps”) with a primary and secondary charge.

 

1905

Start-up of production of the Troisdorf igniting pellet in the blasting cap production plant at Troisdorf (“Züfa“ at Troisdorf, district Cologne) with a priming composition placed onto the electrically triggered incandescent bridge. In combination with a blasting cap, the form of the electrical fired detonator was thus developed for the first time.

 

1907

Wöhler and Matter carried out intensive investigations into azides and their use as initiating detonators (Wöhler’s patent for azides: D.R.P. 196 824).

 

From 1909 onwards

Beginning of the first industrial manufacture of azide blasting caps at Züfa, Troisdorf, using dextrinated lead azide.

 

1911

Beginning of production of the explosive tetryl at Züfa, Troisdorf.

 

1914

Edmund Ritter von Herz is the first to produce the neutral lead salt of trinitroresorcinol (trizinate, lead trizinate) and proposed this substance for use as initiating explosive.

 

1919

Edmund Ritter von Herz obtains a patent (D.R.P. 373 426) for the use of diazodinitrophenol as initiating explosive.

 

1920

Edmund Ritter von Herz obtains a patent (D.R.P. 391 427) for the use of diazopolynitropolyhydroxybenzenes and their salts (“diazinates“) as initiating explosive.

 

1920

Hans Rathsburg obtains a patent (D.R.P. 356 398) for the use of dinitrobenzofuroxane and its salts (“benzanates“) as initiating explosive.

 

1921

Hans Rathsburg Hans Rathsburg proposes tetrazene as primary explosive and sensitiser (high friction and impact sensitivity).

 

From 1921
onwards

Introduction of the Al shell in blasting cap manufacture by Wilhelm Eschbach (Züfa, Troisdorf) and use of a highly flame-sensitive initiating charge consisting of 70% lead azide and 30% lead trizinate.

 

1922

Introduction of the patented “Eschbach detonator “ as electrically triggered delay detonator without igniter cord.

 

From 1923
onwards

W. Eschbach develops the brisance or “Briska caps” in which a highly compacted explosive with a high shattering power (usually tetryl) is used as secondary charge. Further development and incorporation of a solid delay element into the electrical blasting cap.

 

1928

Edmund Ritter von Herz files a patent (D.R.P. 571 219) on the production of a blasting cap free from primary explosives.

 

From 1928
onwards

Hans Rathsburg and Edmund Ritter von Herz obtain a patent (D.R.P. 518 885) for a universally employable and non-rusting priming composition for use in peripheral and central firing ammunition. This composition is first produced in series on an industrial scale at the Stadeln plant of DNAG (Dynamit Nobel AG) at Fürth (Bavaria) and given the trade name “SINOXID“.

 

1929

Josef Meißner, Cologne, develops a process for the continuous production of lead azide and trizinate (D.R.P. 514 012).

 

1931

Edmund Ritter von Herz synthesis for the first time 5-nitrotetrazol and a series of its heavy metal salts (e.g. mercury-5-nitrotetrazolate) and files a patent for this high performance initiating explosive (D.R.P. 562 511).

 

1932

Introduction of a new patented gas-free and electrically triggered detonator by W. Eschbach, Züfa Troisdorf (gas free Eschbach ignitor).

 

Around 1935

The British navy introduces for the first time a DDT (Deflagration to Detonation Transition) detonator free from primary explosive for the navy A.P. (Armour Piercing) shell. This system consisted of a highly contained tubular tetryl charge which was fired with black gunpowder.

 

Around 1940

Introduction of a multiple layer igniting pellet which contained, in the first layer which is consequently in contact with the incandescent bridge, a thermal pyrotechnic mixture (“first fire”) with a particularly rapid response.
This mixture suspended in nitrocellulose lacquer consisted of either 90% lead picrate and 10% silicon or of 77% lead picrate, 18,5% cerium magnesium alloy (“mixed metal”) and 4.5% charcoal powder. These fuseheads (A ignitors) consisted of up to three layers differing in their composition.

 

Around 1943

Development of the EBW (Exploding Bridge Wire) detonator by Luis Alvarez as part of the Manhattan project in the U.S.A.

