AU784682B1 - Explosive compositions - Google Patents
Explosive compositions Download PDFInfo
- Publication number
- AU784682B1 AU784682B1 AU34652/89A AU3465289A AU784682B1 AU 784682 B1 AU784682 B1 AU 784682B1 AU 34652/89 A AU34652/89 A AU 34652/89A AU 3465289 A AU3465289 A AU 3465289A AU 784682 B1 AU784682 B1 AU 784682B1
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- Australia
- Prior art keywords
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- explosive
- composition
- per cent
- binder
- 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.)
- Expired
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- 239000000203 mixture Substances 0.000 title claims description 77
- 239000002360 explosive Substances 0.000 title claims description 54
- 239000011230 binding agent Substances 0.000 claims description 48
- 239000004698 Polyethylene Substances 0.000 claims description 27
- 229920000573 polyethylene Polymers 0.000 claims description 27
- 239000000945 filler Substances 0.000 claims description 23
- 229920002367 Polyisobutene Polymers 0.000 claims description 22
- -1 polyethylene Polymers 0.000 claims description 21
- 229920000642 polymer Polymers 0.000 claims description 21
- 229920003023 plastic Polymers 0.000 claims description 10
- 239000004033 plastic Substances 0.000 claims description 10
- 239000004014 plasticizer Substances 0.000 claims description 10
- 239000000446 fuel Substances 0.000 claims description 9
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 235000006708 antioxidants Nutrition 0.000 claims description 7
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000001993 wax Substances 0.000 claims description 6
- POCJOGNVFHPZNS-ZJUUUORDSA-N (6S,7R)-2-azaspiro[5.5]undecan-7-ol Chemical class O[C@@H]1CCCC[C@]11CNCCC1 POCJOGNVFHPZNS-ZJUUUORDSA-N 0.000 claims description 5
- 239000007822 coupling agent Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims 1
- 235000019808 microcrystalline wax Nutrition 0.000 claims 1
- 239000004200 microcrystalline wax Substances 0.000 claims 1
- 239000000463 material Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 239000004615 ingredient Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 101100083334 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) PIB2 gene Proteins 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- SNIOPGDIGTZGOP-UHFFFAOYSA-N Nitroglycerin Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- QUAMCNNWODGSJA-UHFFFAOYSA-N 1,1-dinitrooxybutyl nitrate Chemical compound CCCC(O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QUAMCNNWODGSJA-UHFFFAOYSA-N 0.000 description 2
- YSIBQULRFXITSW-OWOJBTEDSA-N 1,3,5-trinitro-2-[(e)-2-(2,4,6-trinitrophenyl)ethenyl]benzene Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1\C=C\C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O YSIBQULRFXITSW-OWOJBTEDSA-N 0.000 description 2
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 description 2
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 description 2
- VWSWIUTWLQJWQH-UHFFFAOYSA-N 2-butyl-6-[(3-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CCCCC1=CC(C)=CC(CC=2C(=C(CCCC)C=C(C)C=2)O)=C1O VWSWIUTWLQJWQH-UHFFFAOYSA-N 0.000 description 2
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000000028 HMX Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- BSPUVYFGURDFHE-UHFFFAOYSA-N Nitramine Natural products CC1C(O)CCC2CCCNC12 BSPUVYFGURDFHE-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- BJXXCOMGRRCAGN-XPWSMXQVSA-N [2,2-bis(hydroxymethyl)-3-[(e)-octadec-9-enoyl]oxypropyl] (e)-octadec-9-enoate Chemical compound CCCCCCCC\C=C\CCCCCCCC(=O)OCC(CO)(CO)COC(=O)CCCCCCC\C=C\CCCCCCCC BJXXCOMGRRCAGN-XPWSMXQVSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 2
