EP0070932A2 - Initial-Explosivstoff für Zünder und Verfahren zu dessen Herstellung - Google Patents
Initial-Explosivstoff für Zünder und Verfahren zu dessen Herstellung Download PDFInfo
- Publication number
- EP0070932A2 EP0070932A2 EP81303418A EP81303418A EP0070932A2 EP 0070932 A2 EP0070932 A2 EP 0070932A2 EP 81303418 A EP81303418 A EP 81303418A EP 81303418 A EP81303418 A EP 81303418A EP 0070932 A2 EP0070932 A2 EP 0070932A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- lead
- styphnate
- azide
- solution
- initiatory
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002360 explosive Substances 0.000 title claims abstract description 18
- 230000000977 initiatory effect Effects 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims description 13
- 150000001540 azides Chemical class 0.000 claims abstract description 33
- 239000013078 crystal Substances 0.000 claims abstract description 24
- WETZJIOEDGMBMA-UHFFFAOYSA-L lead styphnate Chemical compound [Pb+2].[O-]C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C([O-])=C1[N+]([O-])=O WETZJIOEDGMBMA-UHFFFAOYSA-L 0.000 claims abstract description 24
- 229940046892 lead acetate Drugs 0.000 claims abstract description 16
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003607 modifier Substances 0.000 claims abstract description 9
- 239000004375 Dextrin Substances 0.000 claims abstract description 8
- 229920001353 Dextrin Polymers 0.000 claims abstract description 8
- 235000019425 dextrin Nutrition 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 6
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- 239000002178 crystalline material Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 43
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000037452 priming Effects 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 description 8
- 230000003068 static effect Effects 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- IXHMHWIBCIYOAZ-UHFFFAOYSA-N styphnic acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C(O)=C1[N+]([O-])=O IXHMHWIBCIYOAZ-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- AGUIVNYEYSCPNI-UHFFFAOYSA-N N-methyl-N-picrylnitramine Chemical group [O-][N+](=O)N(C)C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O AGUIVNYEYSCPNI-UHFFFAOYSA-N 0.000 description 2
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000000026 Pentaerythritol tetranitrate Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- NVYSURDBVCQFBV-UHFFFAOYSA-L magnesium;2,4,6-trinitrobenzene-1,3-diolate Chemical compound [Mg+2].[O-]C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C([O-])=C1[N+]([O-])=O NVYSURDBVCQFBV-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229960004321 pentaerithrityl tetranitrate Drugs 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B35/00—Compositions containing a metal azide
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0008—Compounding the ingredient
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B41/00—Compositions containing a nitrated metallo-organic compound
- C06B41/02—Compositions containing a nitrated metallo-organic compound the compound containing lead
- C06B41/08—Compositions containing a nitrated metallo-organic compound the compound containing lead with a metal azide or a metal fulminate
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
- C06C7/00—Non-electric detonators; Blasting caps; Primers
Definitions
- This invention relates to detonators for explosives and is concerned with an initiatory explosive (also known as a primary explosive) suitable for use in such detonators and a method of preparing it.
- an initiatory explosive also known as a primary explosive
- Detonators for explosives normally consist of a metal tube closed at one end and containing a base charge of a highly brisant explosive, for example PETN (an abbreviation for pentaerythritol tetranitrate), Tetryl (2,4,6-trinitrophenyl methyl nitramine) or RDX (1,3,5-trinitro-1,3,5-triazacyclohexane), on.which is disposed a smaller sensitive priming charge composed ' of an initiatory explosive which can be set off, for example, by a spark from an electrically ignited fusehead or by heat or flame from a safety fuse.
- a highly brisant explosive for example PETN (an abbreviation for pentaerythritol tetranitrate), Tetryl (2,4,6-trinitrophenyl methyl nitramine) or RDX (1,3,5-trinitro-1,3,5-triazacyclohexane)
- ASA an abbreviation for a mixture of lead azide (Pb(N 3 ) 2 ), lead styphnate (lead 2,4,6-trinitro-resorcinate) and aluminium).
- ASA normally contains about 70 parts by weight of the lead azide, about 30 parts by weight of the lead styphnate and about 2.5 percent by weight (of the ASA) of fine light aluminium powder.
- Lead styphnate is mixed with lead azide to combine the desirable properties of flame sensitiveness of lead styphnate and the high disruptive power of lead azide.
- Lead azide by itself has just an acceptable level of flame sensitiveness if its purity is more than 98%. However, such a pure lead azide is relatively more sensitive to friction and impact and is more hazardous to manufacture and handle. Pure lead.azide is used in military explosives where the disruptive power of the material is required to be as high as possible.
- Commercial lead azide is manufactured using hydrophilic colloids such as dextrin, gelatin, or carboxymethyl cellulose as desensitisers and crystal habit modifiers. These reduce the purity of lead azide to about 95% but render it safer to handle. Such lead azide is however not adequately sensitive to ignition from a safety fuse and therefore cannot be used for ordinary non-electric detonators.
