EP0514000A1 - Explosive comprising a foamed sensitizer - Google Patents
Explosive comprising a foamed sensitizer Download PDFInfo
- Publication number
- EP0514000A1 EP0514000A1 EP92303297A EP92303297A EP0514000A1 EP 0514000 A1 EP0514000 A1 EP 0514000A1 EP 92303297 A EP92303297 A EP 92303297A EP 92303297 A EP92303297 A EP 92303297A EP 0514000 A1 EP0514000 A1 EP 0514000A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- explosive
- gas
- foam
- explosive composition
- liquid
- 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 140
- 239000000203 mixture Substances 0.000 claims abstract description 90
- 239000006260 foam Substances 0.000 claims abstract description 83
- 239000007788 liquid Substances 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004088 foaming agent Substances 0.000 claims abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 19
- 239000008258 liquid foam Substances 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims description 51
- 239000000839 emulsion Substances 0.000 claims description 41
- 239000003795 chemical substances by application Substances 0.000 claims description 40
- 238000005422 blasting Methods 0.000 claims description 32
- 239000000446 fuel Substances 0.000 claims description 27
- 150000003839 salts Chemical class 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 11
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical group OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 9
- 238000005187 foaming Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 230000001804 emulsifying effect Effects 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000005018 casein Substances 0.000 claims description 4
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical group NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims description 4
- 235000021240 caseins Nutrition 0.000 claims description 4
- 230000000994 depressogenic effect Effects 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 229920002367 Polyisobutene Polymers 0.000 claims description 3
- 230000006641 stabilisation Effects 0.000 claims description 3
- 238000011105 stabilization Methods 0.000 claims description 3
- 229920005549 butyl rubber Polymers 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000011800 void material Substances 0.000 abstract description 5
- 239000007762 w/o emulsion Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 18
- 239000012071 phase Substances 0.000 description 16
- 239000000654 additive Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- -1 such as Substances 0.000 description 8
- 230000035945 sensitivity Effects 0.000 description 7
- 239000005662 Paraffin oil Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000009472 formulation Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229920005652 polyisobutylene succinic anhydride Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 235000018102 proteins Nutrition 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- CUNWUEBNSZSNRX-RKGWDQTMSA-N (2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol;(z)-octadec-9-enoic acid Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O CUNWUEBNSZSNRX-RKGWDQTMSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004166 Lanolin Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 229940039717 lanolin Drugs 0.000 description 3
- 235000019388 lanolin Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229960005078 sorbitan sesquioleate Drugs 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- HZTVIZREFBBQMG-UHFFFAOYSA-N 2-methyl-1,3,5-trinitrobenzene;[3-nitrooxy-2,2-bis(nitrooxymethyl)propyl] nitrate Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O.[O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O HZTVIZREFBBQMG-UHFFFAOYSA-N 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 238000005474 detonation Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-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
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 244000303965 Cyamopsis psoralioides Species 0.000 description 1
- 108010082495 Dietary Plant Proteins Proteins 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- 244000187656 Eucalyptus cornuta Species 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- 108010044091 Globulins Proteins 0.000 description 1
- 102000006395 Globulins Human genes 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 102000004895 Lipoproteins Human genes 0.000 description 1
- 108090001030 Lipoproteins Proteins 0.000 description 1
- 102000014171 Milk Proteins Human genes 0.000 description 1
- 108010011756 Milk Proteins Proteins 0.000 description 1
- UGHVFDVVZRNMHY-NXVVXOECSA-N Oleyl laurate Chemical compound CCCCCCCCCCCC(=O)OCCCCCCCC\C=C/CCCCCCCC UGHVFDVVZRNMHY-NXVVXOECSA-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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 244000305267 Quercus macrolepis Species 0.000 description 1
- 235000016976 Quercus macrolepis Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- IJCWFDPJFXGQBN-RYNSOKOISA-N [(2R)-2-[(2R,3R,4S)-4-hydroxy-3-octadecanoyloxyoxolan-2-yl]-2-octadecanoyloxyethyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCCCCCCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCCCCCCCCCCCC IJCWFDPJFXGQBN-RYNSOKOISA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000021120 animal protein Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 229920006248 expandable polystyrene Polymers 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 150000002195 fatty ethers Chemical class 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000021239 milk protein Nutrition 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 239000004533 oil dispersion Substances 0.000 description 1
- 210000002787 omasum Anatomy 0.000 description 1
- 235000014366 other mixer Nutrition 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229940100515 sorbitan Drugs 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 239000001589 sorbitan tristearate Substances 0.000 description 1
- 235000011078 sorbitan tristearate Nutrition 0.000 description 1
- 229960004129 sorbitan tristearate Drugs 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase
- C06B47/14—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase comprising a solid component and an aqueous phase
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/002—Sensitisers or density reducing agents, foam stabilisers, crystal habit modifiers
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase
- C06B47/14—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase comprising a solid component and an aqueous phase
- C06B47/145—Water in oil emulsion type explosives in which a carbonaceous fuel forms the continuous phase
Definitions
- the present invention relates to explosive compositions and, in particular, to sensitized explosive compositions.
- Semisolid colloidal dispersions of water-bearing explosives or blasting agents are well known. These products typically comprise an oxidizing component, usually predominantly ammonium nitrate, a fuel component and water. These blasting agents are referred to in the art as slurry explosives (or as water gels), and as emulsion-type explosives.
- Slurry explosives typically comprise a discontinuous fuel phase which is dispersed in a continuous aqueous solution of the oxidizer salt. Thickening agents are added to the aqueous phase in order to increase the viscosity of the explosive, or to effect gelation, and thus stabilize the structure of the explosive.
- Emulsion explosives typically comprise a discontinuous aqueous oxidizer salt solution which is dispersed in a continuous fuel phase. Emulsifying agents are generally added to the dispersion to stabilize the dispersion.
- additives to both slurry and emulsion explosives to modify the performance of the blasting agent is similarly well known.
- additives include, for example, the addition of aluminum or ammonium nitrate to the explosive to increase the strength and/or sensitivity of the blasting agent.
- One method of addition of voids in a blasting agent is the addition of hollow glass microballoons to an emulsion explosive. While this method provides a suitable means for the creation of voids within the blasting agent, the microballoons are relatively expensive and can be difficult to handle due to their low bulk density.
- microballoons which products also have particles containing one or a number of gas bubbles, such as, for example, inorganic hollow microspheres made of glass, sirasu (Japanese volcanic ash), silicon sand, or sodium silicate and the like, is also known. These materials suffer from the same disadvantages as glass microballoons.
- Edamura et al disclose in U.S. Patent No. 4,543,137, the use of a gas-retaining agent, such as, those made from foamed polystyrene, foamed polyurethane and the like.
- the gas-retaining agents of Edamura et al can have a rigid structure similar to the inorganic microballoons described hereinabove, and which can be brittle and subject to breakage during handling or can be made soft and spongy so as to be more resistant to inadvertent breakage during handling.