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- POCJOGNVFHPZNS-UHFFFAOYSA-N isonitramine Natural products OC1CCCCC11CNCCC1 POCJOGNVFHPZNS-UHFFFAOYSA-N 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- UZGLIIJVICEWHF-UHFFFAOYSA-N octogen Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UZGLIIJVICEWHF-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- 239000000015 trinitrotoluene Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- RDLIBIDNLZPAQD-UHFFFAOYSA-N 1,2,4-butanetriol trinitrate Chemical compound [O-][N+](=O)OCCC(O[N+]([O-])=O)CO[N+]([O-])=O RDLIBIDNLZPAQD-UHFFFAOYSA-N 0.000 description 1
- ZQXWPHXDXHONFS-UHFFFAOYSA-N 1-(2,2-dinitropropoxymethoxy)-2,2-dinitropropane Chemical compound [O-][N+](=O)C([N+]([O-])=O)(C)COCOCC(C)([N+]([O-])=O)[N+]([O-])=O ZQXWPHXDXHONFS-UHFFFAOYSA-N 0.000 description 1
- LSLGCKBDVWXMSH-UHFFFAOYSA-N 1-[1-(2,2-dinitropropoxy)ethoxy]-2,2-dinitropropane;1-(2,2-dinitropropoxymethoxy)-2,2-dinitropropane Chemical compound [O-][N+](=O)C([N+]([O-])=O)(C)COCOCC(C)([N+]([O-])=O)[N+]([O-])=O.[O-][N+](=O)C(C)([N+]([O-])=O)COC(C)OCC(C)([N+]([O-])=O)[N+]([O-])=O LSLGCKBDVWXMSH-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- JSOGDEOQBIUNTR-UHFFFAOYSA-N 2-(azidomethyl)oxirane Chemical compound [N-]=[N+]=NCC1CO1 JSOGDEOQBIUNTR-UHFFFAOYSA-N 0.000 description 1
- MKWKGRNINWTHMC-UHFFFAOYSA-N 4,5,6-trinitrobenzene-1,2,3-triamine Chemical compound NC1=C(N)C([N+]([O-])=O)=C([N+]([O-])=O)C([N+]([O-])=O)=C1N MKWKGRNINWTHMC-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 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 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 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 1
- 239000000026 Pentaerythritol tetranitrate Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- LYAGTVMJGHTIDH-UHFFFAOYSA-N diethylene glycol dinitrate Chemical compound [O-][N+](=O)OCCOCCO[N+]([O-])=O LYAGTVMJGHTIDH-UHFFFAOYSA-N 0.000 description 1
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000001087 glyceryl triacetate Substances 0.000 description 1
- 235000013773 glyceryl triacetate Nutrition 0.000 description 1
- 229960003711 glyceryl trinitrate Drugs 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QCOXCILKVHKOGO-UHFFFAOYSA-N n-(2-nitramidoethyl)nitramide Chemical compound [O-][N+](=O)NCCN[N+]([O-])=O QCOXCILKVHKOGO-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229960004321 pentaerithrityl tetranitrate Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- JDFUJAMTCCQARF-UHFFFAOYSA-N tatb Chemical compound NC1=C([N+]([O-])=O)C(N)=C([N+]([O-])=O)C(N)=C1[N+]([O-])=O JDFUJAMTCCQARF-UHFFFAOYSA-N 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- AGCQZYRSTIRJFM-UHFFFAOYSA-N triethylene glycol dinitrate Chemical compound [O-][N+](=O)OCCOCCOCCO[N+]([O-])=O AGCQZYRSTIRJFM-UHFFFAOYSA-N 0.000 description 1
- IPPYBNCEPZCLNI-UHFFFAOYSA-N trimethylolethane trinitrate Chemical compound [O-][N+](=O)OCC(C)(CO[N+]([O-])=O)CO[N+]([O-])=O IPPYBNCEPZCLNI-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
- C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
- C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
- C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Molecular Biology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
CO0MMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION (Original) FOR OFFICE USE Class Int. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority: %elated Art: Name of Applicant: Address of Applicant: MEC 5YsTF-N& PLL.
Royal Ordnancc pie 5 Griff in Heuse The Gtran Leaden WC2w [;RR
-BNGLAD
car IkzA taVrle L-o ixoh SLA/1 Y9 0 ~0 Actual Inventor(s): .Address for Service: Deirdre HALLAM Ronald Edward HOLLANDS DAVIES COLLISON, Patent Attorneys# 1 Little Collins Street, Melbourne, 3000.
Complete specification for the invention entitled: "EXPLOSIVE COMPOSITIONSw Thie following statement is a full description of this invention, including the best method of performing it known to us 1- ROP0069 0@ 5 0 The present invention relates to explosive compositions, particularly plastic mouldable explosive compositions.
