GB2313371A

GB2313371A - A high temperature stable, low input energy primer/detonator

Info

Publication number: GB2313371A
Application number: GB9007635A
Authority: GB
Inventors: Coodly P Ramaswamy
Original assignee: Breed Automotive Technology Inc
Current assignee: Breed Automotive Technology Inc
Priority date: 1990-04-04
Filing date: 1990-04-04
Publication date: 1997-11-26
Anticipated expiration: 2010-04-04
Also published as: CA2014123C; GB9406458D0; GB9007635D0; CA2014123A1; GB2313371B

Abstract

A method for the manufacture of primers/detonators with 90-99.99% reliability and achieving high sensitivity , able to withstand temperatures within the range of -40{C to 200* superscript 0 *C and able to withstand temperature cycling and humidity for 95% RH at 95* superscript 0 *C to -40{C involves the use of mechanical and chemical sensitizers in lieu of tetracene, the utilization of oxidizers as sensitizers, the utilization of high energy fuels, and a method of co-precipitating the primary explosive and mechanical sensitizer. A primer initiating composition may comprise potassium chlorate, antimony sulfide, glass powder, lead thiocyanate and a material selected from sulphur, selenium, titanium and zirconium.

Description

A HIGH TEMPERATURE STABLE. LOW INPUT ENERGY PRIMER/DETONATOR Backaround of the Invention The invention relates to a method of manufacturing primers/detonators stable at high temperatures up to 100'C or better, having an all-fire impact sensitivity of 1.0 inch-oz or less, and high degree of reliability.

The invention more particularly relates to the development of a primer/detonator, which can function with a very high degree of reliability at temperatures as low as -4OC, as high as 100'C or better, and function equally well at ambient temperatures, and should have an all-fire sensitivity to impact of 1 inch-oz or less in the aforementioned temperature range.

The explosive industry uses a variety of primers/detonators.

Basically these devices consist of a primary explosive component initiated by stab (friction) or impact, an intermediate explosive composition to be set-off by the primer composition, and a base charge of secondary explosive like RDX or HMX to give the desired output to perform work, which may be to set off another explosive device in the ignition train. One of the common low input energy primers/detonators is an M55 Detonator, which is extensively used in ordnance for anti-personnel and anti-vehicular munition systems. The make up of these detonators consist of: (a) A primary explosive composition containing basic lead styphnate, dextrinated lead azide, antimony sulfide, barium nitrate, and tetracene.

(b) An intermediate explosive charge of RD 1333 lead azide.

(c) RDX as secondary explosive.

These detonators/primers are set-off by stab action with a firing pin and show a sensitivity of about 0.80 inch-oz at 99.998 reliability and 95% confidence level. In this detonator system, while basic lead styphnate and dextrinated lead azide fill their role as the main primary explosives, barium nitrate fills the role as a supplier of oxygen to the system and the antimony sulfide as a fuel cum mechanical sensitizer, because of its hih melting point. But it is tetracene that plays a unique and important role. It is a chemical sensitizer with the unique property that makes the system function at an input sensitivity or energy below 1 inch-oz.

While tetracene is an excellent sensitizer and one of the best which explosive chemists have developed, its inherent weakness is that when temperatures higher than 85 C are encountered, the primers begin to fail. With heat aging above 85 C, the tetracene begins to decompose and leak out from the primer. Sensitivity starts to decrease at 95 C, after 100 hours, the impact energy required will be increased by at least a factor of 3.

While there are many applications for primers/detonators that would function reliably at temperatures of 100-C or higher (like high cycle firing machine guns), a civilian application is in the automobile crash air bags used in motor vehicles for protecting occupants in crashes. In self-contained air bag modules involving mechanical sensors, the primers are used to ignite the propellant system, which then generates the gas to inflate the air bag. The industry standards demand that air bag systems function reliably at as high a temperature as 100it; and at the same time function equally reliably at -40iC. Also, industry standards demand that they function with a high degree of reliability and have a long shelf life.

The operating parameters expected for primers/detonators to fulfill the aforesaid, as well as similar requirements can be summed up as follows: (i) The composition used in the primer should be easy to manufacture and capable of loading in automatic industry machines used for manufacture of primers/detonators.

(ii) They should be safe for handling, particularly in systems using lead styphnate, where protection against static electricity may be an important safety factor.