- These soft and spongy gas-retaining agents are produced by foaming a foaming agent in a thermoplastic resin and allowing the thermoplastic resin to set and thus entrap gas within the resin structure.
- In-situ generation of air or gas voids within the blasting agent is an alternative method over the addition of gas filled microballoons and, typically, comprises the addition of a material which reacts in the blasting agent to generate a gas bubble.
- This gas bubble is entrained within the blasting agent by the viscous nature of the semisolid blasting agent.
- the generation of a gas void within the blasting agent by an in-situ chemical reaction is termed within the industry as chemical gassing.
- a third route to introducing gas voids into an explosive blasting agent is to mechanically agitate the blasting agent composition in order to entrain an occluded gas void within the blasting agent.
- This route has the disadvantage of intensive mechanical agitation of a sensitized explosive and can be subject to poor long-term blasting stability as gas is slowly lost from the blasting agent.
- a further route to the production of gas voids within an explosive blasting agent is described by Curtin and Yates in U.K. Patent Application No. 2,179,035, wherein a gas bubble generating agent is added to the blasting agent prior to or while the blasting agent is subjected to superatmospheric pressure to dissolve at least part of the gas present.
- the blasting agent is returned rapidly to atmospheric pressure and, thus, creates a fine discontinuous gaseous phase in the composition.
- this production route requires the sensitized blasting agent to be prepared under pressure and, thus, requires specialized equipment adapted to handle the pressurized explosive.
- the present invention provides an explosive composition sensitized by gas voids, wherein the gas voids have been distributed in said explosive composition by dispersal of an essentially gas-in-liquid foam.
- the explosive composition comprises an oxidizing salt and a fuel and the explosive composition is a slurry or emulsion explosive.
- bubble in this specification and claims, is used to describe a mass of bibles which have been dispersed in a liquid.
- the bubbles are surrounded by and, thus, separated from each other by thin, flexible films of liquid with, optionally, viscosity control agents or foaming agent molecules absorbed at the gas/liquid interface in order to stabilize the film.
- the gas phase comprises at least 90% by volume of the foam.
- the foam used in the present invention may be produced by introducing or "sparging" a pressurized gas into a closed vessel containing the pressurized liquid component of the foam, mixing and subsequently releasing the pressure on the system so as to create small gas bubbles within the liquid component.
- the foam produced can then be added to and blended into the base explosive composition by, for example, a low shear or a static mixer.
- the pressurized gas used to form the foam can be any gas which is compatible with other components of the explosive.
- the gas is air, carbon dioxide or nitrogen but any other gas could be used provided that the solubility of the gas in the liquid is controllable over the time and temperature range to which the sensitized explosive will be stored prior to use.
- Bubbles can also be dispersed in the liquid carrier to produce a foam by mechanical agitation, such as, for example, by a high shear mixer, such as an Oakes mixer, or by low shear mixing of the liquid carrier to entrain gas voids within the liquid carrier.
- Mechanical agitation in the process of the present invention is, preferably, conducted on a non-explosive liquid carrier and, thus, is inherently safer and more effective than a process of entraining gas voids directly into the explosive composition.
- the foams of the present invention preferably, have a low density in order to effectively lower the density of the explosive to which the foam is added.
- the foam has a density of less than 0.2 g/ml and, more preferably, below 0.1g/ml and, even more preferably, below 0.06g/ml.
- the liquid phase which surrounds the individual bubbles will begin to drain so as to create a thinner layer at the top of the bubble than at the bottom.
- the thinner layer will break causing coalescence of the bubble or loss of gas from the foam and the loss or drainage of the carrier liquid from the foam.
- the loss of gas is, thus, related to the 'drainage' rate of the foam in that the gas volume is reduced as liquid drains from the foam.
- the stability of the foam can, thus, be measured by determining the half-life of the foam wherein the half-life is the time taken for the loss of half of the gas volume from the foam. The half-life is, thus, an indication of the shelf life of the foam after the foam is produced.
- Control of the drainage rate and, thus, control of the half-life of the foam can be influenced and effectively controlled by the addition to the foam of additives which stabilize the liquid film around the bubble. If the foam is to be incorporated in the explosive shortly after it is produced, for example, within one to four minutes of production, foam stability is not as critical as for foams which are prepared and later added to the explosives.
- Additives such as high viscosity polyisobutylene, act to increase the viscosity of the liquid film around the gas bubble.
- additional additives such as foaming agents are, preferably, added to the liquid carrier in order to assist in formation of the foam.
- the foams of the present invention preferably, comprise a gas, a foaming agent, a viscosity control agent and a liquid carrier.
- the foaming agent provides a film around the gas bubbles in order to prevent them from bursting or coalescing.
- typical foaming agents would include materials such as proteins, and, more specifically, milk proteins, egg proteins, animal proteins, vegetable proteins, fish proteins, ond any mixture thereof.
- the foaming agent can also be a protein derivative or associated product, such as, phospholipids, lipoproteins, collagens, hydrolyzed proteins, and globulins. Steroids may also be used as a foaming agent.
- the foaming agent may also include surfactants, such as, for example, FC740* or FC751* which are perfluorinated surfactants, or mixtures of other surfactants.
- surfactants such as, for example, FC740* or FC751* which are perfluorinated surfactants, or mixtures of other surfactants.
- Other foaming agents include lanolin oil, derivatives of succinic anhydride, glycerol monostearate, steryl octazylene phosphate and long chain alcohols. * Trade Mark
- Casein is a mixture of proteins extracted from milk solids or soya beans, and can be used as is or can be fractionated into a water soluble portion or an oil soluble portion, each of which can be separately used as a foaming agent.
- the casein used may be totally or partially soluble in the oil but is, generally, dispersable so as to not be detrimental to foam production.
- the stability of the foam may also be enhanced by the addition of solid particles, such as, carbon black, talc or other materials known in the foam stabilization art.
- Viscosity in the foam can be controlled by the addition of viscosity control agent materials, such as, for example, high viscosity polyisobutylene, butyl rubber, natural rubber, bifunctional high molecular weight acids and the like and mixtures thereof to the liquid carrier which will increase the viscosity of the liquid component of the foam.
- viscosity control agent materials such as, for example, high viscosity polyisobutylene, butyl rubber, natural rubber, bifunctional high molecular weight acids and the like and mixtures thereof to the liquid carrier which will increase the viscosity of the liquid component of the foam.
- the viscosity of the oil selected will also influence the ease with which the foam can be produced and the drainage rate of the foam. Selection of the oil will, thus, depend on, inter alia , the method of manufacture of the foam, mixing conditions, temperature, residence times, pressure, type of gas and the like.
- the foam can be added to sensitize any suitable explosive material wherein gas voids are advantageous.
- Explosive materials include, in particular, emulsion or slurry explosives but also include propellants, high have explosives, such as, Heavy ANFO, modified emulsions, cast explosives, nitro ester based systems, and TNT, RDX or NG based systems.