- Lead styphnate is much more flame sensitive than lead azide. Its disruptive power is however lower. It suffers from another serious drawback in that it is not only highly prone to static electrification during its handling in the dry state, but it is also capable of being fired at very low levels (140 ergs) of static electrical energy. Handling of dry lead styphnate is therefore hazardous and accidents are quite frequent in filling operations. When lead styphnate is mixed with lead azide in the manufacture of ASA mixture, the resultant mixture also has similar hazards of static electrification and firing by low level static electrical energy.
- a method of preparing an initiatory explosive comprising lead azide and lead styphnate, which comprises bringing into contact an aqueous solution of lead acetate and an aqueous solution of a water-soluble styphnate and sodium azide in the presence of at least one crystal habit modifier so as to cause the solutions to react and thereby form a precipitate which is a homogeneous crystalline material composed of isogonous mixed crystals of lead azide and lead styphnate.
- the precipitation conditions are such as to produce both lead azide and lead styphnate in the same crystal habit capable of forming isogonous or mixed crystals.
- the special feature of this invention is the homogeneity of the intergrown crystals which have the appearance of a single species irrespective of the proportions of the constituent lead azide and lead styphnate present in the material.
- a solution containing lead acetate and a solution containing a water-soluble styphnate and sodium azide are introduced simultaneously into a reactor vessel in carefully controlled concentrations.
- Available free alkali required during the reaction may be provided by adding an appropriate amount of basic lead acetate to the lead acetate solution.
- the alkali may be provided by addition to the azide/styphnate solution of potassium hydroxide. Control of available alkalinity is, however, better if it is in the form of basic lead acetate.
- the water-soluble styphnate may be potassium styphnate, magnesium styphnate or ammonium styphnate and may be prepared in situ by reaction of styphnic acid with an appropriate base, e.g. potassium hydroxide or aqueous ammonia.
- an appropriate base e.g. potassium hydroxide or aqueous ammonia.
- the crystal habit modifier may be incorporated in the lead acetate solution and/or in the azide/ styphnate solution, and/or may be present in the reactor vessel into which the two solutions are introduced. Thus two or more different modifiers can be employed if desired.
- suitable crystal habit modifiers for use in the present invention are dextrin and carboxymethyl cellulose.
- the pH of the reacting solutions (which will generally be approximately neutral, i.e. 6.5 to 7.5, when basic lead acetate is used to control the available free alkali) is controlled and crystal habit modifiers are added to ensure that isogonous mixed crystals of lead azide and lead styphnate are formed, resulting in a uniform free flowing product without much crystal debris or dust.
- the amount of lead styphnate precipitated together with lead azide will depend on the free alkali available during the reaction and hence can be controlled by varying either the quantity of basic lead acetate added to the lead acetate solution or the quantity of potassium hydroxide added to the azide/ styphnate solution.
- a large variety of products useful as initiatory explosives is thus possible.
- a styphnate content of 20% to 30% is generally aimed at in the final product, to ensure both adequate disruptive power and flame sensitiveness.
- the initiatory explosive prepared in accordance with the invention is designated as LSA.
- LSA prepared in accordance with the invention has adequate flame sensitiveness for firing either by a safety fuse or by an electric fusehead. It does not develop significant or dangerous levels of static charge during handling and the level of energy in terms of a static charge required to fire the material is very much higher than that needed for ASA. LSA is also quite satisfactory as regards its sensitiveness to friction and mechanical impact as shown in the following table:-
- LSA can be used by itself as a priming charge in detonators and there is no necessity to mix it with aluminium powder, or graphite or anti-static agents.
- LSA made according to this invention is thus considerably superior to ASA in regard to ease of manufacture, safety in handling and homogeneity without in any way detracting from the performance characteristics desired for an initiatory explosive for electric and non-electric detonators.
- a solution of lead acetate (100 g/l) was prepared with distilled or deionised water. The pH of the solution was 5.5 to 5.9. To 10 litres of this solution, 500 ml. of a dextrin solution (15% W/V) in water were added.
- a solution of sodium azide (25 g/l)was prepared in distilled or deionised water. To 10 litres of this solution, 75 g. of solid potassium hydroxide were added followed by 84 g. of dry styphnic acid. The resulting solution was stirred until all the styphnic acid had dissolved. The free alkali (calculated as potassium hydroxide) in the final solution was 2.5 - 2.8 g/l. 350 ml. of an aqueous solution (1.5% W/V) of carboxymethyl cellulose were then added.
- a solution of lead acetate (250 g/1) was prepared in distilled or deionised water.
- the pH of the solution was between 5.5 and 5.9.
- To 5 litres of this solution were added 235 ml. of an aqueous dextrin solution (15% W/V) and 700 ml, of an aqueous basic lead acetate solution (20% W/V).
- the pH of the final solution was between 6.5 and 7.3.