A known explosive composition manufactured by 5 the present Applicants, which composition has been in service use by the UK Ministry of Defence for many years comprises RDX, a particulate high explosive filler, incorporated in a binder which comprises liquid paraffin gelled to form a grease together with other minor additives. This composition is detonator sensitive (ie does not require a booster initiation) and is a plastic material which may be moulded like putty under light pressure by the user into a desired shape eg to fill a cavity or to line an edge between mating surfaces.
This known composition suffers from the problems that the low molecular weight liquid components of the binder tend to migrate causing the composition to become brittle during its service life, the low temperature (-20° 0
C)
mouldability of the material is poor and binder ingredients tend to exude at elevated temperatures.
-2- It is the purpose of the present invention to provide a novel plastic mouldable explosive composition in which the aforementioned problems are reduced or eliminated.
According to the present invention there is provided a plastic mouldable explosive composition comprising a gelled binder and a particulate explosive filler contained in the binder, wherein the binder comprises a blend of a polyethylene wax polymer together with a tackifying resin comprising a polyisobutene polymer.
By a "polyethylene polymer" is meant a polymer comprising ethylene optionally copolymerised with one or more than other compounds, the ethylene content forming at least 50, desirably at least per cent by weight of the polymer.
By a "polyisobutene polymer" is meant polyisobutene optionally copolymerised with one or more other compounds, the isobutene content forming at least 50, desirably at least 90, per cent by weight of the polymer.
The relative proportions of the components of the binder depend upon the grades of the components employed in the blend. The most suitable amount of 25 the polyethylene wax polymer in the blend will in many cases be in the range 2 to 35 per cent by weight especially when the polyethylene polymer has a molecular weight in the inclusive range 3,000 to 15,000. However, the amount of the polyethylene wax polymer may be present in an amount of up to per cent by weight of the blend with the tackifying resin when the polyethylene polymer has a low molecular weight, eg. in the range 3,000 to 7,000.
Any liquid polyisobutene having a molecular weight of from 500 to 7,000, preferably from 500 to 5,000 may be used in or as the tackifying resin.
S-3- Preferred compositions comprise binders including polyisobutene having a molecular weight of from 500 to 5000 and a polyethylene having a molecular weight of from 3000 to 13000, polyisobutene forming 85 per cent by weight or more of the polyisobutene/polyethylene blend.
Optional additives to the binder blend in the explosive composition according to the present invention comprise: micrystalline wax forming up to 10 per cent by weight of the binder; a plasticiser having a viscosity of less than 50 cst preferably less than 2 cst at 20°C and o having a melting point less than OC, the 15 plasticiser forming up to 20 per cent by weight of the binder; an anti-oxidant forming up to 1 per cent by weight of the binder.
For example, a suitable plasticiser comprising 20 a quantity of material selected from one or more known energetic plasticisers such as GAP (glycidyl azide polymer), BDNPA/F(bis-2,2-dinitropylacetal/formal), bis-(2,2-dinitropropyl)formal, bis (2,2,2-trinitroethyl)formal bis(2-fluoro-2,2 dinitroethyle)formal, diethylene glycol dinitrate, glycerol trinitrate, glycol trinitrate, triethylene glycol dinitrate, trimethylolethane trinitrate, butanetriol trinitrate, or 1,2,4-butanetriol trinitrate may be added to form the binder.
Alternatively, or in addition the binder may incorporate one or more known non-energetic plasticisers such as one or more esters of phthalic, adipic or sebacic acid. For example the optional plasticiser may comprise a dialkyl phthalate eg. dibutyl phthalate or diethyl phthalate or may be selected from triacetin, -4tricresyl phosphate, polyalkylene glycols and their alkyl ether derivatives, eg. polyethylene glycol, polypropylene glycol, diethylene glycol butylether and dioctyl sebacate.
As suitable optional anti-oxidant compounds polymerised trimethyl dihydroquinone; or 2,2'-methylene-bis (4-methyl-6-butylphenol); or pentaerythrityl-tetrakis(3,3,5-ditertbutyl-4-hydroxyp henyl)propionate may be incorporated in the binder in an extent of up to 1 per cent, eg. about 0.5 per cent, by weight of the binder.
Preferably at least 75% desirably at least 88% by weight of the explosive filler in the composition according to the present invention is *000 15 constituted by one or more heteroalicyclic nitramine compounds. Nitramine compounds are those containing at least one N-NO 2 group.