- the liquid carrier used to prepare the foam is a liquid which is, preferably, compatible with the continuous phase of the explosive and into which the preferred additives of the foaming system can be dispersed or dissolved.
- the liquid carrier may take part in the detonation as a fuel or comprise an oxidizer, a sensitizer, or it may be non-reacting.
- slurry explosive water miscible liquids are preferred.
- the most preferred liquid for slurry explosives is water as a solvent or dispersion medium for desired additives or solutes.
- liquids are non-aqueous oils and solvents which are miscible with the organic liquid phase.
- liquids or liquifiable materials which act as fuels in the explosive reaction.
- fuels include, for example, paraffin oil and fuel oil.
- the liquid carrier need not be perfectly compatible with the continuous phase of the explosive provided that the explosive composition created remains sufficiently stable to allow adequate storage stability based on the proposed use of the explosive composition.
- Emulsion explosives includes low and essentially non-aqueous emulsions.
- the liquid carrier wilt preferably, contribute to the total fuel phase present in the emulsion explosive and, thus, may be described as a fuel for the explosive, as described hereinabove.
- a non-aqueous liquid in a slurry explosive may also provide fuel value to the explosive composition.
- a viscosity control agent can also be reduced or eliminated.
- the present invention provides a gassed explosive composition as described hereinabove wherein the gassing is achieved by a dispersed pre-formed foam and of which the liquid in said gas-in-liquid foam comprises a liquid or liquifiable fuel and a foaming agent.
- the liquid carrier is water
- a material to the water which acts as a freezing point depressant and, thus, make the base explosive composition and/or the foam, to which the foam has been added, more stable in cold temperatures.
- a preferred freezing point depressant is ammonium nitrate.
- low-freezing point, water miscible liquids or liquid mixtures, such as, ethylene glycol and water can be used as a liquid carrier in place of water.
- the foam once produced, is added to a base explosive composition, which base explosive composition is an insufficiently or non-sensitized emulsion or slurry explosive.
- the foam is, preferably, added to the base explosive composition shortly after its production, in order to minimize the need to create foams which are stable for long periods of time. It has been our experience that the use of foams having a half life of greater than one to four minutes is desirable in order to have sufficient time to mix the foam into the explosive composition.
- the foam is, preferably, added to the base explosive composition by a low shear mixing technique, such as, a static mixer or a ribbon mixer. During addition of the foam, the foam is broken and its gas bubbles are merely dispersed within the base explosive composition. At this stage, there is generally no need for intense mechanical agitation to entrain additional gas voids within the explosive composition.
- the present invention thus, provides an explosive as described hereinabove wherein the explosive composition is an emulsion explosive.
- the liquid carrier used to prepare the gas-in-liquid foam, which is to be added to the emulsion explosive, in a fuel is an explosive as described hereinabove.
- the present invention also provides an explosive as described hereinabove wherein the explosive composition is a slurry explosive and, preferably, the liquid carrier used to prepare the gas-in-liquid foam, which is to be added to the slurry explosive, is water.
- the base explosive composition to which the foam sensitizer is added can be any chemically compatible emulsion or slurry explosive, which base explosive compositions are described in the prior art.
- These base explosive compositions generally consist of an oil-in-water or water in-oil dispersion of an aqueous solution of an oxidizing salt and a fuel.
- the oxidizing salt may be any of the oxygen-containing salts typically used in the industry. These salts include, for example, nitrates, chlorates, and perchlorates. Most preferred, are salts, such as, sodium nitrate, calcium nitrate, potassium nitrate, and, most preferably, ammonium nitrate or mixtures thereof.
- the oxidizing salt is dissolved in water to provide the continuous phase of the explosive composition.
- the oxidizing salt may be melted, (e.g. as an eutectic mixture) to provide a liquid which can be dispersed as a discontinuous phase into the fuel or, more preferably, may be dispersed into the fuel as a concentrated aqueous solution.
- the fuel phase may be any liquid or liquifiable fuel known within the explosives art and may be the same as or different than the fuel used in the preparation of the foam. Suitable materials include mineral oil, waxes, paraffin oils, benzene, toluene, xylenes, and mixtures of petroleum distillates such as gasoline, kerosene and diesel fuel.
- An emulsion explosive formed as an embodiment of the present invention preferably, also include stabilizing surfactants, such as, for example, a mixture of sorbitan sesquioleate and a polyisobutylene succinic anhydride (PIBSA) based surfactant.
- stabilizing surfactants such as, for example, a mixture of sorbitan sesquioleate and a polyisobutylene succinic anhydride (PIBSA) based surfactant.
- PIBSA polyisobutylene succinic anhydride
- soribitan esters such as, sorbitan sesquioleate, sorbitan mono-oleate, sorbitan mono-almitate, sorbitan mono-stearate and sorbitan tristearate
- the mono- and di-glycerides of fat-forming fatty acids soya bean lecithin ond derivatives of lanolin, such as, isopropyl esters of lanolin fatty acids, mixtures of higher molecular weight fatty alcohols and wax estes
- ethoxylated fatty ethers such as, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyalkylene oleyl laurate
- subsituted oxazolines such as, 2-oleyl-4,4′-bis-(hydroxymethyl)-2-oxazolines.
- Suitable mixtures of such conventional emuls such as, 2-oleyl-4,4′-bis-(hydroxymethyl)-2-o
- the present invention provides an emulsion explosive comprising a continuous fuel phase, a discontinuous oxidizer phase and a surfactant for stabilization of said emulsion which emulsion has been sensitized by the addition of a gas-in-liquid foam.
- the slurry explosives formed as an embodiment of the present invention preferably, also include viscosity controlling additives, such as, for example, guar in order to increase to viscosity of the explosives so as to entrain the gas voids from the foam in the sensitized explosive formed.
- viscosity controlling additives such as, for example, guar
- the explosive compositions of the present invention may also comprise additional additives to enhance or modify the properties of the explosive blasting agent.
- additional additives are commonly known within the explosives industry and include the solid dopes and sensitizers commonly added to emulsions, such as, aluminum, ferrosilicon, TNT, AN, MAN, PETN and the like.
- additional sensitizing agents such as, for example, glass microballoons, may also be used in combination with the foams of the present invention.
- the present invention also provides a method of manufacturing a sensitized explosive composition
- a method of manufacturing a sensitized explosive composition comprising: preparing a base explosive composition by emulsifying an aqueous solution of on oxidizer salt in a liquid or liquifiable fuel, or by emulsifying a liquid or liquifiable fuel in an aqueous solution of an oxidizer salt; preparing an essentially gas-in-liquid foam by mixing a carrier liquid with a foaming agent to form a foaming solution and subjecting said solution to mechanical agitation, such as in a high shear mixer, low shear, or a static mixer, or other mixers known to those skilled in the art of foam manufacture, or to a pressurized gas sparge, or allowing it to foam by chemical reaction in the foam system, and blending said gas-in-liquid foam into said base explosive composition.
