USRE26115E - Aqueous explosive slurries containing sulfur compounds having a low coeffi- cient of expansion - Google Patents
Aqueous explosive slurries containing sulfur compounds having a low coeffi- cient of expansion Download PDFInfo
- Publication number
- USRE26115E USRE26115E US26115DE USRE26115E US RE26115 E USRE26115 E US RE26115E US 26115D E US26115D E US 26115DE US RE26115 E USRE26115 E US RE26115E
- Authority
- US
- United States
- Prior art keywords
- explosive
- expansion
- composition
- sodium
- nitrate
- 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
Links
- 239000002360 explosive Substances 0.000 title description 76
- 239000002002 slurry Substances 0.000 title description 36
- 150000003464 sulfur compounds Chemical class 0.000 title description 6
- 239000000203 mixture Substances 0.000 description 98
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 229910001868 water Inorganic materials 0.000 description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 25
- 229910052782 aluminium Inorganic materials 0.000 description 23
- -1 thiosulfate anion Chemical class 0.000 description 22
- VWDWKYIASSYTQR-UHFFFAOYSA-N Sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 16
- AKHNMLFCWUSKQB-UHFFFAOYSA-L Sodium thiosulphate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 16
- 235000019345 sodium thiosulphate Nutrition 0.000 description 16
- 239000003921 oil Substances 0.000 description 15
- 239000012530 fluid Substances 0.000 description 14
- 229910001959 inorganic nitrate Inorganic materials 0.000 description 14
- 230000001235 sensitizing Effects 0.000 description 13
- 231100000202 sensitizing Toxicity 0.000 description 13
- 239000000446 fuel Substances 0.000 description 12
- DVARTQFDIMZBAA-UHFFFAOYSA-O Ammonium nitrate Chemical compound [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 description 11
- 239000004615 ingredient Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-L Sulphite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 9
- 239000002562 thickening agent Substances 0.000 description 9
- 235000010344 sodium nitrate Nutrition 0.000 description 8
- 239000004317 sodium nitrate Substances 0.000 description 8
- 239000007799 cork Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 7
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229920002907 Guar gum Polymers 0.000 description 5
- 239000004698 Polyethylene (PE) Substances 0.000 description 5
- 125000004432 carbon atoms Chemical group C* 0.000 description 5
- 239000000665 guar gum Substances 0.000 description 5
- 235000010417 guar gum Nutrition 0.000 description 5
- 229960002154 guar gum Drugs 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 150000003871 sulfonates Chemical class 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 4
- 239000000015 trinitrotoluene Substances 0.000 description 4
- 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 3
- 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 3
- 229960004321 Pentaerithrityl tetranitrate Drugs 0.000 description 3
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 description 3
- 229960000968 Pentaerythritol Tetranitrate Drugs 0.000 description 3
- 239000000026 Pentaerythritol tetranitrate Substances 0.000 description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000001351 cycling Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003349 gelling agent Substances 0.000 description 3
- 230000002427 irreversible Effects 0.000 description 3
- 235000012054 meals Nutrition 0.000 description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 3
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical class [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000003981 vehicle Substances 0.000 description 3
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N Barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 229960005069 Calcium Drugs 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
- YIXJRHPUWRPCBB-UHFFFAOYSA-N Magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N Potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N Strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000003159 antacid agent Substances 0.000 description 2
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 2
- 239000003830 anthracite Substances 0.000 description 2
- 230000001458 anti-acid Effects 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000001603 reducing Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000000087 stabilizing Effects 0.000 description 2
- 235000021307 wheat Nutrition 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- RMBFBMJGBANMMK-UHFFFAOYSA-N 2,4-Dinitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O RMBFBMJGBANMMK-UHFFFAOYSA-N 0.000 description 1
- WHJKCPTVEYZNOG-UHFFFAOYSA-N 6-(hydroxymethyl)-5-methoxy-2-[4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane-3,4-diol Chemical group COCC1OC(OC)C(OC)C(OC)C1OC1C(O)C(O)C(OC)C(CO)O1 WHJKCPTVEYZNOG-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N Aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 229960003563 Calcium Carbonate Drugs 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229940105329 Carboxymethylcellulose Drugs 0.000 description 1
- 244000068645 Carya illinoensis Species 0.000 description 1
- 235000009025 Carya illinoensis Nutrition 0.000 description 1
- 229920002301 Cellulose acetate Polymers 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- FYGDTMLNYKFZSV-MRCIVHHJSA-N Dextrin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)OC1O[C@@H]1[C@@H](CO)OC(O[C@@H]2[C@H](O[C@H](O)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O FYGDTMLNYKFZSV-MRCIVHHJSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- 229960002900 Methylcellulose Drugs 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 229920000715 Mucilage Polymers 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 241000282372 Panthera onca Species 0.000 description 1
- 235000010451 Plantago psyllium Nutrition 0.000 description 1
- 244000090599 Plantago psyllium Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004965 Silica aerogel Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- AGUIVNYEYSCPNI-UHFFFAOYSA-N Tetryl 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
- HWKQNAWCHQMZHK-UHFFFAOYSA-N Trolnitrate Chemical compound [O-][N+](=O)OCCN(CCO[N+]([O-])=O)CCO[N+]([O-])=O HWKQNAWCHQMZHK-UHFFFAOYSA-N 0.000 description 1
- WXVPJSABLBARMB-UHFFFAOYSA-N [O-2].[Zn+2].[N+](=O)([O-])[O-].[Na+] Chemical compound [O-2].[Zn+2].[N+](=O)([O-])[O-].[Na+] WXVPJSABLBARMB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000004948 alkyl aryl alkyl group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 235000010210 aluminium Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000008135 aqueous vehicle Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium(0) Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- 230000003247 decreasing Effects 0.000 description 1
- 230000001419 dependent Effects 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- HGCYUAJUOYGULZ-UHFFFAOYSA-N dialuminum;dicalcium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Ca+2].[Ca+2] HGCYUAJUOYGULZ-UHFFFAOYSA-N 0.000 description 1
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229920002457 flexible plastic Polymers 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- TZKHCTCLSRVZEY-UHFFFAOYSA-L magnesium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical class [Mg+2].[O-]S([O-])(=O)=S TZKHCTCLSRVZEY-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged Effects 0.000 description 1
- 230000002441 reversible Effects 0.000 description 1
- 239000012056 semi-solid material Substances 0.000 description 1
- 231100000489 sensitizer Toxicity 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 1
- 239000001187 sodium carbonate Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 1
- BRPNNYXZQLLLSN-UHFFFAOYSA-N sodium;dodecane Chemical compound [Na+].CCCCCCCCCCC[CH2-] BRPNNYXZQLLLSN-UHFFFAOYSA-N 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- 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
Definitions
- This invention relates to aqueous explosive slurries resistant to expansion upon exposure to elevated temperatures due to an unusually low ccefiicient of expansion with temperature.