Heteroalicyclic nitramines bear a ring containing
N-NO
2 groups. Such ring or rings may contain for 20 example from two to ten carbon atoms and from two to ten ring nitrogen atoms. Examples of preferred heteroalicyclic nitramines are RDX(cyclo-l,3,5-trimethylene-2,4,6-trinitramine, hexagen), HMX 25 (cyclo-l,3,5,7-tetramethylene-2,4,6,8-tetranitramine, octogen and mixtures thereof. The filler may alternatively be selected from TATND (tetranitro-tetraminodecalin, HNS (hexanitrostilbene) NTO(3-nitro-l,2,4-thiazol-5one), and TATB 30 (triaminotrinitrobenzene).
Preferably, the explosive filler comprises from 50% to 100% by weight of RDX.
Other highly energetic filler materials may be used in place of or in addition to the compounds specified above. Examples of other suitable known highly energetic materials include picrite (nitroguanidine), aromatic nitramines such as tetryl, ethylene dinitramine, and nitrate esters such as nitroglycerine (glycerol trinitrate), butane triol trinitrate or pentaerythritol tetranitrate, trinitrotoluene (TNT), inorganic oxidisers such as ammonium salts, eg. ammonium nitrate or ammonium perchlorate, and energetic alkali metal and alkaline earth metal salts.
Known metallic fuels such as aluminium powder may be added to form part of the energetic solids filler, eg. forming 1 to 50 per cent, eg. up to per cent by weight of the total composition.
Alternative metal fuels include magnesium, magnesium/aluminium alloy. Metallic fuel is preferably included together with RDX or with RDX 15 and ammonium perchlorate.
The amount of explosive filler incorporated in
O
the binder in the composition according to the present invention depends upon the amount of the filler required to convert the binder from a gel 20 into a plastic mouldable mass but the explosive filler content is conveniently in the range 50 to 95 per cent by weight, desirably 85 to 90 per cent by weight, of the explosive composition.
In the case where the explosive is RDX and the 25 metallic fuel comprises aluminium, the metallic fuel preferably comprises up to 30 per cent by weight of the total composition, being up to 52 per cent by weight of the energetic filler in compositions having up to 88 per cent by weight solids loading.
The compositions according to the present invention may be made by adding the polyethylene to the polyisobutene and other optional ingredients at a temperature above the melting point of the polyethylene and then mixing the two together until a homogeneous liquid is produced. The explosive -6filler is then added as a powder optionally in a water wet condition and optionally with a suitable single organic solvent added to the binder to facilitate processing. Following further stirring to give a further homogeneous mass the product is cast, pressed, extruded or rolled as appropriate into suitable shapes which are allowed to cool to room temperature (250C).
A compatible coupling agent, in an extent of up to 2 per cent by weight of the overall composition, may be added during mixture of the filler with the binder to improve adhesion between the two.
Examples of suitable coupling agents are: silane coupling agents eg 1,2-ethane-diamine, N-(ethynylphenylmethyl)- N-(3-trimethoxysilyl)propylmonohydrochloride or (ii) C 2:CHSi(OCH2CH2OCH 3 20 organotitanate coupling agents eg isopropyltri (dioctylphosphate)titanate.
o A compatible surfactant in an extent of up to 2 per cent by weight of the overall composition may be added to improve workability. Examples of 25 suitable surfactants include eg. lecithin, (ii) polyoxyethylene(20)sorbitan esters, eg monolaurate, monopalmitate or mono-oleate; or (iii) dioctyl ester of sodium sulphonic acid or (iv) pentaerythritoldioleate (PEDO).
A compatible dye, in an extent of up to by weight of the overall composition, may be added during mixture of the filler with the binder as an aid to concealment.
Explosive compositions embodying to the present invention show useful moulding properties similar to those shown by the known material mentioned above, but advantageously show reduced -7migration of liquid binder components (and hence brittleness) with ageing, reduced exudation at elevated temperatures and improved low temperature mouldability.
In addition, the hydrophob6c nature of the binder imparts greater stability, adhesion and workability when the explosive compositions are used underwater.
Examples of the preparation and properties of compositions embodying the present invention will now be described by way of example as follows.