- the present invention also provides a method of blasting which comprises placing an explosive detonator in operative contact with an explosive and detonating said detonator.
- a fuel (or oil) based foaming solution was prepared having the composition shown in Table 1. All percentage figures shown are percent by weight unless otherwise indicated.
- a foam was produced by sparging the foaming solution with a pressuring stream of nitrogen gas.
- a foam was produced having a gas volume of greater than 90% by volume, a foam density of 0.12g/ml and a half life of greater than 45 minutes.
- a water based foaming solution was prepared having the composition as shown in Table 2.
- a foam was produced by mechanically agitating the foaming solution in a high shear mixer.
- a foam was produced having a gas volume of greater than 90% by volume, a foam density of 0.04g/ml and a half life of greater than 30 minutes.
- Emulsion explosive compositions comprising an oil based foam were prepared according to the present invention, having the formulations set out in Table 3.
- the foam was prepared according to the method and formulation as set out in Example 1.
- the oxidizer salt used in these examples was ammonium nitrate or an ammonium nitrate/sodium nitrate mixture.
- Paraffin oil was used for the oil phase in each example and a sufficient amount was added to produce a sensitized emulsion explosive with a 5% total oil phase.
- the total oil phase includes surfactants.
- the oxidizer salt solution was added to the oil phase containing a PIBSA based surfactant and sorbitan sesquioleate mixture while mixing in order to produce an emulsion explosive.
- Examples 3 and 4 were prepared using low shear mixing and Examples 5 and 6 were prepared by high shear mixing. The foam was dispersed into the emulsion by low shear mixing.
- the sensitized emulsion for each example was placed into a 25 or 50 mm cartridge in order to test the blasting ability of the explosive.
- the blasting ability of each composition was measured by determining the cap size needed to detonate the composition.
- the cap size used and the blast result for each example is shown.
- the velocity of detonation (VOD) for a successful blast is indicated.
- Examples 3 and 4 are typical of products which would be sold as "bulk” blasting agents and, thus, cap sensitivity is not expected.
- Examples 5 and 6 are typical of packaged products and cap sensitivity may be desirable.
- explosives could be prepared using the foam sensitizer which had acceptable sensitivity for industrial use.
- Stability of the product produced was measured by storing the explosive composition of Example 6 for 3 months. As is shown in Table 3, the composition had an acceptable VOD after 3 months storage at 22°C.
- the explosive in this example was prepared by first emulsifying in a low shear mixer the AN/SN/water mixture in a paraffin oil and surfactant mixture. The emulsified mixture was, subsequently, mixed with ammonium nitrate prills to produce a doped emulsion and the oil based foam was added to sensitize the explosive.
- the doped emulsion had a VOD of 3970 m/s when initiated with a 40g Pentolite booster charge. The sensitivity of the doped emulsion was industrially acceptable for larger diameter applications.
- the explosive in this example was prepared by first emulsifying in a low shear mixer the AN/SN/water mixture in a paraffin oil and surfactant mixture. The emulsified mixture was, subsequently, mixed with ammonium nitrate prills to produce a Heavy ANFO explosive and the oil based foam was added to sensitize the explosive.
- the doped emulsion had a VOD of 3300 m/s when initiated with a 40g Pentolite booster charge. The sensitivity of the doped emulsion was industrially acceptable for larger diameter applications.
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Abstract
Description
- The present invention relates to explosive compositions and, in particular, to sensitized explosive compositions.
- Semisolid colloidal dispersions of water-bearing explosives or blasting agents are well known. These products typically comprise an oxidizing component, usually predominantly ammonium nitrate, a fuel component and water. These blasting agents are referred to in the art as slurry explosives (or as water gels), and as emulsion-type explosives.
- Slurry explosives typically comprise a discontinuous fuel phase which is dispersed in a continuous aqueous solution of the oxidizer salt. Thickening agents are added to the aqueous phase in order to increase the viscosity of the explosive, or to effect gelation, and thus stabilize the structure of the explosive.
- Emulsion explosives typically comprise a discontinuous aqueous oxidizer salt solution which is dispersed in a continuous fuel phase. Emulsifying agents are generally added to the dispersion to stabilize the dispersion.
- The addition of additives to both slurry and emulsion explosives to modify the performance of the blasting agent is similarly well known. These additives include, for example, the addition of aluminum or ammonium nitrate to the explosive to increase the strength and/or sensitivity of the blasting agent.
- Of particular interest in the present invention is the addition of additives to create small voids within the blasting agent, which voids can be used to control the density of the explosive and to increase the sensitivity of the explosive. These sensitized explosives were described, for example, by Cattermole et al. in U.S. Patent No. 3,674,578; Bluhm in U.S. Patent No. 3,447,978; Wade in U.S. Patent No. 4,110,134 and Clay in U.S. Patent No. 4,181,546.
- One method of addition of voids in a blasting agent is the addition of hollow glass microballoons to an emulsion explosive. While this method provides a suitable means for the creation of voids within the blasting agent, the microballoons are relatively expensive and can be difficult to handle due to their low bulk density.
- The use of similar products to microballoons which products also have particles containing one or a number of gas bubbles, such as, for example, inorganic hollow microspheres made of glass, sirasu (Japanese volcanic ash), silicon sand, or sodium silicate and the like, is also known. These materials suffer from the same disadvantages as glass microballoons.
- Edamura et al disclose in U.S. Patent No. 4,543,137, the use of a gas-retaining agent, such as, those made from foamed polystyrene, foamed polyurethane and the like. The gas-retaining agents of Edamura et al can have a rigid structure similar to the inorganic microballoons described hereinabove, and which can be brittle and subject to breakage during handling or can be made soft and spongy so as to be more resistant to inadvertent breakage during handling.
- These soft and spongy gas-retaining agents are produced by foaming a foaming agent in a thermoplastic resin and allowing the thermoplastic resin to set and thus entrap gas within the resin structure.
- However, this route of adding gas voids to the blasting agent requires the initial preparation of a spongy or rigid microsphere structure which is added to the blasting agent.
- In-situ generation of air or gas voids within the blasting agent is an alternative method over the addition of gas filled microballoons and, typically, comprises the addition of a material which reacts in the blasting agent to generate a gas bubble. This gas bubble is entrained within the blasting agent by the viscous nature of the semisolid blasting agent. The generation of a gas void within the blasting agent by an in-situ chemical reaction is termed within the industry as chemical gassing.
- Chemical gassing of explosives is well known in the slurry and emulsion explosive industry. In U.S. Patents 3,886,010 and 3,706,607, Thornley and Chrisp, respectively, describe the use of chemical gassing agents such as nitrites, weak acids, hydrazine and peroxides in slurry and/or emulsion explosives.