(iii) They should be thoroughly stable at temperatures as high as TOO'C and should function reliably at temperatures as low as -40-C.

(iv) In systems using stab action energy to set off the system, the all-fire energy required for setting off the system should be 1 inch-oz or less, similar to those required for primers using tetracene as the sensitizer, where the all-fire sensitivity value is calculated statistically to 99.99% reliability and 95% confidence level for the entire population.

Summarv of the Invention A principal object of the present invention is to provide conditions of assembly and, make up of detonators for the production of primers/detonators, with a high sensitivity to stab action and a high degree of reliability.

Another object is to eliminate tetracene with its inherent limitation of decomposing at temperatures higher than 85'C and provide a method to use mechanical sensitizers like sand, glass powder, or carborundum in primer mixes to improve both sensitivity to impact and temperature aging.

A further object is to provide a method of the foregoing type with a method to co-precipitate the mechanical sensitizer with an explosive to improve homogeneity and sensitivity.

Still another object is to provide a composition using a powerful oxidizer like potassium chlorate as a sensitizer.

Still another object is to provide a composition, eliminating primary explosives like azide and styphnate and using oxidizers and fuels like potassium chlorate and antimony sulfide, in combination with a mechanical and chemical sensitizer, to achieve a high degree of sensitivity, reliability, and temperature aging properties.

Another important object is to improve the primers of the foregoing type to withstand very high temperature by using high energy fuels like selenium and titanium.

Still another important object is to provide a method of manufacturing detonators with a high degree of reliability at 90%-99.99% reliability and 95% confidence level, and achieve primers/detonators of sensitivity 0.8 inch-oz. to 3.0 inch-oz., having temperature aging properties that would retain sensitivity from -40 C to 2000C and capable of standing temperature cycling and humidity from 95% RH at 950C to -400C.

The above operating parameters may be achieved according to the invention by eliminating tetracene with its inherent limitation of decomposing at temperatures higher than 850C, and replacing it wit mechanical sensitizers, or by developing an entirely different composition system, using ingredients which are highly stable at the temperatures for which the system is being designed.

Other objectives and advantages of the invention will become more apparent to those skilled in the art, as the invention is disclosed in the examples given below: Detailed Ascription EXAMPLE 1 Primer Initiating Composition Basis Lead Styphnate - 40 - 42% )use 15-25 Lead Azide - 20 - 22% )milligrams and Antimony Sulfide - 15 - 20% )consolidate at Barium Nitrate - 15 - 20% ) 70-100 Kpsi Carborundum - 1 - 3% Intermediate charges and the base charge could be varied from the standard intermediate lead azide and base charges like PETN, RDX, or HMX to less powerful output charges, like a mixture of basic lead styphnate, barium nitrate and antimony sulfide or titanium-potassium perchlorate or zirconium-potassium perchlorate.

Detonators assembled as above and initiated by a standard firing pin would stand aging at 100*C and would give a sensitivity of 2-3 inch-oz at 99% reliability and 95% confidence level.

EXAMPLE II Similar to Example I, but replacing carborundum with ground glass powder or pure silica sand-like ottawa sand and in the same sieve size spectrum as for carborundum in Example I and with output charge as desired. Weight of charge and consolidation pressures also as in Example I, would give primers with a sensitivity of 2-3 inch-oz at 90% reliability and 95% confidence level.

EXAMPLE III The reliability of mixing mechanical sensitizers like carborundum, sand and glass powder could be very much improved and thus improve the overall reliability by encapsulating the sensitizer into the primary explosive by co-precipitating the primary explosive and the mechanical sensitizer. As an example, the lead styphnate and mechanical sensitizer like carborundum, sand, or glass powder could be co-precipitated in the proportion they would be present in the final composition. The method of preparation would be as follows: A solution of magnesium styphnate is prepared by neutralizing styphnic acid with magnesium oxide, filtering off the excess magnesium oxide. The mechanical sensitzer is suspended in the magnesium styphnate solution in the proportion it exists in the final mixture. Lead nitrate or lead acetate solution is run down into the mixture of magnesium styphnate and mechanical sensitizer, which is kept stirred at 50*C. The co-precipitated lead styphnate mechanical sensitizer is cooked at 509C for a further period of 10 minutes, filtered washed thrice with distilled water, and used in making the primer composition.