Various suitable materials (the "gelled
OS
9 binder" specified above) were first prepared by the following method, Method A Method A Polyisobutene (PIB), and other optional ingredients such as plasticisers and antioxidants but not the polyethylene were added to a mixing vessel at room temperature (20 The vessel 20 was heated to a temperature of 140 0 C, slow stirring being applied at temperatures above 80 C.
When the temperature reached 115-120 0
°C
polyethylene was added in increments to form a homogenous fluid.
25 The composition formed was cast into moulds or storage vessels and allowed to cool Explosive compositions were prepared from the resulting binder materials produced by Method A according to either of the alternative Method B, Method C or Method D as follows.
An incorporator was heated to a temperature of 95-100 C: Method B The binder material was dissolved in an equal mass of solvent by heating at 60-80°C with stirring to form a suitable lacquer.
-8- The explosive filler eg RDX, including any optional additives such as coupling agent but not metallic fuel, was provided in a water wet condition in a mixer which was heated to a suitable elevated temperature, eg. 80-95°C for RDX.
Binder lacquer was then added carefully followed by stirring with heating then cooling and drying.
After removal of water and solvent, any required metallic fuel, eg powdered aluminium, was added.
Method C An incorporator was preheated at a temperature of 85 to 95°C. Increments of the solid explosive filler in water wet form and the binder were added at intervals followed by mixing of the ingredients after each addition. Water was removed optionally under vacuum and the mixture stirred until homogeneous. The mixture was cooled optionally under vacuum to room temperature stirring being continued during cooling, and then o 20 stored in a container for use.
Method D About one half of the binder ingredients were @5 added to an incorporation preheated to a temperature of 95-100C.
A first increment of wetted nitramine was added and mixed for about 15 minutes at atmospheric pressure, allowing water to evaporate.
Further increments of wetted nitramine were added each being allowed to incorporate for 10-15 minutes before addition of the next. Loose powder of unmixed composition between additions was scraped down.
When all explosive has been added aluminium was put in if required, allowing each increment to incorporate for approximately 10 minutes with scraping down between additions.
-9- The remaining presoftened binder was poured and then incorporated for approximately 1 hour with scraping down every 15-20 minutes. A vacuum was applied if required to ensure complete removal of water.
The material was removed from the mixer either whilst hot, or after first cooling to the desired temperature whilst mixing.
If curing ingredients were to be included the material was cooled to 60-80°C, curing ingredients were added and the resultant material mixed for 15-20 minutes before removal from the incorporator.
Examples of binders made by Method A are given in Tables 1 and 2 as follows.
e*
S.
0
S
*6.
CELLED-POLYETHYLENE BINDER SYSTEMS TABLE 1: COMPOSITION
INGREDIENTS
@0 S 00 go 0*
S
*eg g eg S S @000 OOOg 0 *g.g OS 60 0 0505
C
*0 S 0* S S eg 00 *g g egg g Example Number Bi B2 B3 B4 B5 B6 B7 B8 B9 Bi10 Bil B12 Bi13 B14 B1 5 Polyethylene Type P2 7.5 P2 7.5 P2 7.5 P2 20.0 P2 22.0 P2 25.0 P2 27.0 P2 30.0 P2 35.0 P3 89.5 P3 89.5 P3 89.5 P1 59.5 P1 59.5 P1 59.5 Polyi sobutene Type PIBi 92.0 PIB2 92.0 PIB2 92.0 PIB3 92.0 PIB3 77.5 PIB3 74.5 PIB3 72.5 PIB3 69.5 PIB3 64.5 PIBi 10.0 PIB2 10.0 PIB3 10.0 PIBI 40.0 PIB2 40.0 PIB3 40.0 Antioxidant 0 g.gg S g goog go -11- GELLED-POLYETHYLENE BINDER SYSTEMS ;Continued) TABLE 1: COMPOSITION (Continued)