- While chemical gassing is practised in the industry, its use is limited because of the difficulty in controlling the reaction rate of the chemical gassing reaction. The degree of gassing may be insufficient or may be excessively slow under cold production temperatures and may be excessive under hot conditions so as to provide uncontrollable borehole densities.
- A third route to introducing gas voids into an explosive blasting agent is to mechanically agitate the blasting agent composition in order to entrain an occluded gas void within the blasting agent. This route has the disadvantage of intensive mechanical agitation of a sensitized explosive and can be subject to poor long-term blasting stability as gas is slowly lost from the blasting agent.
- A further route to the production of gas voids within an explosive blasting agent is described by Curtin and Yates in U.K. Patent Application No. 2,179,035, wherein a gas bubble generating agent is added to the blasting agent prior to or while the blasting agent is subjected to superatmospheric pressure to dissolve at least part of the gas present. The blasting agent is returned rapidly to atmospheric pressure and, thus, creates a fine discontinuous gaseous phase in the composition. However, this production route requires the sensitized blasting agent to be prepared under pressure and, thus, requires specialized equipment adapted to handle the pressurized explosive.
- In light of the problems of the gas void addition methods of the prior art, it is an object of the present invention to provide a slurry or emulsion blasting agent which is sensitized by the addition of gas voids, wherein said gas voids are prepared and added to the blasting agent by a route other than those routes described hereinabove.
- Accordingly, the present invention provides an explosive composition sensitized by gas voids, wherein the gas voids have been distributed in said explosive composition by dispersal of an essentially gas-in-liquid foam.
- Preferably, the explosive composition comprises an oxidizing salt and a fuel and the explosive composition is a slurry or emulsion explosive.
- The term "foam" in this specification and claims, is used to describe a mass of bibles which have been dispersed in a liquid. The bubbles are surrounded by and, thus, separated from each other by thin, flexible films of liquid with, optionally, viscosity control agents or foaming agent molecules absorbed at the gas/liquid interface in order to stabilize the film.
- Most of the volume of a foam is the gas phase and typically, the gas phase comprises at least 90% by volume of the foam.
- The foam used in the present invention may be produced by introducing or "sparging" a pressurized gas into a closed vessel containing the pressurized liquid component of the foam, mixing and subsequently releasing the pressure on the system so as to create small gas bubbles within the liquid component. The foam produced can then be added to and blended into the base explosive composition by, for example, a low shear or a static mixer.
- The pressurized gas used to form the foam can be any gas which is compatible with other components of the explosive. Preferably, the gas is air, carbon dioxide or nitrogen but any other gas could be used provided that the solubility of the gas in the liquid is controllable over the time and temperature range to which the sensitized explosive will be stored prior to use.
- Bubbles can also be dispersed in the liquid carrier to produce a foam by mechanical agitation, such as, for example, by a high shear mixer, such as an Oakes mixer, or by low shear mixing of the liquid carrier to entrain gas voids within the liquid carrier. Mechanical agitation in the process of the present invention is, preferably, conducted on a non-explosive liquid carrier and, thus, is inherently safer and more effective than a process of entraining gas voids directly into the explosive composition.
- The foams of the present invention, preferably, have a low density in order to effectively lower the density of the explosive to which the foam is added. Preferably, the foam has a density of less than 0.2 g/ml and, more preferably, below 0.1g/ml and, even more preferably, below 0.06g/ml.
- As soon as a foam is created, the liquid phase which surrounds the individual bubbles will begin to drain so as to create a thinner layer at the top of the bubble than at the bottom. Eventually, the thinner layer will break causing coalescence of the bubble or loss of gas from the foam and the loss or drainage of the carrier liquid from the foam. The loss of gas is, thus, related to the 'drainage' rate of the foam in that the gas volume is reduced as liquid drains from the foam. The stability of the foam can, thus, be measured by determining the half-life of the foam wherein the half-life is the time taken for the loss of half of the gas volume from the foam. The half-life is, thus, an indication of the shelf life of the foam after the foam is produced.
- Control of the drainage rate and, thus, control of the half-life of the foam can be influenced and effectively controlled by the addition to the foam of additives which stabilize the liquid film around the bubble. If the foam is to be incorporated in the explosive shortly after it is produced, for example, within one to four minutes of production, foam stability is not as critical as for foams which are prepared and later added to the explosives.
- Additives, such as high viscosity polyisobutylene, act to increase the viscosity of the liquid film around the gas bubble. Further, additional additives, such as foaming agents are, preferably, added to the liquid carrier in order to assist in formation of the foam.
- Accordingly, the foams of the present invention, preferably, comprise a gas, a foaming agent, a viscosity control agent and a liquid carrier.
- The foaming agent provides a film around the gas bubbles in order to prevent them from bursting or coalescing. typical foaming agents would include materials such as proteins, and, more specifically, milk proteins, egg proteins, animal proteins, vegetable proteins, fish proteins, ond any mixture thereof. The foaming agent can also be a protein derivative or associated product, such as, phospholipids, lipoproteins, collagens, hydrolyzed proteins, and globulins. Steroids may also be used as a foaming agent.
- The foaming agent may also include surfactants, such as, for example, FC740* or FC751* which are perfluorinated surfactants, or mixtures of other surfactants. Other foaming agents include lanolin oil, derivatives of succinic anhydride, glycerol monostearate, steryl octazylene phosphate and long chain alcohols.
* Trade Mark - Casein is a mixture of proteins extracted from milk solids or soya beans, and can be used as is or can be fractionated into a water soluble portion or an oil soluble portion, each of which can be separately used as a foaming agent. The casein used may be totally or partially soluble in the oil but is, generally, dispersable so as to not be detrimental to foam production.
- The stability of the foam may also be enhanced by the addition of solid particles, such as, carbon black, talc or other materials known in the foam stabilization art.
- Viscosity in the foam can be controlled by the addition of viscosity control agent materials, such as, for example, high viscosity polyisobutylene, butyl rubber, natural rubber, bifunctional high molecular weight acids and the like and mixtures thereof to the liquid carrier which will increase the viscosity of the liquid component of the foam.
- Excessively high viscosity in the liquid component of the foam, however, is not desirable since the high viscosity will make preparation of the foam difficult. Thus, an optimum level of viscosity control agent is required in order to ensure that the drainage rate of the foam is low, but that the foam is relatively easy to produce.
- In an oil-based foam, the viscosity of the oil selected will also influence the ease with which the foam can be produced and the drainage rate of the foam. Selection of the oil will, thus, depend on, inter alia, the method of manufacture of the foam, mixing conditions, temperature, residence times, pressure, type of gas and the like.
- The foam can be added to sensitize any suitable explosive material wherein gas voids are advantageous. Explosive materials include, in particular, emulsion or slurry explosives but also include propellants, high have explosives, such as, Heavy ANFO, modified emulsions, cast explosives, nitro ester based systems, and TNT, RDX or NG based systems.