Primer/detonator made up with the above co-precipitated mix and in a manner similar to that in Example I, improves uniformity and gives a primer with a sensitivity of 3-3.5 inch-oz at 99.99% reliability and a 95% confidence level.

EXAMPLE IV The mix in Example I could be sensitized by using a more powerful oxidizer in place of tetracene. A typical mix made with the following composition: Lead Styphnate - 40% Lead Azide - 20% Antimony Sulfide - 15% Barium Nitrate - 20% Potassium Chlorate - 5% The composition in Example IV can be used in place of the primary mix in Example I and primers/detonators made as in Example I, using 25 mgms of the primer composition, consolidated at 100 K.psi gives detonators/primers with a sensitivity of 3.1 inch-oz at 99.99% reliability and 95% confidence level.

EXAMPLE V A completely new approach is by going away from the conventional primary explosives and still achieve a high degree of sensitivity. This is achieved by using a combination of mechanical and chemical sensitizers. A typical example of such a type is: Potassium Chlorate - 35 - 37% Antimony Sulfide - 52 - 56% Glass Powder - 2 - 3% Sulfur - 3 - 4% Lead Thiocyanate - 4 - 6% The detonator/primer made using the above primary mix, using 15-25 mgms of the mix pressed at 70-100 Kpsi, has an all-fire stab sensitivity of 0.80 inch-oz at 99.99% reliability and 95% confidence level. The base charge could be varied to suit the output desired. Its functionally reliable after aging both at 40 C and 100 C for extended periods, without any significant loss in sensitivity.

EXAMPLE VI The sulfur in Example V can be substituted with high energetic fuels like selenium, titanium, or zirconium. They would maintain the sensitivity and at the same time allow them to be used up to 200"C without loss in sensitivity.

The scope and ambit of the invention is not limited to the materials, conditions of processing, and assembly of the primer/detonator mentioned. As an example, co-precipitating the lead azide and lead styphate in the proportion it exists in the composition would achieve a higher degree of sensitivity or replace part of the oxidizer in Examples I to III with a more powerful oxidizer like potassium chlorate. Judicious combination of the ingredients could lead to higher sensitivity and higher output. Similarly, newer designs of the firing pin with more acute included angle from 26 used in standard pin up to 14 and also more edges on the pins to develop more hot spots for initiation would make the system function at lesser impact energy.

Thus, the several aforementioned objects and advantages are most effectively attained by the invention which has important application in the ordinance, automobile crash air bag and other fields having need for primers/detonators. Although several embodiments have been disclosed in detail herein, it should be understood that this invention is in no sense limited thereby.

Claims

1. A composition eliminating primary explosives suc as azide and styphnate, and comprised of oxidizers and fuels used in combination with a sensitizer to achieve a high degree of sensitivity, reliability, and temperature aging properties.

2. A method of forming a primer initiating composition comprising basic lead styphnate, lead azide, antimony sulfide, barium nitrate, and a mechanical sensitizer, preferably comprising one or more of carborundum, ground glass powder or pure silica sand, more especially carborundum, using preferably 15-25 mgms.

of the said composition as the Primary charge and consolidating preferably at 70-100 kpsi.

3. A method as claimed in Claim 2, wherein the primer initiating composition is assembled in a detonator/ primer capable of withstanding aging within the temperature range of from -400C to 1000C and providing a sensitivity which is preferably of 2 to 3 inch - ozs. at 99.99% reliability and 95% confidence level.

4. A method as claimed in Claim 2, wherein a relatively less powerful output charge is coupled with the primer, the output charge being a mixture selected from the group of materials consisting of basic lead styphnate, barium nitrate and antimony sulfide.

5. A method as claimed in Claim 2, wherein a relatively less powerful output charge is coupled with the primer, the output charge being selected from a group of material consisting of titanium-potassium perchlorate and zirconium-potassium perchlorate.

6. A method as claimed in any one of Claims 2 to 5, wherein the mechanical sensitizer is ground glass powder.

7. A method as claimed in any one of Claims 2 to 5, wherein the mechanical sensitizer is pure silica sand.

8. A method as claimed in any one of Claims 2 to 5, wherein potassium chlorate is used as a sensitizer, preferably in lieu of the carborundum or other mechanical sensitizer and the mixture is consolidated preferably at 100 kpsi.

9. A composition substantially as described in Example I or Example II herein.

9. A method of improving the overall reliability of the primer/detonator by encapsulating a sensitizer into a primary explosive by co-precipitating the primary explosive and a sensitizer.