- Explosive slurries containing appreciable quantities of water or other fluids have recently become of considerable interest in the explosive art. These mixtures have a greater versatility than dry mixtures, because they can be used under conditions where water cannot be excluded.
- the fluid content of the slurries is more than that which is absorbed by the components of the mixture, and is sufficient to act at least in :part as a suspending agent for the explosive ingredients. Such a fluid content in most cases ranges from about 0.5% to more than 30%, depending upon the materials present in the mixture, and upon the consistency desired.
- a slurry having a reasonably stiff consistency, containing as little as 10% fluid, may be preferred for use in bulk in wet bore holes where the composition may be diluted with fluids such as water already present. Thickening or gelling agents are employed when thick slurries are required containing high proportions of fluids. A slurry that can be poured may be desired for use in bulk in dry bore holes, and such a slurry is easily obtained by using a rather large portion of fluid, for example, to 50%, without a thickening or gelatinizing agent.
- the explosive compositions do not return to their original size, but to a size short of that.
- the explosive composition contained within the cartridge continuously exerts an undue pressure on the plastic container which is sufficient in time to cause rupture. Rupture is, of course, undesirable whenever it occurs.
- the high expansion coefficient may be due, in some small part at least, to phase changes or changes in hydration of the inorganic nitrate, it appears that only when aluminum is present does the volume change assume large and undesirable proportions.
- explosive slurries based on inorganic nitrates, aluminum and water can be so formulated as to have a low coeflicient of expansion with temperature, by incorporating therein a small amount of a thiosulfate or organic sulfonate.
- a thiosulfate or organic sulfonate not only do the compositions of the invention display a markedly reduced tendency to expand on heating, but if they expand, they return to approximately their original normal dimensions when the temperature is again lowered. Thus, they display essentially no irreversible expansion characteristics.
- the explosive slurrics of this invention are therefore more readily stored under a wide range of temperatures, and hence are safer to handle and use over such temperatures.
- the thiosulfates M S O which can be employed can be represented by the following formula:
- M is a cation and m and n are integers taken to satisfy the valences of M and the thiosulfate anion S 0
- Exemplary are the sodium, potassium, lithium, ammonium, calcium, barium and magnesium thiosulfates, which may be either in the anhydrous form or in the form of the respective hydrates.
- the organic hydrocarbon sulfonates which can be employed have the general formula RSO M, where M is a cation, such as alkali metal, such as sodium and potassium, ammonium, an alkaline earth metal, such as calcium or magnesium, or an organic amine such as triethanolarnine, and R is an organic hydrocarbon group, such as an alkyl, aryl, arylalkyl, alkylaryl or cycloalkyl group containing from about three to about fifty carbon atoms.
- Such hy drocarbon groups can also be substituted with carbonyl groups, ester groups, ehter group s, sulfide groups, culfuryl groups and additional sulfonate groups.
- Typical are the sodium petroleum hydrocarbon sulfonates, and the sodium benzene sulfonates, such as sodium benzene sulfonates, sodium dodecyl benzene sulfonate and sodium keryl benzene sulfonate.
- the benzene sulfonates have the structural formula:
- M is a cation and R is hydrogen or an alkyl group of from one to thirty carbon atoms.
- a preferred class of hydrocarbon sulfonates are the ester-substituted sulfonates. Such compounds have the structural formulas:
- R R and R are hydrocarbon groups containing from about one to about fifty carbon atoms.
- R and R can for example each be alkyl, aryl, alkylaryl, arylalkyl or cycloalkyl, and R can be a bivalent alkylene, arylene, alkylarylene, arlyalkylene or cycloalkylene group.
- R is a bivalent alkylene group and contains from about two to ten carbon atoms, and R, and R are alkyl groups containing from about five to about twenty carbon atoms.
- thiosulfate or sulfonate will be made with regard to the fluid or fluid mixture used as a vehicle for the slurry. It should be soluble or easily dispersible in the vehicle. If only certain compounds are available, their solubility characteristics may determine the nature of the vehicle. Thus, water or aqueous vehicles are usually required for the thiosulfates.
- the organic sulfonates can be used with water, oil, or mixtures thereof.
- the oxidizing agent employed in the explosive slurry of this invention should be an inorganic nitrate.
- Ammonium nitrate and nitrates of the alkali and alkaline earth metals such as sodium nitrate, potassium nitrate, calcium nitrate, magnesium nitrate, strontium nitrate and barium nitrate, are exemplary inorganic nitrates. Mixtures of several nitrates such as, for example, mixtures of sodium and ammonium nitrates, also yield excellent results.
- the inorganic nitrates may be fine, coarse, or a blend of fine and coarse materials. Mill and prill inorganic nitrates are quite satisfactory. For best results, the inorganic nitrates are usually fine grained.
- nitrate oxidizers there is generally employed one or more fuels, including metal fuels and carbonaceous fuels, and an amount of water or water and oil sufficient to give the mixture the consistency desired, be it the consistency of a semi-solid material or the consistency of a free-flowing slurry.
- fuels including metal fuels and carbonaceous fuels
- water or water and oil sufficient to give the mixture the consistency desired, be it the consistency of a semi-solid material or the consistency of a free-flowing slurry.
- a sensitizing explosive can also be included, as an optional component.
- the preferred sensitizing explosive is nitrostarch, but any sensitizing explosive known to the art can be used, alone or in admixture.
- Known sensitizing explosives which are useful include, for example, trinitrotoluene, dinitrotoluene, pentaerythritol tetranitrate, nitrostarch, tri- [methylolethene] methylolerhane trinitrate, pentolite (a mixture of equal parts by weight of pentaerythritol tetranitrate and trinitrotoluene), cyclonite (RDX, cyclotrimethylene trinitramine), nitrocellulose, Composition B (a mixture of up to 60% RDX, up to 40% TNT and l to 4% wax) Cycloto] (Composition B without the wax), tetryl, and smokeless powder such as carbine ball powder.
- the amount of thiosulfate or sulfonate required for a low coefficient of expansion in accordance with this invention is small. Generally, from 1 to 3% is employed for optimum results, although amounts as low as 0.3% give a reduction in the coefficient of expansion. More than about 3% would not usually be employed, as such large amounts are unnecessary to achieve the desired result, and therefore wasteful.
- nitrate oxidizer and of sensitizing explosive if used, will depend upon the sensitivity and explosive shock wave desired and these, again, are dependent upon the particular nitrate and sensitizing explosive.