- The liquid carrier used to prepare the foam is a liquid which is, preferably, compatible with the continuous phase of the explosive and into which the preferred additives of the foaming system can be dispersed or dissolved. The liquid carrier may take part in the detonation as a fuel or comprise an oxidizer, a sensitizer, or it may be non-reacting.
- In a slurry explosive, water miscible liquids are preferred. In particular, the most preferred liquid for slurry explosives is water as a solvent or dispersion medium for desired additives or solutes.
- For an emulsion explosive, preferred liquids are non-aqueous oils and solvents which are miscible with the organic liquid phase. Most preferred, however, are liquids or liquifiable materials which act as fuels in the explosive reaction. Typically, fuels include, for example, paraffin oil and fuel oil. However, the liquid carrier need not be perfectly compatible with the continuous phase of the explosive provided that the explosive composition created remains sufficiently stable to allow adequate storage stability based on the proposed use of the explosive composition.
- Emulsion explosives includes low and essentially non-aqueous emulsions.
- The liquid carrier wilt, preferably, contribute to the total fuel phase present in the emulsion explosive and, thus, may be described as a fuel for the explosive, as described hereinabove. In the preparation of the foam, however, it is desirable to minimize the amount of liquid used in the production of the foam in order to maximize the amount of liquid which is available for pre-formation of the base emulsion explosive.
- The use of a non-aqueous liquid in a slurry explosive may also provide fuel value to the explosive composition.
- With the selection of a liquid carrier of a suitable viscosity, such as, for example, high viscosity paraffin oil, the use of a viscosity control agent can also be reduced or eliminated.
- Accordingly, the present invention provides a gassed explosive composition as described hereinabove wherein the gassing is achieved by a dispersed pre-formed foam and of which the liquid in said gas-in-liquid foam comprises a liquid or liquifiable fuel and a foaming agent.
- When the liquid carrier is water, it is preferable to add a material to the water which acts as a freezing point depressant and, thus, make the base explosive composition and/or the foam, to which the foam has been added, more stable in cold temperatures. A preferred freezing point depressant is ammonium nitrate. However, low-freezing point, water miscible liquids or liquid mixtures, such as, ethylene glycol and water can be used as a liquid carrier in place of water. The foam, once produced, is added to a base explosive composition, which base explosive composition is an insufficiently or non-sensitized emulsion or slurry explosive. The foam is, preferably, added to the base explosive composition shortly after its production, in order to minimize the need to create foams which are stable for long periods of time. It has been our experience that the use of foams having a half life of greater than one to four minutes is desirable in order to have sufficient time to mix the foam into the explosive composition.
- The foam is, preferably, added to the base explosive composition by a low shear mixing technique, such as, a static mixer or a ribbon mixer. During addition of the foam, the foam is broken and its gas bubbles are merely dispersed within the base explosive composition. At this stage, there is generally no need for intense mechanical agitation to entrain additional gas voids within the explosive composition.
- The present invention, thus, provides an explosive as described hereinabove wherein the explosive composition is an emulsion explosive. Preferably, the liquid carrier used to prepare the gas-in-liquid foam, which is to be added to the emulsion explosive, in a fuel.
- Further, the present invention also provides an explosive as described hereinabove wherein the explosive composition is a slurry explosive and, preferably, the liquid carrier used to prepare the gas-in-liquid foam, which is to be added to the slurry explosive, is water.
- The base explosive composition to which the foam sensitizer is added can be any chemically compatible emulsion or slurry explosive, which base explosive compositions are described in the prior art. These base explosive compositions generally consist of an oil-in-water or water in-oil dispersion of an aqueous solution of an oxidizing salt and a fuel.
- The oxidizing salt may be any of the oxygen-containing salts typically used in the industry. These salts include, for example, nitrates, chlorates, and perchlorates. Most preferred, are salts, such as, sodium nitrate, calcium nitrate, potassium nitrate, and, most preferably, ammonium nitrate or mixtures thereof. In slurry explosives, the oxidizing salt is dissolved in water to provide the continuous phase of the explosive composition. For an emulsion explosive, the oxidizing salt may be melted, (e.g. as an eutectic mixture) to provide a liquid which can be dispersed as a discontinuous phase into the fuel or, more preferably, may be dispersed into the fuel as a concentrated aqueous solution.
- The fuel phase may be any liquid or liquifiable fuel known within the explosives art and may be the same as or different than the fuel used in the preparation of the foam. Suitable materials include mineral oil, waxes, paraffin oils, benzene, toluene, xylenes, and mixtures of petroleum distillates such as gasoline, kerosene and diesel fuel.
- An emulsion explosive formed as an embodiment of the present invention, preferably, also include stabilizing surfactants, such as, for example, a mixture of sorbitan sesquioleate and a polyisobutylene succinic anhydride (PIBSA) based surfactant. These PIBSA based surfactants are described in Canadian Patent no. 1,244,463 (Baker). However, any surfactant of use in the emulsion explosive art may be used to prepare the emulsion to be used in the present invention.
- Many suitable conventional emulsifiers have been described in detail in the literature and include, for example, soribitan esters, such as, sorbitan sesquioleate, sorbitan mono-oleate, sorbitan mono-almitate, sorbitan mono-stearate and sorbitan tristearate, the mono- and di-glycerides of fat-forming fatty acids, soya bean lecithin ond derivatives of lanolin, such as, isopropyl esters of lanolin fatty acids, mixtures of higher molecular weight fatty alcohols and wax estes, ethoxylated fatty ethers, such as, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyalkylene oleyl laurate, and subsituted oxazolines, such as, 2-oleyl-4,4′-bis-(hydroxymethyl)-2-oxazolines. Suitable mixtures of such conventional emulsifiers may also be selected for use, together with one or more modifiers, in the compositions of the present invention.
- Accordingly, the present invention provides an emulsion explosive comprising a continuous fuel phase, a discontinuous oxidizer phase and a surfactant for stabilization of said emulsion which emulsion has been sensitized by the addition of a gas-in-liquid foam.
- The slurry explosives formed as an embodiment of the present invention, preferably, also include viscosity controlling additives, such as, for example, guar in order to increase to viscosity of the explosives so as to entrain the gas voids from the foam in the sensitized explosive formed.
- The explosive compositions of the present invention may also comprise additional additives to enhance or modify the properties of the explosive blasting agent. The use of these additives is commonly known within the explosives industry and include the solid dopes and sensitizers commonly added to emulsions, such as, aluminum, ferrosilicon, TNT, AN, MAN, PETN and the like. Further, additional sensitizing agents, such as, for example, glass microballoons, may also be used in combination with the foams of the present invention.