INGREDIENTS
00 0@ 0 0 006 0 00 SO 0000 0*00
S
OS
0 9 S S 05 S 0O 00 6 0* *0 0 0 *0e 0 Example Number B1 6 B17 B1 8 B1 9 B20 B21 B22 B23 B24 B25 B26 B27 B28 B29 Polyethylene Type P2 22.0 P2 22.0 P1 22.0 P1 22.0 P1 22.0 P3 22.0 P3 7.5 P1 7.5 P2 7.5 P3 7.5 P2 5.0 P2 7.5 P2 7.5 P2 7.5 Polyisobutene Type PIB4 77.5 PIB3 77.5 PiB5 77.5 PIB4 77.5 PIB3 77.5 PIB5 77.5 PIB3 92.0 PIB3 92.0 PIBI 92.0 PIBi 92.0 PIBi 94.5 PIB3 87.0 PIBI 87.0 PIB2 92.0 Antioxidant DOS 0 0@50e0 0 0 ~00056
S
-12- GELLED-POLYETHYLENE/POLYISOBtJTENE BINDER SYSTEMS TABLE 2: PROPERTIES Example Number 0O S 0* 0O 0@ 0 0 0*S S 0e 0 0 0 0eeO OS OS 0 0 00 S. S 0O 0 00 0* 0 000 0 Bi B2 B3 B4 B5 B6 B7 B8 B9 B10 Bli B1 2 B1 3 B1 4 B1 5
TMD
(g/cm3 0.906 0.911 0.916 0.915 0.915 0.915 0.915 0.915 0.915 0.907 0.907 0.908 0.906 0.908 0.910 Softening Point 0
C)
21 23 28 34 35 94 94 98 98 100 101 98 96 96 101 Pen et rat ion (mm x 10-1) 273 253 218 228 223 213 200 178 8 6 a 000000 0 0 005500 0 0 -13- GELLED-POLYETHYLENE/POLYISOBUITENE BINDER SYSTEMS (Continued) TABLE 2: PROPERTIES (Continued) Example Number 0 0O 00 0O S S
S
0O 0 0 0000 0000
S
0O Se 0 0e OS S
S.
00 0 0O 60 0 000 0 B1 6 Bl17 B18 B19 B20 B21 B22 B23 B24 B25 B26 B27 B28 B29 Softening Point 0C 96 89 87 94 87 67 57 87 92 Penetration (mm x 101
S
0 a 555005 In Table 1 the Antioxidant is 2,2'-methylene-bis-(4-methyl-6-butylphenol).
In Table 1 the polyethylene is as follows: Type P1: Molecular weight n8000.
Type P2: molecular weight n12000 Type P3: Molecular weight n4000 In Table 1 the polyisobutene type is as follows: Type PIBI: molecular weight n1300 Type PlB2: molecular weight n2100 -14- Type PIB3: molecular weight n2400 Type PIB4: molecular weight n3800 Type PIB5: molecular weight n5800.
Type PIB6: molecular weight n780 Type PIB7: molecular weight n1000 In Table 1 DOS is the plasticiser dioctyl sebacate.
In Table 2 TMD is theoretical maximum density.
In Table 2 the softening point is measured according to the known standard ASTM D36-8 (British Standard BS4692:1972) In Table 2 the penetration is measured according to the known standard ASTM-2884-82 using a 100g weight and a 20s drop at 25 0
C.
Examples of explosive compositions made by Method B or C using binder materials listed in Table 1 are listed in Tables 3 and 4 as follows.
00*** .S 6 .0 O 0 0 PLASTIC EXPLOSIVE COMPOSITIONS EMPLOYING GELLED-POLYETHYLENE/POLYISOBUTENE
BINDERS
TABLE 3: COMPOSITION Explosive Binder Solids Loading Composition Example %w/w %v/v Example Number Number El B2 88.0 78.8 *E2 Bl 88.0 78.7 uE3 B5 88.0 78.8 E4 B98.07.
B16 88.0 78.8 E6 B17 88.0 78.8 E6 B18 88.0 78.7 E8 B22 88.0 78.8 E8 B23 88.0 78.6 us.B4.8. 7.
0Ell B23 88.0 78.6 .5**E12 B25 88.0 78.6 00 0 Eli B26 88.0 78.6 E14 B28 88.0 78.6 000:E15 B28 88.0 78.6 *:o:E16 B5 88.0 78.8 -16- PLASTIC EXPLOSIVE COMPOSITIONS
EMPLOYING
GELLED-POLYETHYLENE/POLYISOBUTENE
BINDERS
TABLE 4:
PROPERTIES
0 0 0 0 0* C *e C.0 El E2 E3 E4 E5 E6 E7 E8 E9 El 0 Ell E12 E13 El14 El16
TMD
(g/cm3 1.613 1.612 1.615 1.615 1.614 1.612 1.614 1.611 1 .611 1.610 1.610 1.610 1.612 1.610 1.610 1.615 Penetration (mm x 101) 16 30 11 8 11 22 28 27 24 31 87 weight Loss on Ageing 2.1 .18 .27 0.46 0.00 1.10 In Table 3 the solids loading comprises particulate
RDX
the remainder of the explosive composition being the binder material (eg. Bi, B2 etc).