- the proportions are not critical in any way.
- the nitrate oxidizer is used in an amount within the range from about to about 95%
- the sensitizing explosive can be used in an amount within the range from 0 to about 40% by weight of the explosive composition. From about to about sensitizing explosive and from about 50 to about 70% nitrate oxidizer give the best results.
- Sensitizing explosives of any particle size can be used. They can, for example, be fine, coarse, or a blend of fine and coarse material. Some materials, such as nitrostarch, are commercially available as very finely-divided powders, and so also is trinitrotoluene. Such available materials are employed to advantage, because in most cases they tend to produce compositions having a greater explosive effect.
- the explosive compositions of the invention include aluminum, preferably in particulate form, for example aluminum powder, atomized aluminum, granular aluminum, or flake aluminum, which also serves as a lubricity-improving agent.
- Aluminum can be used in the form of alloys such as aluminum-magnesium alloys.
- Other metal fuels can also be used in conjunction with the aluminum, such as, for example, magnesium and ferrosilicon.
- the metal fuel will usually comprise from about 0.5% to about 20% and preferably from 0.5 to 15% of the composition, of which fuel at least is aluminum. If the amount of aluminum exceeds 15%, best stabilization is obtained if the aluminum is coarse, i.e., if at least 50% of the particles are mesh or larger.
- a carbonaceous fuel can be included, such as powdered coal, petroleum oil, coke dust, charcoal, bagasse, dextrine, starch, wood meal, flour bran, pecan meal, and similar nut shell meals.
- a carbonaceous fuel when present will comprise from about 0.5 to about 30% of the mixture. Mixtures of metal and carbonaceous fuels can be used, if desired.
- An antacid, or other stabilizing material such as zinc oxide, calcium carbonate, aluminum oxide, and sodium carbonate, can also be added.
- Such ingredients will comprise from about 0.3 to about 2% of the mixture.
- the amount of water and other fiuid employed in the composition will vary with the consistency desired of the final mixture. Generally, when a semi-solid mixture is desired, especially for use in preparing cartridges, as little as 0.5% of water or mixture of water and other fluid such as oil can be used, and generally not more than 10% is needed. Where free-flowing slurries are desired, larger amounts of water or aqueous mixtures are generally employed, in most cases within the range of from about 10 to about 40%, although in some cases as much as 50% of fluid can be used.
- This slurry can be decreased to meet any need by incorporating a thickening or gelatinizing agent.
- a thickening or gelatinizing agent should be soluble or dispersible in the dispersing fluid and inert to the other ingredients present.
- the thickened slurry can be used to form explosive cartridges in the same manner as the slurries normally having a semi-solid consistency.
- An oil slurry can be thickened by any of the noncarbonaceous inorganic oil thickeners useful in making thickened oils and greases, such as finely divided silica, available under the trade names Cab-O-Sil and Ludox, and silica aerogels, for example Santocel ARD and Santocel C, and like inorganic gelling agents, such as alumina, attapulgite and bentonite, can be used.
- silica aerogels for example Santocel ARD and Santocel C, and like inorganic gelling agents, such as alumina, attapulgite and bentonite, can be used.
- Other oil-gelling agents are disclosed in U.S. Patent Nos. 2,655,476 and 2,711,393. These are well known materials, and any of these known to the art can be used.
- the amount of such thickening agent will depend on the consistency desired, and usually will be within the range from 0 up to about 5%.
- Enough thickener can be added to gel the oil, and water-proofing agents such as are disclosed in 5 US. Patent Nos. 2,554,222, 2,655,476 and 2,711,393 also can be incorporated as well to impart water resistance to the gelled oil slurry.
- An aqueous slurry can be thickened by any watersolu-ble or water-dispersible thickener, such :as, for example, carboxymethyl cellulose, methyl cellulose, guar gum, psyllium seed mucilage, and pregelatinized starches such as Hydroseal 3B.
- as for example, carboxymethyl cellulose, methyl cellulose, guar gum, psyllium seed mucilage, and pregelatinized starches such as Hydroseal 3B.
- the amount of such thickening agent will depend on the consistency desired, and usually will be within the range from to about 5%.
- the explosive of the invention can, if desired, be fired with the aid of a booster charge.
- Any conventional cap-sensitive booster charge available in the art can be employed.
- Pentaerythritol tetranitrate, Composition B and pentolite are exemplary.
- the booster charge preferably is non-shock or impact sensitive. The amount of booster charge required depends, of course, upon the amount and sensitivity of the explosive mixture.
- the explosive mixture is readily prepared by simple mixing of the ingredients.
- the solid materials including the thiosulfate or sulfonate, the inorganic nitrates and sensitizing explosives, if any, fuels, and antacid, if any, would usually be mixed at first, to form a homogeneous blend, and the slurrying liquid and slurry liquid thickener, if required, would be added with stirring to bring the mixture to the desired consistency
- the consistency is usually comparable to that of a gelled oil or thick, barely pourable mixture, and the mixture is filled or extruded into open-ended containers, using conventional filling or extrusion equipment, to produce the explosive package.
- the containers can be formed of any container material not dissolved or attacked by the slurry liquid or liquids.
- Heavy plastic is inexpensive and available in sufficient thickness of wall, and is therefore preferred.
- Typical plastic and cellulosic materials which can be used include polyethylene, ethyl cellulose, cellulose acetate, polypropylene, polytetrafluoroethylene, nylon, polyvinyl chloride, polystyrene and p-olyvinylidene chloride, and nonferrous metals, such as tin, copper and aluminum.
- Fibrous materials such as wood, paper, and cardboard can be used, if waterproofed or otherwise made resistant to the slurrying liquid.
- EXAMPLE 1 An explosive mixture of semi-solid consistency (A in the table below) was prepared using nitrostarch, fine grained mill ammonium nitrate, fine grained mill sodium nitrate, flake aluminum, anhydrous sodium thiosulfate, water and the additional ingredients noted in the table below.
- the nitrostarch oil and mixed nitrates were thoroughly blended and were then added to the zinc oxide, flake aluminum, guar gum and sodium carboxymethyl cellulose.
- the sodium thiosulfate was dissolved in the water and then added to the mixture.
- the proportions of the final explosive compositions were as follows:
- Composition A was quite stiif, and was easily extruded through conventional extrusion nozzles into cartridges 36 inches long by 1% inches in diameter made of string wrapped paper encased in polyethylene, 2 to 3 mils in thickness.
- a 4 gram cast pentolite booster containing a No. 6 blasting cap was inserted into the cartridge. The cartridge was then inserted in a bore hole 2% inches in diameter. The cartridge was fired, and gave a detonation rate greater than 5000 meters per second, indicating that the composition was a satisfactory explosive.