- In a further aspect, the present invention also provides a method of manufacturing a sensitized explosive composition comprising:
preparing a base explosive composition by emulsifying an aqueous solution of on oxidizer salt in a liquid or liquifiable fuel, or by emulsifying a liquid or liquifiable fuel in an aqueous solution of an oxidizer salt;
preparing an essentially gas-in-liquid foam by mixing a carrier liquid with a foaming agent to form a foaming solution and subjecting said solution to mechanical agitation, such as in a high shear mixer, low shear, or a static mixer, or other mixers known to those skilled in the art of foam manufacture, or to a pressurized gas sparge, or allowing it to foam by chemical reaction in the foam system, and
blending said gas-in-liquid foam into said base explosive composition. - In a still yet further aspect, the present invention also provides a method of blasting which comprises placing an explosive detonator in operative contact with an explosive and detonating said detonator.
- The invention will now be described by way of example only, with reference to the following examples.
-
- A foam was produced by sparging the foaming solution with a pressuring stream of nitrogen gas. A foam was produced having a gas volume of greater than 90% by volume, a foam density of 0.12g/ml and a half life of greater than 45 minutes.
-
- A foam was produced by mechanically agitating the foaming solution in a high shear mixer. A foam was produced having a gas volume of greater than 90% by volume, a foam density of 0.04g/ml and a half life of greater than 30 minutes.
- Emulsion explosive compositions comprising an oil based foam were prepared according to the present invention, having the formulations set out in Table 3. In each example, the foam was prepared according to the method and formulation as set out in Example 1.
- The oxidizer salt used in these examples was ammonium nitrate or an ammonium nitrate/sodium nitrate mixture.
- Paraffin oil was used for the oil phase in each example and a sufficient amount was added to produce a sensitized emulsion explosive with a 5% total oil phase. The total oil phase includes surfactants.
- In each example, the oxidizer salt solution was added to the oil phase containing a PIBSA based surfactant and sorbitan sesquioleate mixture while mixing in order to produce an emulsion explosive. Examples 3 and 4 were prepared using low shear mixing and Examples 5 and 6 were prepared by high shear mixing. The foam was dispersed into the emulsion by low shear mixing.
- The sensitized emulsion for each example was placed into a 25 or 50 mm cartridge in order to test the blasting ability of the explosive.
- The blasting ability of each composition was measured by determining the cap size needed to detonate the composition. Thus, in Table 3 under blast results, the cap size used and the blast result for each example is shown. Where measured, the velocity of detonation (VOD) for a successful blast is indicated.
- Examples 3 and 4 are typical of products which would be sold as "bulk" blasting agents and, thus, cap sensitivity is not expected. Examples 5 and 6 are typical of packaged products and cap sensitivity may be desirable. In all examples, explosives could be prepared using the foam sensitizer which had acceptable sensitivity for industrial use.
- Stability of the product produced was measured by storing the explosive composition of Example 6 for 3 months. As is shown in Table 3, the composition had an acceptable VOD after 3 months storage at 22°C.
-
- The explosive in this example was prepared by first emulsifying in a low shear mixer the AN/SN/water mixture in a paraffin oil and surfactant mixture. The emulsified mixture was, subsequently, mixed with ammonium nitrate prills to produce a doped emulsion and the oil based foam was added to sensitize the explosive. The doped emulsion had a VOD of 3970 m/s when initiated with a 40g Pentolite booster charge. The sensitivity of the doped emulsion was industrially acceptable for larger diameter applications.
-
- The explosive in this example was prepared by first emulsifying in a low shear mixer the AN/SN/water mixture in a paraffin oil and surfactant mixture. The emulsified mixture was, subsequently, mixed with ammonium nitrate prills to produce a Heavy ANFO explosive and the oil based foam was added to sensitize the explosive. The doped emulsion had a VOD of 3300 m/s when initiated with a 40g Pentolite booster charge. The sensitivity of the doped emulsion was industrially acceptable for larger diameter applications.
- Having described specific embodiments of the present invention, it will be understood that modification thereof may be suggested to those skilled in the art and it is intended to cover all such modifications as fall within the scope of the appended claims.
Claims (18)
- A explosive composition sensitized by gas voids, wherein the gas voids have been distributed in said explosive composition by dispersal of an essentially gas-in-liquid foam.
- An explosive composition as claimed in Claim 1 wherein the liquid in said gas-in-liquid foam comprises a liquid or liquifiable fuel and a foaming agent.
- An explosive composition as claimed in Claim 2 wherein said foaming agent is casein or a perfluorinated surfactant or a mixture thereof.
- An explosive composition as claimed in Claim 2 additionally comprising a viscosity control agent.
- An explosive composition as claimed in Claim 4 wherein said viscosity control agent is polyisobutylene or butyl rubber.
- An explosive composition as claimed in Claim 1 wherein the liquid in said gas-in-liquid foam comprises water and a foaming agent.
- An explosive composition as claimed in Claim 6 wherein said foaming agent is water soluble casein, or a perfluorinated surfactant or a mixture thereof.
- An explosive composition as claimed in Claim 6 wherein said gas-in-liquid foam additionally comprises a freezing point depressant.
- An explosive composition as claimed in Claim 8 wherein said freezing point depressant is ammonium nitrate.
- An explosive composition as claimed in Claim 1 wherein said explosive composition comprises an oxidizing salt and a fuel.
- An explosive composition as claimed in Claim 10 wherein said composition is an emulsion explosive.
- An explosive composition as claimed in Claim 10 wherein said composition is a slurry explosive.
- An explosive composition as claimed in Claim 1 wherein said gas-in-liquid foam comprises at least 90% by volume gas.
- An explosive composition as claimed in Claim 13 wherein said gas is carbon dioxide or nitrogen.
- An explosive composition as claimed in Claim 1 wherein said gas-in-liquid foam has a foam half-life of greater than 4 minutes.
- An emulsion explosive comprising a continuous fuel phase, a discontinuous oxidizer phase and a surfactant for stabilization of said emulsion which emulsion has been sensitized by the addition of a gas-in-liquid foam.