- a solution of sodium azide (86 g/1) was prepared in distilled or deionised water. To 5 litres of this solution were added 180 ml. of ammonia solution (25% W/V) followed by 150 g. of dry styphnic acid. The resulting solution was stirred until all the styphnic acid had dissolved. Ammonia if present in excess (as detected by smell) was removed by warming. The solution was then cooled and 600 ml. of an aqueous solution (3% W/V) of carboxymethyl cellulose were added. The pH of the final solution was adjusted to between 7 and 7.3 with ammonia or acetic acid.
- the precipitation was carried out as described in Example 1 using 300 ml. of an aqueous solution of dextrin, 3.4 litres of solution A and 3.2 litres of solution B. The contents of the precipitation vessel were then allowed to cool to ambient temperature and to settle. The resulting precipitated crystals were washed in the vessel with water three times, with decantation in between washings. The resulting product was then sieved through a 52 mesh sieve, filtered and dried.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Air Bags (AREA)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT81303418T ATE12385T1 (de) | 1981-07-24 | 1981-07-24 | Initial-explosivstoff fuer zuender und verfahren zu dessen herstellung. |
| EP81303418A EP0070932B1 (de) | 1981-07-24 | 1981-07-24 | Initial-Explosivstoff für Zünder und Verfahren zu dessen Herstellung |
| DE8181303418T DE3169539D1 (en) | 1981-07-24 | 1981-07-24 | Initiatory explosive for detonators and method of preparing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP81303418A EP0070932B1 (de) | 1981-07-24 | 1981-07-24 | Initial-Explosivstoff für Zünder und Verfahren zu dessen Herstellung |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0070932A2 true EP0070932A2 (de) | 1983-02-09 |
| EP0070932A3 EP0070932A3 (en) | 1983-10-05 |
| EP0070932B1 EP0070932B1 (de) | 1985-03-27 |
Family
ID=8188358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP81303418A Expired EP0070932B1 (de) | 1981-07-24 | 1981-07-24 | Initial-Explosivstoff für Zünder und Verfahren zu dessen Herstellung |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0070932B1 (de) |
| AT (1) | ATE12385T1 (de) |
| DE (1) | DE3169539D1 (de) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8192568B2 (en) | 2007-02-09 | 2012-06-05 | Alliant Techsystems Inc. | Non-toxic percussion primers and methods of preparing the same |
| US8202377B2 (en) | 2007-02-09 | 2012-06-19 | Alliant Techsystems Inc. | Non-toxic percussion primers and methods of preparing the same |
| US8206522B2 (en) | 2010-03-31 | 2012-06-26 | Alliant Techsystems Inc. | Non-toxic, heavy-metal free sensitized explosive percussion primers and methods of preparing the same |
| US8282751B2 (en) | 2005-03-30 | 2012-10-09 | Alliant Techsystems Inc. | Methods of forming a sensitized explosive and a percussion primer |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8641842B2 (en) | 2011-08-31 | 2014-02-04 | Alliant Techsystems Inc. | Propellant compositions including stabilized red phosphorus, a method of forming same, and an ordnance element including the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB187012A (en) * | 1921-07-11 | 1922-10-11 | Edmund Von Herz | A process for the manufacture of detonating compositions for detonators or primers |
| DE1011337B (de) * | 1953-02-16 | 1957-06-27 | Ici Ltd | Verfahren zur Herstellung von Zuendmassen |
-
1981
- 1981-07-24 EP EP81303418A patent/EP0070932B1/de not_active Expired
- 1981-07-24 AT AT81303418T patent/ATE12385T1/de not_active IP Right Cessation
- 1981-07-24 DE DE8181303418T patent/DE3169539D1/de not_active Expired
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8282751B2 (en) | 2005-03-30 | 2012-10-09 | Alliant Techsystems Inc. | Methods of forming a sensitized explosive and a percussion primer |
| US8460486B1 (en) | 2005-03-30 | 2013-06-11 | Alliant Techsystems Inc. | Percussion primer composition and systems incorporating same |
| US8192568B2 (en) | 2007-02-09 | 2012-06-05 | Alliant Techsystems Inc. | Non-toxic percussion primers and methods of preparing the same |
| US8202377B2 (en) | 2007-02-09 | 2012-06-19 | Alliant Techsystems Inc. | Non-toxic percussion primers and methods of preparing the same |
| US8454770B1 (en) | 2007-02-09 | 2013-06-04 | Alliant Techsystems Inc. | Non-toxic percussion primers and methods of preparing the same |
| US8454769B2 (en) | 2007-02-09 | 2013-06-04 | Alliant Techsystems Inc. | Non-toxic percussion primers and methods of preparing the same |
| US8206522B2 (en) | 2010-03-31 | 2012-06-26 | Alliant Techsystems Inc. | Non-toxic, heavy-metal free sensitized explosive percussion primers and methods of preparing the same |
| US8470107B2 (en) | 2010-03-31 | 2013-06-25 | Alliant Techsystems Inc. | Non-toxic, heavy-metal free explosive percussion primers and methods of preparing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3169539D1 (en) | 1985-05-02 |
| EP0070932A3 (en) | 1983-10-05 |
| ATE12385T1 (de) | 1985-04-15 |
| EP0070932B1 (de) | 1985-03-27 |
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