In Table 4 penetration is measured to the known standard ASTM-2284-82 using a 100g weight and a 20s drop at 0C -17dxn Table 4 ageing comprises 3 months at a temperature of 0
C.
I~ Tble4 te 'C&oim.t relate to the erset~ efthe explosivecrp~~o t2'C Examples of hazard data for Examples E14 and E15 are as follows: E14 figure of insensitiveness: 110 (RDX Mallet Friction (steel on steel) 0% These tests are specified in Sensitiveness Collaboration Committee (SCC) Manual No 3.
0* 0*
Claims (19)
1. A plastic mouldable explosive composition comprising a gelled binder and a particulate explosive filler contained in the binder, wherein the binder comprises a blend of a polyethylene wax polymer together with a tackifying resin comprising a polyisobutene polymer.
2. A plastic mouldable explosive composition as claimed in claim 1 and wherein the polyethylene polymer comprises ethylene optionally copolymerised with one or more other compounds, the ethylene C content forming at least q0 per cent by weight of the polymer.
3. A plastic mouldable explosive composition as claimed in claim 1 e•g. or claim 2 and wherein the polyisobutene polymer comprises isobutene optionally copolymerised with one or more other compounds, the isobutene content forming at least 9O per cent by weight of the polymer.
4. An explosive composition as claimed in any one of the eel Opreceding claims and wherein the amount of the polyethylene wax polymer in the 4emosition is in the range 2 to 35 per cent by weight.
An explosive composition as claimed in claim 4 and wherein the polyethylene polymer has a molecular weight in the inclusive range 3,000 to 15,000.
6. An explosive composition as claimed in any one of the preceding claims and wherein the polyisobutene polymer comprises a liquid polyisobutene having a molecular weight of from 500 to 7,000.
7. An explosive composition as claimed in any one of the preceding claims and wherein the composition comprises a binder including a polyisobutene having a molecular weight of from 500 to 5000 and a polyethylene having a molecular weight of from 3000 to 13000, the polyisobutene forming 85 per cent by weight or more of the polyisobutene/polyethylene blend.
8. An explosive composition as claimed in any one of the preceding claims and wherein the composition comprises as an additive to the binder one or more of the following; microcrystalline wax forming up to 10 per cent by weight of the binder; a plasticiser having a viscosity of less than 50 cst at 20 0 C, the plasticiser forming up to 20 per cent by weight of the binder; an anti-oxidant forming up to 1 per cent by weight of the Sbinder.
9. An explosive composition as claimed in any one of the preceding claims and wherein at least 75% by weight of the explosive filler in the composition is constituted by one or more heteroalicyclic nitramine compounds.
An explosive composition as claimed in claim 9 and wherein the explosive filler comprises from 50% to 100% by weight of RDX o based on the total weight of filler.
11. An explosive composition as claimed in any one of the preceding claims and wherein the explosive filler forms from 85 to 90 per cent by weight of the explosive composition.
12. An explosive composition as claimed in any one of the preceding claims and wherein the filler comprises from 1 to 50 per cent by weight of a metallic fuel based on the total weight of the composion
13. An explosive composition as claimed in claim 12 and wherein the filler comprises RDX as explosive and aluminium as metallic fuel, the aluminium comprising up to 52 per cent by weight of the energetic filler.
14. A composition as claimed in any one of the preceding claims and which comprises an explosive-to-binder compatible coupling agent in an extent of up to 2 per cent by weight of the overall composition.
An explosive composition as claimed in any one of the preceding claims and which includes a compatible surfactant in an extent of up to 2 per cent by weight of the overall composition.
16. An explosive composition as claimed in any one of the preceding claims and including a compatible dye, in an extent of up to by weight of the overall composition.