- each cycle included heating the cartridges at to 125 F. for 7 to 7 /4 hours, approximately equal to the time they might be subjected to that temperature under conditions of use, and then lowering the temperature to 66 to 68 F. After each cycle three diameter measurements were taken, at marked places on each cartridge, at both end and the center and the measurements were averaged, and reported as the average diameter of the cartridge at each cycle.
- test included a series of control cartridges prepared in the same manner except that the control explosive composition (B) did not contain sodium thiosulfate.
- Table I show the exceptionally low cefficient of expansion of the compositions of this invention.
- Cartridges Nos. 1 to 6 which were filled with explosive compositions containing sodium thiosulfate in accordance with this invention, showed a total increase in diameter over the entire treating period ranging from only 0.23% to 1.5.
- Five of the cartridges containing the explosive composition of this invention showed a percent increase in diameter of less than 0.8% over the entire cycle.
- none of the cartridges containing the explosive compositions of this invention had expanded sufficiently during the test to cause the rupture of the polyethylene cartridge.
- This composition was [bumped] bump loaded into /z by 6" test tubes, which were stoppered, leaving no air space, and stored at a temperature between 100 and 130 F. for five months. No expansion sufficient to blow off the test tube stopper was noted, indicating that no appreciable expansion of the explosive composition had occurred.
- EXAMPLE 3 Two compositions were prepared to show that the sulfur containing compound of this invention actually exerts its stabilizing action upon the nitrate and the aluminum components of the explosive slurry.
- the two compositions each contained 85 parts of sodium nitrate, 12 parts of flake aluminum and 3 parts of water. Two parts of sodium thiosulfate pentahydrate was then added to one of the compositions.
- Each of the compositions was placed in a test tube filled to within about one half inch of the brim and the tubes were then tightly stoppered. The test tubes were then placed in a water bath maintained at 98 C. The object of this experiment was to determine the time necessary for the cork to be forced out of the test tube because of the expansion of the nitrate-aluminum slurry.
- composition which did not contain sodium thiosulfate expanded sufiiciently so as to force the cork out of the test tube 24 minutes after immersion in the water bath.
- the composition embodying this invention i.e., the composition containing sodium thiosulfate had not expanded sufficiently to force the cork from the test tube after two hundred minutes, when the test was stopped.
- the same experiment was repeated, using 3 parts of anhydrous hours. The results are indicated in Table II. sodium thiosulfate in place of the 2 parts of the sodium Table II AVERA GE DIAMETER INCHES, AFTER HEATING, AT TEMPERATURE FOR TIME 24 hrs. at 106" 614111 5. 211392 24 hrs. at125 17 hrs. at 113 Increase in diameter Cartridge Initial, 1 cooled to F., cooled to F., Cooled to F., cooled to N0. F. 72 1*. 66 F. 66 F. 66 F.
- This example shows that sodium thiosulfate and the dioctyl ester of sodium sulfoscuccinic acid substantially inhibited thermal expansion of the composition.
- the coefficient of expansion of sodium nitrate varies with impurities in the batch, and this accounts for the fact that the composition in Example 3 forced the cork from the tube in 24 minutes, while the composition of the example required 85 minutes.
- Composition B was as good an explosive as the thiosulfate-free material A, but had a very low coetficient of expansion.
- An aqueous slurried explosive composition characterized by a low coefficient of expansion with temperature comprising an inorganic nitrate oxidizer in an amount within the range from about to about 95%, particulate aluminum in an amount within the range from about 0.5 to about an aqueous liquid in an amount to form a slurry, a sulfur compound selected from the group consisting of inorganic thiosulfates and organic sulfonates in an amount sutficient to inhibit the thermal expansion of the slurry.
- An aqueous slurried explosive in accordance with claim 1 containing sutficient water to impart to the composition a semi-solid consistency.
- An aqueous slurried explosive in accordance with claim 1 comprising a thickening agent in an amount to increase the consistency of the composition.
- An aqueous slurried explosive in accordance with claim 1 comprising an explosive sensitizer.
- a method of reducing the coefficient of thermal expansion of aqueous slurried explosive compositions comprising an inorganic nitrate oxidizer in an amount within the range from about 10 to about particulate aluminum in an amount within the range from about 0.5 to about 20%, and an aqueous liquid in an amount to form a slurry, which comprises incorporating therein a sulfur compound selected from the group consisting of inorganic thiosulfates and organic sulfonates in an amount sufiicient to inhibit thermal expansion.
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Description
United States Patent AQUEOUS EXPLOSIVE SLURRIES CONTAINING SULFUR COMPOUNDS HAVING A LOW COEFFI- ClENT 0F EXPANSION William L. Schwoyer, Allentown, Pa., assignor to Trojan Powder Company, Allentown, Pa., a corporation of New York No Drawing. Original No. 3,222,232, dated Dec. 7, 1965, Ser. No. 350,550, Mar. 9, 1964. Application for reissue Feb. 1, 1966, Ser. No. 532,500
Claims. (Cl. 149-41) Matter enclosed in heavy brackets appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.
This application is a C0nt1'miaIi0nin part of application Serial No. 226,728, filed September 27, 1962, now abandoned.
This invention relates to aqueous explosive slurries resistant to expansion upon exposure to elevated temperatures due to an unusually low ccefiicient of expansion with temperature.
Explosive slurries containing appreciable quantities of water or other fluids have recently become of considerable interest in the explosive art. These mixtures have a greater versatility than dry mixtures, because they can be used under conditions where water cannot be excluded. The fluid content of the slurries is more than that which is absorbed by the components of the mixture, and is sufficient to act at least in :part as a suspending agent for the explosive ingredients. Such a fluid content in most cases ranges from about 0.5% to more than 30%, depending upon the materials present in the mixture, and upon the consistency desired.
A slurry having a reasonably stiff consistency, containing as little as 10% fluid, may be preferred for use in bulk in wet bore holes where the composition may be diluted with fluids such as water already present. Thickening or gelling agents are employed when thick slurries are required containing high proportions of fluids. A slurry that can be poured may be desired for use in bulk in dry bore holes, and such a slurry is easily obtained by using a rather large portion of fluid, for example, to 50%, without a thickening or gelatinizing agent.
Such slurries, however, present a packaging problem not encountered with dry mixtures, because, due to their liquid content, they have a high coefllcient of expansion with temperature. This expansion creates special difliculties when explosive slurries are packaged in flexible plastic containers, since the explosive slurry must fill the entire plastic container so that air is excluded therefrom, leaving no air space for expansion. This means that the container must either expand and contract with the slurried contents, or rupture. Even if it expands, dimensions change, usually unevenly, with the result that the container may become oversized for a particular bore hole, and wedge at a bend in the bore hole, if it even fits the hole.