- A method of manufacturing a sensitized explosive composition comprising:
preparing a base explosive composition by emulsifying an aqueous solution of an oxidizer salt in a liquid or liquifiable fuel, or by emulsifying a liquid or liquifiable fuel in an aqueous solution of an oxidizer salt;
preparing an essentially gas-in-liquid foam by mixing a carrier liquid with a foaming agent to form a foaming solution and subjecting said solution to mechanical agitation or to a pressurized gas sparge or allowing it to foam by chemical reaction in the foam system; and
blending said gas-in-liquid foam into said base explosive composition. - A method of blasting comprising placing an explosive detonator in operative contact with an explosive as claimed in Claim 1 and detonating said detonator.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002040346A CA2040346C (en) | 1991-04-12 | 1991-04-12 | Explosive comprising a foamed sensitizer |
| CA2040346 | 1991-04-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0514000A1 true EP0514000A1 (en) | 1992-11-19 |
| EP0514000B1 EP0514000B1 (en) | 1998-01-28 |
Family
ID=4147388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP92303297A Expired - Lifetime EP0514000B1 (en) | 1991-04-12 | 1992-04-13 | Explosive comprising a foamed sensitizer |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0514000B1 (en) |
| JP (1) | JPH05279159A (en) |
| CN (1) | CN1057289C (en) |
| AU (1) | AU660967B2 (en) |
| CA (1) | CA2040346C (en) |
| DE (1) | DE69224230T2 (en) |
| GB (1) | GB2258461B (en) |
| MX (1) | MX9201658A (en) |
| NZ (1) | NZ242107A (en) |
| TW (1) | TW278070B (en) |
| ZA (1) | ZA922155B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001002318A1 (en) * | 1999-06-30 | 2001-01-11 | Orica Explosives Technology Pty Ltd | Manufacture of emulsion explosives |
| WO2002081411A3 (en) * | 2001-04-05 | 2002-12-27 | Istrochem A S | Modifier of emulsion explosive |
| CN112537993A (en) * | 2020-11-10 | 2021-03-23 | 安徽雷鸣科化有限责任公司 | Fluidized water gel explosive |
| CN114621042A (en) * | 2022-03-10 | 2022-06-14 | 安徽理工大学 | Powdery emulsion explosive for explosive welding |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5456729A (en) * | 1992-04-09 | 1995-10-10 | Ici Canada Inc. | Sensitizer and use |
| CN119191922A (en) * | 2024-09-13 | 2024-12-27 | 江西威源民爆器材有限责任公司 | A special foaming agent for preparing emulsion explosive and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3447978A (en) * | 1967-08-03 | 1969-06-03 | Atlas Chem Ind | Ammonium nitrate emulsion blasting agent and method of preparing same |
| DE1813175A1 (en) * | 1968-12-06 | 1970-07-02 | Du Pont | Compressed explosive bars on inorganic salt - and non explosive fuel |
| DE1930503A1 (en) * | 1969-06-16 | 1971-01-14 | Dynamit Nobel Ag | Explosive foam |
| GB1270319A (en) * | 1969-09-05 | 1972-04-12 | Ireco Chemicals | Method for preparing slurry explosive compositions of variable and controlled density |
| AU510416B2 (en) * | 1976-11-29 | 1980-06-26 | Ici Australia Limited | Explosive compositions |
| US4525225A (en) * | 1984-03-05 | 1985-06-25 | Atlas Powder Company | Solid water-in-oil emulsion explosives compositions and processes |
| GB2160857A (en) * | 1984-06-29 | 1986-01-02 | Peter Christian Shann | Explosive compositions |
| EP0228354A1 (en) * | 1985-12-23 | 1987-07-08 | Nitro Nobel Aktiebolag | A method for the preparation of a water-in-oil type emulsion eyplosive and an oxidizer composition for use in the method |
| FR2624112A1 (en) * | 1987-12-02 | 1989-06-09 | Ici Australia Operations |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1014356A (en) * | 1974-02-21 | 1977-07-26 | Canadian Industries Limited | Stabilized air bubble-containing explosive compositions |
-
1991
- 1991-04-12 CA CA002040346A patent/CA2040346C/en not_active Expired - Fee Related
-
1992
- 1992-03-24 ZA ZA922155A patent/ZA922155B/en unknown
- 1992-03-24 NZ NZ242107A patent/NZ242107A/en unknown
- 1992-03-26 TW TW081102342A patent/TW278070B/zh active
- 1992-04-09 AU AU14808/92A patent/AU660967B2/en not_active Ceased
- 1992-04-09 JP JP4088939A patent/JPH05279159A/en active Pending
- 1992-04-10 MX MX9201658A patent/MX9201658A/en unknown
- 1992-04-11 CN CN92102663A patent/CN1057289C/en not_active Expired - Fee Related
- 1992-04-13 GB GB9208130A patent/GB2258461B/en not_active Expired - Fee Related
- 1992-04-13 EP EP92303297A patent/EP0514000B1/en not_active Expired - Lifetime
- 1992-04-13 DE DE69224230T patent/DE69224230T2/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3447978A (en) * | 1967-08-03 | 1969-06-03 | Atlas Chem Ind | Ammonium nitrate emulsion blasting agent and method of preparing same |
| DE1813175A1 (en) * | 1968-12-06 | 1970-07-02 | Du Pont | Compressed explosive bars on inorganic salt - and non explosive fuel |
| DE1930503A1 (en) * | 1969-06-16 | 1971-01-14 | Dynamit Nobel Ag | Explosive foam |
| GB1270319A (en) * | 1969-09-05 | 1972-04-12 | Ireco Chemicals | Method for preparing slurry explosive compositions of variable and controlled density |
| AU510416B2 (en) * | 1976-11-29 | 1980-06-26 | Ici Australia Limited | Explosive compositions |
| US4525225A (en) * | 1984-03-05 | 1985-06-25 | Atlas Powder Company | Solid water-in-oil emulsion explosives compositions and processes |
| GB2160857A (en) * | 1984-06-29 | 1986-01-02 | Peter Christian Shann | Explosive compositions |
| EP0228354A1 (en) * | 1985-12-23 | 1987-07-08 | Nitro Nobel Aktiebolag | A method for the preparation of a water-in-oil type emulsion eyplosive and an oxidizer composition for use in the method |
| FR2624112A1 (en) * | 1987-12-02 | 1989-06-09 | Ici Australia Operations |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001002318A1 (en) * | 1999-06-30 | 2001-01-11 | Orica Explosives Technology Pty Ltd | Manufacture of emulsion explosives |
| WO2002081411A3 (en) * | 2001-04-05 | 2002-12-27 | Istrochem A S | Modifier of emulsion explosive |
| RU2286326C2 (en) * | 2001-04-05 | 2006-10-27 | Истрочем, А.С. | Modifying agent for emulsion explosive substance |
| CN112537993A (en) * | 2020-11-10 | 2021-03-23 | 安徽雷鸣科化有限责任公司 | Fluidized water gel explosive |
| CN114621042A (en) * | 2022-03-10 | 2022-06-14 | 安徽理工大学 | Powdery emulsion explosive for explosive welding |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9208130D0 (en) | 1992-05-27 |
| GB2258461A (en) | 1993-02-10 |
| MX9201658A (en) | 1992-10-01 |
| CA2040346A1 (en) | 1992-10-13 |
| GB2258461B (en) | 1994-10-05 |
| JPH05279159A (en) | 1993-10-26 |
| ZA922155B (en) | 1992-12-30 |
| DE69224230T2 (en) | 1998-05-28 |
| CN1065652A (en) | 1992-10-28 |
| EP0514000B1 (en) | 1998-01-28 |
| DE69224230D1 (en) | 1998-03-05 |
| CN1057289C (en) | 2000-10-11 |
| TW278070B (en) | 1996-06-11 |
| CA2040346C (en) | 2001-06-12 |
| AU1480892A (en) | 1992-10-15 |
| AU660967B2 (en) | 1995-07-13 |
| NZ242107A (en) | 1995-02-24 |
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