17. An explosive composition as claimed in any one of the preceding claims and substantially the same as one of the specific Explosive Compositions described herein. 0 o.0 0
18. An explosive product moulded from an explosive composition ,0 0! as described in any one of the preceding claims.
19. An explosive composition as claimed in claim 1, ooo0 substantially as hereinbefore described with reference to the Examples. 00 0 -2-0.--The-steps, features, compositions* and-oe-uRd •••referred to or indicated in the specificat-ionand/or 066 claims of this application, indIv9idually or o• collectively, and-any and all combinations of any two o K• o-r- eof said steps or features. (.00 0 Dated this llth day of May 1989 oo0&AM 9YVTEMS PL /I O BRoyal Ordnanoc plo9 By its Patent Attorneys DAIVES COLLISON
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8811127 | 1988-05-11 | ||
| GB8811127A GB2365420B (en) | 1988-05-11 | 1988-05-11 | Explosive compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU784682B1 true AU784682B1 (en) | 2006-06-01 |
Family
ID=10636711
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU34652/89A Expired AU784682B1 (en) | 1988-05-11 | 1989-05-11 | Explosive compositions |
Country Status (5)
| Country | Link |
|---|---|
| AU (1) | AU784682B1 (en) |
| CA (1) | CA1341570C (en) |
| FR (1) | FR2893614B1 (en) |
| GB (1) | GB2365420B (en) |
| SE (1) | SE529845C2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102006049090A1 (en) * | 2006-10-18 | 2008-04-30 | Clariant International Limited | Uploaded adhesive composition through the use of metallocene waxes |
| GB2555764B (en) * | 2015-10-12 | 2022-06-15 | Lewtas Science & Tech Ltd | Improvements in or relating to energetic materials |
| GB2565031B (en) * | 2017-04-10 | 2023-02-22 | Lewtas Science & Tech Ltd | Improvements in or relating to energetic materials |
| CN116606398B (en) * | 2023-05-15 | 2024-05-17 | 湖北航天化学技术研究所 | Fluorine-containing macromolecular bonding agent and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4203786A (en) * | 1978-06-08 | 1980-05-20 | Allied Chemical Corporation | Polyethylene binder for pyrotechnic composition |
| EP0254618A1 (en) * | 1986-07-21 | 1988-01-27 | Societe Nationale Des Poudres Et Explosifs | Preformed inhibitor based on rubber gum for a composite propellant with a polyurethane binder |
| US4875949A (en) * | 1988-05-18 | 1989-10-24 | The United States Of America As Represented By The Secretary Of The Army | Insensitive binder for propellants and explosives |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1082641A (en) * | 1963-03-14 | 1967-09-06 | Secr Defence | Explosive compositions |
| GB2176878B (en) * | 1979-08-14 | 1987-09-03 | Royal Ordnance Plc | Hollow charges |
-
1988
- 1988-05-11 GB GB8811127A patent/GB2365420B/en not_active Expired - Lifetime
-
1989
- 1989-05-11 SE SE8901693A patent/SE529845C2/en not_active IP Right Cessation
- 1989-05-11 FR FR8906206A patent/FR2893614B1/en not_active Expired - Lifetime
- 1989-05-11 CA CA000599369A patent/CA1341570C/en active Active
- 1989-05-11 AU AU34652/89A patent/AU784682B1/en not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4203786A (en) * | 1978-06-08 | 1980-05-20 | Allied Chemical Corporation | Polyethylene binder for pyrotechnic composition |
| EP0254618A1 (en) * | 1986-07-21 | 1988-01-27 | Societe Nationale Des Poudres Et Explosifs | Preformed inhibitor based on rubber gum for a composite propellant with a polyurethane binder |
| US4875949A (en) * | 1988-05-18 | 1989-10-24 | The United States Of America As Represented By The Secretary Of The Army | Insensitive binder for propellants and explosives |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2365420B (en) | 2002-05-29 |
| SE8901693L (en) | 2006-07-05 |
| CA1341570C (en) | 2008-03-25 |
| SE529845C2 (en) | 2007-12-11 |
| FR2893614A1 (en) | 2007-05-25 |
| GB8811127D0 (en) | 2001-12-05 |
| FR2893614B1 (en) | 2008-06-27 |
| SE8901693D0 (en) | 1989-05-11 |
| GB2365420A (en) | 2002-02-20 |
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