Expansion and contraction within the resiliency limits of the plastic cartridge can be tolerated, and by selecting an appropriate type, grade and thickness of plastic material, the relative expansion coetlicients can even be matched. However, some explosive mixtures, particularly those employing an inorganic nitrate as an oxidizer and a metal such as aluminum as a fuel, have an unusually high expansion coefficient, and require either thick containers, to prevent rupture, or very thin containers which have a high coefficient of expansion. Neither alternative is very desirable. In addition, such explosive slurries have a tendency to expand irreversibly. That is, upon being subjected to relatively hot day temperatures, the slurrics will expand, but when the temperature decreases, as at Re. 26,115 Reissued Nov. 22, 1966 nightfall or during normal climatic changes, the explosive compositions do not return to their original size, but to a size short of that. As a result, the explosive composition contained within the cartridge continuously exerts an undue pressure on the plastic container which is sufficient in time to cause rupture. Rupture is, of course, undesirable whenever it occurs.
While it is believed that the high expansion coefficient may be due, in some small part at least, to phase changes or changes in hydration of the inorganic nitrate, it appears that only when aluminum is present does the volume change assume large and undesirable proportions.
It has now been found, in accordance with the invention, that explosive slurries based on inorganic nitrates, aluminum and water can be so formulated as to have a low coeflicient of expansion with temperature, by incorporating therein a small amount of a thiosulfate or organic sulfonate. Not only do the compositions of the invention display a markedly reduced tendency to expand on heating, but if they expand, they return to approximately their original normal dimensions when the temperature is again lowered. Thus, they display essentially no irreversible expansion characteristics. The explosive slurrics of this invention are therefore more readily stored under a wide range of temperatures, and hence are safer to handle and use over such temperatures.
The thiosulfates M S O which can be employed can be represented by the following formula:
i! O O n M is a cation and m and n are integers taken to satisfy the valences of M and the thiosulfate anion S 0 Exemplary are the sodium, potassium, lithium, ammonium, calcium, barium and magnesium thiosulfates, which may be either in the anhydrous form or in the form of the respective hydrates.
The organic hydrocarbon sulfonates which can be employed have the general formula RSO M, where M is a cation, such as alkali metal, such as sodium and potassium, ammonium, an alkaline earth metal, such as calcium or magnesium, or an organic amine such as triethanolarnine, and R is an organic hydrocarbon group, such as an alkyl, aryl, arylalkyl, alkylaryl or cycloalkyl group containing from about three to about fifty carbon atoms. Such hy drocarbon groups can also be substituted with carbonyl groups, ester groups, ehter group s, sulfide groups, culfuryl groups and additional sulfonate groups. Typical are the sodium petroleum hydrocarbon sulfonates, and the sodium benzene sulfonates, such as sodium benzene sulfonates, sodium dodecyl benzene sulfonate and sodium keryl benzene sulfonate. The benzene sulfonates have the structural formula:
SO M
Where M is a cation and R is hydrogen or an alkyl group of from one to thirty carbon atoms.
A preferred class of hydrocarbon sulfonates are the ester-substituted sulfonates. Such compounds have the structural formulas:
wherein M is a cation as above and R R and R are hydrocarbon groups containing from about one to about fifty carbon atoms. R and R can for example each be alkyl, aryl, alkylaryl, arylalkyl or cycloalkyl, and R can be a bivalent alkylene, arylene, alkylarylene, arlyalkylene or cycloalkylene group. Preferably, R is a bivalent alkylene group and contains from about two to ten carbon atoms, and R, and R are alkyl groups containing from about five to about twenty carbon atoms.
The choice of thiosulfate or sulfonate will be made with regard to the fluid or fluid mixture used as a vehicle for the slurry. It should be soluble or easily dispersible in the vehicle. If only certain compounds are available, their solubility characteristics may determine the nature of the vehicle. Thus, water or aqueous vehicles are usually required for the thiosulfates. The organic sulfonates, on the other hand, can be used with water, oil, or mixtures thereof.
The oxidizing agent employed in the explosive slurry of this invention should be an inorganic nitrate. Ammonium nitrate and nitrates of the alkali and alkaline earth metals, such as sodium nitrate, potassium nitrate, calcium nitrate, magnesium nitrate, strontium nitrate and barium nitrate, are exemplary inorganic nitrates. Mixtures of several nitrates such as, for example, mixtures of sodium and ammonium nitrates, also yield excellent results. The inorganic nitrates may be fine, coarse, or a blend of fine and coarse materials. Mill and prill inorganic nitrates are quite satisfactory. For best results, the inorganic nitrates are usually fine grained.
In addition to the nitrate oxidizers, there is generally employed one or more fuels, including metal fuels and carbonaceous fuels, and an amount of water or water and oil sufficient to give the mixture the consistency desired, be it the consistency of a semi-solid material or the consistency of a free-flowing slurry. A sensitizing explosive can also be included, as an optional component.
The preferred sensitizing explosive is nitrostarch, but any sensitizing explosive known to the art can be used, alone or in admixture. Known sensitizing explosives which are useful include, for example, trinitrotoluene, dinitrotoluene, pentaerythritol tetranitrate, nitrostarch, tri- [methylolethene] methylolerhane trinitrate, pentolite (a mixture of equal parts by weight of pentaerythritol tetranitrate and trinitrotoluene), cyclonite (RDX, cyclotrimethylene trinitramine), nitrocellulose, Composition B (a mixture of up to 60% RDX, up to 40% TNT and l to 4% wax) Cycloto] (Composition B without the wax), tetryl, and smokeless powder such as carbine ball powder.
The amount of thiosulfate or sulfonate required for a low coefficient of expansion in accordance with this invention is small. Generally, from 1 to 3% is employed for optimum results, although amounts as low as 0.3% give a reduction in the coefficient of expansion. More than about 3% would not usually be employed, as such large amounts are unnecessary to achieve the desired result, and therefore wasteful.
The relative proportions of nitrate oxidizer, and of sensitizing explosive if used, will depend upon the sensitivity and explosive shock wave desired and these, again, are dependent upon the particular nitrate and sensitizing explosive. The proportions are not critical in any way. For optimum effect, the nitrate oxidizer is used in an amount within the range from about to about 95%, and the sensitizing explosive can be used in an amount within the range from 0 to about 40% by weight of the explosive composition. From about to about sensitizing explosive and from about 50 to about 70% nitrate oxidizer give the best results.