 

1950 - 1960

In the U.K., the use of stray current secured and primary explosives-free DDT detonators is investigated intensively. This work was carried out mainly by the A.R.D.E..(Armament Research and Development Establishment) military research institutes at Fort Halstead, Sevenoaks, Kent and at times also by E.R.D.E. (Explosives Research & Development Establishment) in Waltham Abbey, Essex, under the guidance of M. Griffiths, H. Rowson and T.H. Quarry. This basic development work was classified as “confidential“ by the MOD, London, and consequently not published.
Part of this work was later continued in the U.S.A. by R. H. Dinegar et. al. in the Los Alamos Labs, New Mexico, published in the form of several reports and a patent was filed for it (U.S. 4316412 of 1982).

 

Around 1960

At the Züfa laboratory at Troisdorf, research is carried out under the guidance of Dr. Prasnick for new and non-colloidal crystal modifiers for an improved production of lead azide. This work finally led to a process for the production of o.d. lead “azide“ (o.d. = without dextrin), by means of which a non-hygroscopic, almost bead-shaped product with a purity of up to 99% can be produced.

 

1965

Development of the slapper or EFI (Exploding Foil Initiator) detonator by John Stroud at the Lawrence Livermore National Laboratory, U.S.A.

 

From 1970
onwards

The Swedish company Nitro Nobel AB markets for the first time the non-electric detonator system NONEL for use in industrial blasting technology. The NONEL method is a push pipe system which is based on the development work of Pers Anders Persson.

 

1971

At the Stadeln plant of DNAG near Fürth, metal layer detonators with an insulating body of glass or ceramic and a layer ignition bridge of tantalum/tantalum nitride are produced for the first time on the basis of development work carried out by Uwe Brede, Heinz Gawlick and Peter Röh.

 

1970 - 1977

At the British E.R.D.E. (Explosives Research & Development Establishment) at Waltham Abbey, Essex intensive but finally unsuccessful research is carried out under the guidance of J. M. Jenkins and J. R. White into new substitutes for lead azide. However, this work leads to a basic improvement of the synthesis of mercury and silver salts of 5-nitrotetrazol. (U.S. 4094879 of 1978).
Similar work which deals with the improved preparation of mercury 5-nitrotetrazol is carried out in the U.S.A. by W. Gilligan and M. Kamlet at NSWC (Naval Surface Weapons Centre) at Silver Spring, Maryland.

 

1978 - 1979

In the development laboratory of DNAG Stadeln at Fürth, Bavaria, development work was started on the basis of the initiating work carried out by Werner Siegelin and Wolfgang Spranger by the two chemists Rainer Hagel and Klaus Redecker on atoxic, i.e. lead-free and barium-free priming compositions for hand-fired ammunition. As a result of the improvement of analytical methods (e.g. introduction of AAS in routine analysis), the background to this work consisted of industrial medical investigations in the U.S.A. into stand and supervisory personnel of covered shooting ranges operated by the authorities. In this case, very high lead values were in some cases detected in the blood which could be reduced only slightly by an improved the suction filter system and complete jacketing of the bullet. The main source of lead emission was the trizinate used in conventional SINOXID percussion.
This work was successfully completed in 1979 with the introduction of the “SINTOX” percussion cap (DE 2952069 of 1979).


From 1980
onwards

Introduction of the NME detonator (non-mass explosive) by DNAG, Cologne, using an 88% “o. D. lead azide“ (without dextrin) which was introduced into a separate protection shell. Delivery of the first noxious substance-reduced “SINTOX” ammunition worldwide in the 9 mm calibre Parabellum to the German police by the Stadeln plant of DNAG.


From 1987
onwards
In 1987, U.S. Patent 4,708,060 for the Semiconductor Bridge (SCB) Initiator was issued to R.W Bickes, Jr. and A.C. Schwarz employees of Sandia National Laboratories/USA. When initiated by a very low-current impulse, the polysilicon-defined bridge bursts into plasma discharge rapidly transporting a high flow of energy into the surrounding explosive/pyrotechnical mixture. The special characteristic of this polysilicon-on-silicon layered igniter is a relatively short response time of a few tens of microseconds. SCB igniters offer a high insensitivity to electrostatic discharge and transient currents. SCBs are manufactured by SCB Technologies, Inc. in Albuquerque NM, USA.
From 1993
Official approval of the electronic DYNATRONIC detonator system of Dynamit Nobel AG, Cologne (Troisdorf). The basis of this technology consisted of the development work carried out on the military detonator electronics for the antitank mine 2 (TA2).