10. A method of mixing a mechanical sensitizer with a primary explosive by co-precipitating said sensitizer and explosives in the proportion they are present in the final composition by the following method: a. preparing a solution of magnesium styphnate by neutralizing styphnic acid with magnesium oxide, filtering off the excess magnesium oxide; b. suspending the mechanical sensitizer in the magnesium styphnate solution in the proportion it exists in the final composition; and c. adding solutions selected from the group consisting of lead nitrate and lead acetate to the mixture of magnesium styphnate and the mechanical sensitizer, stirring and heating, preferably at 500C, preferably for 10 minutes.

11. A method of forming a primer initiating composition comprising potassium chlorate, antimony sulfide, a mechanical sensitizer preferably comprising one or more of carborundum, silica sand or glass powder, more especially glass powder, a fuel comprising one or more of sulfur and a high energy fuel such as selenium, titanium or zirconium, more especially sulfur, and lead thiocyanate, using preferably 15-25 mgms of the mix consolidated preferably at 70-100 kpsi as the primer charge.

12. A method as claimed in Claim 11, wherein the fuel is a high energy fuel.

13. A method as claimed in Claim 11, wherein the fuel is selenium.

14. A method as claimed in Claim 11, wherein the fuel is titanium.

15. A method as claimed in Claim 11, wherein the fuel is zirconium.

16. A consolidated mixture of a primer initiating composition comprising basic lead styphnate, lead azide, antimony sulfide, barium nitrate, and a material selected from the group consisting of carborundum, ground glass powder, pure silica sand and potassium chlorate.

17. A consolidated mixture of a primer initiating composition comprising potassium chlorate, antimony sulfide, glass powder, lead thiocyanate and a material selected from the group consisting of sulfur, selenium, titanium and zirconium.

18. A method as claimed in Claim 2, wherein the primer initiating composition is assembled in a detonator/ primer capable of withstanding aging within the temperature ranging from -400C to 2000C and providing sensitivity of preferably 0.80 inch-oz. at 99.99% reliability and 95% confidence level.

19. A composition as claimed or referred to in any one of Claims 1 to 18, which is free of tetracene.

20. A composition substantially as described in any one of Examples I to VI herein.

21. Any novel feature or novel combination of features disclosed herein.

AMENDMENTS '1 MS HAVE BEEN FILED AS FOLLOWS: 1. A method of forming a primer initiating composition comprising potassium chlorate, antimony sulfide, a mechanical sensitizer preferably comprising one or more of carborundum, silica sand or glass powder, more especially glass powder, a fuel comprising one or more of sulfur and a high energy fuel such as selenium, titanium or zirconium, more especially sulfur, and lead thiocyanate, using preferably 15-25 mgms of the mix consolidated preferably at 70-100 kpsi as the primer charge, the composition being free of tetracene and the consolidated mixture being capable of being assembled in a detonator/primer capable of withstanding aging within the temperature range -40 C to 100 C and providing sensitivity of 0.8 inch-oz. to 3.5 inch-oz. at 90%-99% reliability and 95% confidence level.

2. A method as claimed in Claim 1, wherein the fuel is a high energy fuel.

3. A method as claimed in Claim 1, wherein the fuel is selenium.

4. A method as claimed in Claim 1, wherein the fuel is titanium.

5. A method as claimed in Claim 1, wherein the fuel is zirconium.

6. A consolidated mixture of a primer initiating composition comprising potassium chlorate, antimony sulfide, glass powder, lead thiocyanate and a material selected from the group consisting of sulfur, selenium, titanium and zirconium, the consolidated mixture being free of tetracene and being capable of being assembled in a detonator/primer capable of withstanding aging within the temperature range -40 C to 100or and providing sensitivity of 0.8 inch-oz. to 3.5 inch-oz. at 90%-99.99% reliability and 95% confidence level.

7. A consolidated mixture as claimed in Claim 6 or a method as claimed in Claim 1, wherein the detonator/primer is capable of withstanding aging within the temperature range -40 C to 200 C.

8. A consolidated mixture as claimed in Claim 6 or Claim 7, or a method as claimed in Claim 1, wherein the detonator/primer provides sensitivity of 0.8 inchoz. to 3.0 inch-oz. at 90%-99.99% reliability and 95% confidence level.