When the amount of sensitizing explosive is in the lower part of the range, or zero, a large booster is needed. At amounts beyond the sensitizing eflect falls off, and is no longer proportional to the amount of sensitizing explosive added, and therefore amounts beyond 40% are not usually used.
Sensitizing explosives of any particle size can be used. They can, for example, be fine, coarse, or a blend of fine and coarse material. Some materials, such as nitrostarch, are commercially available as very finely-divided powders, and so also is trinitrotoluene. Such available materials are employed to advantage, because in most cases they tend to produce compositions having a greater explosive effect.
In addition to these materials, as has been indicated, the explosive compositions of the invention include aluminum, preferably in particulate form, for example aluminum powder, atomized aluminum, granular aluminum, or flake aluminum, which also serves as a lubricity-improving agent. Aluminum can be used in the form of alloys such as aluminum-magnesium alloys. Other metal fuels can also be used in conjunction with the aluminum, such as, for example, magnesium and ferrosilicon.
The metal fuel will usually comprise from about 0.5% to about 20% and preferably from 0.5 to 15% of the composition, of which fuel at least is aluminum. If the amount of aluminum exceeds 15%, best stabilization is obtained if the aluminum is coarse, i.e., if at least 50% of the particles are mesh or larger.
In addition to the metal fuel, a carbonaceous fuel can be included, such as powdered coal, petroleum oil, coke dust, charcoal, bagasse, dextrine, starch, wood meal, flour bran, pecan meal, and similar nut shell meals. A carbonaceous fuel when present will comprise from about 0.5 to about 30% of the mixture. Mixtures of metal and carbonaceous fuels can be used, if desired.
An antacid, or other stabilizing material, such as zinc oxide, calcium carbonate, aluminum oxide, and sodium carbonate, can also be added. Such ingredients will comprise from about 0.3 to about 2% of the mixture.
The amount of water and other fiuid employed in the composition will vary with the consistency desired of the final mixture. Generally, when a semi-solid mixture is desired, especially for use in preparing cartridges, as little as 0.5% of water or mixture of water and other fluid such as oil can be used, and generally not more than 10% is needed. Where free-flowing slurries are desired, larger amounts of water or aqueous mixtures are generally employed, in most cases within the range of from about 10 to about 40%, although in some cases as much as 50% of fluid can be used.
In the case of oil, of course, the viscosity of the oil is a factor to be taken into consideration in determining the amount of fluid added. When mixtures of oil and Water are used, there would generally be employed from 2 to 10% water and from 10 to 30% oil, to give a slurry having a satisfactory fluidity.
The consistency of this slurry, particularly of a freeflowing slurry, can be decreased to meet any need by incorporating a thickening or gelatinizing agent. In this way, it is possible to prepare a thick slurry containing a large proportion of fluid for use in bulk in dry bore holes. The thickening agent should be soluble or dispersible in the dispersing fluid and inert to the other ingredients present. The thickened slurry can be used to form explosive cartridges in the same manner as the slurries normally having a semi-solid consistency.
An oil slurry can be thickened by any of the noncarbonaceous inorganic oil thickeners useful in making thickened oils and greases, such as finely divided silica, available under the trade names Cab-O-Sil and Ludox, and silica aerogels, for example Santocel ARD and Santocel C, and like inorganic gelling agents, such as alumina, attapulgite and bentonite, can be used. Other oil-gelling agents are disclosed in U.S. Patent Nos. 2,655,476 and 2,711,393. These are well known materials, and any of these known to the art can be used. The amount of such thickening agent will depend on the consistency desired, and usually will be within the range from 0 up to about 5%. Enough thickener can be added to gel the oil, and water-proofing agents such as are disclosed in 5 US. Patent Nos. 2,554,222, 2,655,476 and 2,711,393 also can be incorporated as well to impart water resistance to the gelled oil slurry.
An aqueous slurry can be thickened by any watersolu-ble or water-dispersible thickener, such :as, for example, carboxymethyl cellulose, methyl cellulose, guar gum, psyllium seed mucilage, and pregelatinized starches such as Hydroseal 3B. The amount of such thickening agent will depend on the consistency desired, and usually will be within the range from to about 5%.
The explosive of the invention can, if desired, be fired with the aid of a booster charge. Any conventional cap-sensitive booster charge available in the art can be employed. Pentaerythritol tetranitrate, Composition B and pentolite are exemplary. The booster charge preferably is non-shock or impact sensitive. The amount of booster charge required depends, of course, upon the amount and sensitivity of the explosive mixture.
The explosive mixture is readily prepared by simple mixing of the ingredients. The solid materials, including the thiosulfate or sulfonate, the inorganic nitrates and sensitizing explosives, if any, fuels, and antacid, if any, would usually be mixed at first, to form a homogeneous blend, and the slurrying liquid and slurry liquid thickener, if required, would be added with stirring to bring the mixture to the desired consistency Where cartridges are to be formed, the consistency is usually comparable to that of a gelled oil or thick, barely pourable mixture, and the mixture is filled or extruded into open-ended containers, using conventional filling or extrusion equipment, to produce the explosive package.
The containers can be formed of any container material not dissolved or attacked by the slurry liquid or liquids. Heavy plastic is inexpensive and available in sufficient thickness of wall, and is therefore preferred. Typical plastic and cellulosic materials which can be used include polyethylene, ethyl cellulose, cellulose acetate, polypropylene, polytetrafluoroethylene, nylon, polyvinyl chloride, polystyrene and p-olyvinylidene chloride, and nonferrous metals, such as tin, copper and aluminum. Fibrous materials such as wood, paper, and cardboard can be used, if waterproofed or otherwise made resistant to the slurrying liquid.
The following examples in the opinion of the inventor represent the preferred embodiments of this invention:
EXAMPLE 1 An explosive mixture of semi-solid consistency (A in the table below) was prepared using nitrostarch, fine grained mill ammonium nitrate, fine grained mill sodium nitrate, flake aluminum, anhydrous sodium thiosulfate, water and the additional ingredients noted in the table below. The nitrostarch oil and mixed nitrates were thoroughly blended and were then added to the zinc oxide, flake aluminum, guar gum and sodium carboxymethyl cellulose. The sodium thiosulfate was dissolved in the water and then added to the mixture. The proportions of the final explosive compositions were as follows:
Ingredients A B Invention Control Percent Percent Nitrostareh 25.8 26.2 Mill ammonium nitr 45 .1 47 .0 Mill sodium nitrate. 15 .5 14 .2 Flake eluminutn. 1.9 2.0 Zinc oxide 0.8 1.0 Sodium carboxymethyl cellulose 1 .0 1,0 Guar gum 0.7 0,8 011 N o. 5 0 .3 Sodium thiosulfate (anhydrous)... 1.2 r Water 7.1 I 7.8
Composition A was quite stiif, and was easily extruded through conventional extrusion nozzles into cartridges 36 inches long by 1% inches in diameter made of string wrapped paper encased in polyethylene, 2 to 3 mils in thickness. A 4 gram cast pentolite booster containing a No. 6 blasting cap was inserted into the cartridge. The cartridge was then inserted in a bore hole 2% inches in diameter. The cartridge was fired, and gave a detonation rate greater than 5000 meters per second, indicating that the composition was a satisfactory explosive.
Six of the cartridges so prepared were then subjected to expansion tests in four cycles. Each cycle included heating the cartridges at to 125 F. for 7 to 7 /4 hours, approximately equal to the time they might be subjected to that temperature under conditions of use, and then lowering the temperature to 66 to 68 F. After each cycle three diameter measurements were taken, at marked places on each cartridge, at both end and the center and the measurements were averaged, and reported as the average diameter of the cartridge at each cycle.
The test included a series of control cartridges prepared in the same manner except that the control explosive composition (B) did not contain sodium thiosulfate.
The results are recorded below in Table I. The difference between the initial diameter and the diameter after each of the cycles represents the irreversible expansion that has been acquired by the explosive composition. A burst cartridge is indicated by Table I AVERAGE DIAMETER IN INCHES AFTER HEATING AT TEMPERATURE AND TIME INDICATED Cartridge 7 hrs. at 100 7% hrs. at 7 hrs. at 7 hrs. at Increase in diameter No.with Initial, 66 E, cooled to 111) 1 E, cooled to F., cooled to No. thiosulfnte F. 66 F. cooled to 66 I 68 F.
composition 68 F. Total Percent 1. 293 1. 293 1. 300 1. 303 1. 313. 0. (I20 1. 5 1.277 1. 277 1. 280 1. 283 1. 257 0. (110 O. 78 1. 297 1. 293 1. 297 1. 2117 1 3110 0. 003 0. 23 1.270 I. 270 1. 273 l. 277 l 281] (1.011) (1.79 1. $3 1.273 1.273 1.277 1 283 0.010 O 78 1. 273 1. 277 1. 280 1. 280 1 283 0. D10 78 Control (no thiosuhate) 1. 297 l. 307 1. 330 C) I. 303 1.320 I. 343 1. 360 1. 287 1. 293 1. 3(13 1. 330 l. 287 1. 293 l. 303 1. 320 1. 273 1.283 1.290 1.307 1. 300 1.318 1.323 C) 1. 287 1. 290 1. 300 1. 313
fro
*The polyethylene cartridge burst at one end during the heating portion of the cycle, the explosive composition escaping therem.
The results of Table I show the exceptionally low cefficient of expansion of the compositions of this invention. Cartridges Nos. 1 to 6, which were filled with explosive compositions containing sodium thiosulfate in accordance with this invention, showed a total increase in diameter over the entire treating period ranging from only 0.23% to 1.5. Five of the cartridges containing the explosive composition of this invention showed a percent increase in diameter of less than 0.8% over the entire cycle. In addition, none of the cartridges containing the explosive compositions of this invention had expanded sufficiently during the test to cause the rupture of the polyethylene cartridge.
In contrast, four out of the seven cartridges which contained the control composition, the same composition as in Cartridges Nos. 1 to 6, except for the absence of sodium thiosulfate, were unable to withstand the test conditions, and ruptured as a result of the expansion of the explosive composition beyond the elastic limit of the polyethylene container during the course of the heating cycles. Of the three control compositions which survived the test conditions, No. 8 showed an increase in diameter of 6.4% and Nos. 12 and 13 showed increases of 3.3% and 4.4% respectively. It can only be assumed that had the four ruptured cartridges been able to survive the temperatures, their percent increase in diameter would have exceeded the 6.4% withstood by composition No. 8.
Thus, it can be seen that the presence of a small quantity of sodium thiosulfate not only decreases the amount of irreversible expansion suffered by the explosive composition but also inhibits the reversible thermal expansion acquired by the explosion compositions.
In order to test the effect of prolonged heating on the explosive compositions of this invention additional cartridges containing Composition A were subjected to a more rigorous test. After preparation, the cartridges were first held at a temperature of 70 F. for 24 hours and the diameters measured. The temperature was then raised to 105" F., maintained for 24 hours, and thereafter cooled to 72 F. for 24 hours. The temperature was then raised to 92 F., maintained for 6% hours, and lowered to 66 F. for 18 hours. Thereafter, the cartridges were maintained at 125 F. for 24 hours and then at 66 F. for 24 hours. The temperature was then raised to 113 F. for 17 hours and cooled to 66 F. for 7 8 EXAMPLE 2 The following explosive composition was mixed as in Example 1:
Ingredient: Percent Nitrostarch 22.75 Mill ammonium nitrate 48.15 Mill sodium nitrate 14.25 Flake aluminum 2.00 Sodium thiosulfate (anyhydrous) 1.00 Guar gum 1.00 Sodium carboxymethyl cellulose 0.60 Zinc oxide 1.00
Water 9.25
This composition was [bumped] bump loaded into /z by 6" test tubes, which were stoppered, leaving no air space, and stored at a temperature between 100 and 130 F. for five months. No expansion sufficient to blow off the test tube stopper was noted, indicating that no appreciable expansion of the explosive composition had occurred.
EXAMPLE 3 Two compositions were prepared to show that the sulfur containing compound of this invention actually exerts its stabilizing action upon the nitrate and the aluminum components of the explosive slurry. The two compositions each contained 85 parts of sodium nitrate, 12 parts of flake aluminum and 3 parts of water. Two parts of sodium thiosulfate pentahydrate was then added to one of the compositions. Each of the compositions was placed in a test tube filled to within about one half inch of the brim and the tubes were then tightly stoppered. The test tubes were then placed in a water bath maintained at 98 C. The object of this experiment was to determine the time necessary for the cork to be forced out of the test tube because of the expansion of the nitrate-aluminum slurry. It was found that the composition which did not contain sodium thiosulfate expanded sufiiciently so as to force the cork out of the test tube 24 minutes after immersion in the water bath. The composition embodying this invention, i.e., the composition containing sodium thiosulfate had not expanded sufficiently to force the cork from the test tube after two hundred minutes, when the test was stopped. The same experiment was repeated, using 3 parts of anhydrous hours. The results are indicated in Table II. sodium thiosulfate in place of the 2 parts of the sodium Table II AVERA GE DIAMETER INCHES, AFTER HEATING, AT TEMPERATURE FOR TIME 24 hrs. at 106" 614111 5. 211392 24 hrs. at125 17 hrs. at 113 Increase in diameter Cartridge Initial, 1 cooled to F., cooled to F., Cooled to F., cooled to N0. F. 72 1*. 66 F. 66 F. 66 F.
Total Percent 1. 267 1 273 1. 2 7 1 200 1. 293 0. 026 1. 6 1. 260 1 267 1. 207 1 270 1. 270 0. 010 0. 79 1. 273 1 263 1. 270 1 270 1. 270 -0. 003 0 1. 287 1 290 1. 287 1 310 1.313 0. 026 2. 0 1. 283 1 270 1. 280 1 280 1. 277 0. 006 0 1. 283 1 293 1. 293 1 333 1. 320 0. 037 2. 9 1. 277 1 280 1. 293 1 290 1. 200 0. 013 1. 0 1. 277 1 277 1. 280 1 2st) 1. 283 0. 006 0. 47 1. 273 1 273 1.273 1 207 1. 287 0. 014 17 0 1. 283 1 290 1. 290 1 300 1. 303 0. 020 1. 0 1. 270 1 270 1. 263 1 300 1. 300 0. 030 2. 4 1. .247 1 307 1. 313 1 317 1. 317 0. 020 1. 6 1. 290 1 280 l. 277 1 293 1. 300 0. 010 0. 78 1.307 1 307 1.303 1 330 1.333 0. 034 2. 6 1. 273 1 277 1. 273 1 280 1. 277 0. 004 0. 31 1. 287 1 297 1. 297 1 310 1.310 0. 023 1.8 1. 250 1 250 1. 253 1 260 1. 260 0. 010 0. 80 1. 260 1 273 1. 267 1 270 1. 276 0. 016 1. 3 1. 303 1 303 1. 317 1 363 I. 350 0. 047 3. 6
These results show that the explosive compositions of this invention are capable of withstanding very severe storage conditions.
thiosulfate pentahydrate used previously. After 305 minutes, when the test was stopped, the cork had still not been forced from the test tube.
9 EXAMPLE 4 A series of additional experiments was run using 85 parts of sodium nitrate, 12 parts of flake aluminum and 3 parts of water as the basic explosive composition. A thiosulfate or sulfonate was added, as noted in Table III below. Test tubes were filled with the composition and tightly corked, and the test tubes then immersed in water baths at 98 C. in order to determine the length of time necessary for the cork to be forced from the tube. This time is noted in Table III.
After this time, test was stopped without the cork having been forced from the tube.
This example shows that sodium thiosulfate and the dioctyl ester of sodium sulfoscuccinic acid substantially inhibited thermal expansion of the composition. The coefficient of expansion of sodium nitrate varies with impurities in the batch, and this accounts for the fact that the composition in Example 3 forced the cork from the tube in 24 minutes, while the composition of the example required 85 minutes.
EXAMPLE 5 Two explosive compositions were prepared as in Example l of the following ingredients:
Parts by weight Ingredients Nitrostarch Mill ammonium nitrate. Mill sodium nitrate Zinc oxide Unbleached wheat ilou Anthracite eoal. Flake aluminum Atomized alurninurn Mineral oil (100 S.S.U.)- Carbon black Sodium thiosuliate (anhydrous) Water Compositions A and B were substantially identical in explosive properties, but Composition B was found to have negligible coefiicient of expansion, as compared to Composition A without sodium thiosulfate.
EXAMPLE 6 Two explosive compositions were prepared as in Example l of the following ingredients:
Parts by weight Ingredients Nitrostarch 12. 30 12. 30 Mill ammonium nitrate 41. 00 41. 00 (To-arse ammonium nitrate 25. 00 25. 00 Mill sodium nitratc 9. 04 9. 04 Zinc oxide 0.20 0. 20 Unbleached wheat 110 r 3. 50 3. 50 Anthracite coal 2. b0 2. 50 Flake aluminum I 1.50 1. 50 Mineral Oil (100 S.S.U. a 135 0. 25 0. 25 Carbon black 0. 01 0.01 Sodium thiosultate (anhydrous). 1. 50 Water 5. 00 5. 00
The results indicated that Composition B was as good an explosive as the thiosulfate-free material A, but had a very low coetficient of expansion.
EXAMPLE 7 Two explosive slurry formulations were made up to the following formulations:
These formulations were packed in 1% x 8" cartridges and subjected to storage tests cycling between temperatures of 86 to 106 F. for a period of 46- days. Following are the results of the tests:
Limit of Limit of variation variation Density 1.39 1.38 1.40 1.36 Gain or loss in cc./volurnofr01n 150 cc. +10 +10 +2 3 Percent expansion (86 F.) +6.6 +6.6 +1.4 2.1
The results show that the sodium thiosulfate held expansion to a minimum under the test conditions.
EXAMPLE 8 Four explosive slurries were made up to the following formulation:
A B O D Ammonium nitrate, Monsanto Percent Percent Percent Percent E-Z prills 65. 65.00 21.50 21 .25 Sodium nitrate, mill 5.00 5.00 38.00 38 .00 Aluminum granules (Almeg M 30) 15 .00 15 .00 Riflle coal 1 .00 l .00 Guar gum (Jaguar 0.75 0.75 0.50 0.50
ater 13.00 13.00 14 .00 14.00 Sodium thiosuliate (anhydrous) 0.25 0.25
These formulations were packed in 1%" x 8" cartridges and subjected to storage tests cycling between temperatures of 86 to 106 F. for a period of 46 days. Following are the results of the tests:
Gain or loss in tie/volume from ee- Percent expansion The results show that the sodium thiosulfate (B and D) prevented expansion under the test conditions.
EXAMPLE 9 to the mixture. The proportions of the final explosive compositions were as follows:
These formulations were packed in 1 1" x 8" cartridges and subjected to storage tests cycling between temperatures of [68] 86 to 106 F. for a period of 7 days. Fol lowing are the results of the tests:
Gain or loss in (o/volume from 165 cc Percent expansion The results show that the sodium benzene sulfonate (B) prevented expansion under the test conditions.
The following is claimed:
1. An aqueous slurried explosive composition characterized by a low coefficient of expansion with temperature comprising an inorganic nitrate oxidizer in an amount within the range from about to about 95%, particulate aluminum in an amount within the range from about 0.5 to about an aqueous liquid in an amount to form a slurry, a sulfur compound selected from the group consisting of inorganic thiosulfates and organic sulfonates in an amount sutficient to inhibit the thermal expansion of the slurry.
2. An aqueous slurried explosive in accordance with claim 1 in which the sulfur compound is an inorganic thiosulfate.
3. An aqueous slurried explosive in accordance with claim 2 in which the thiosulfate is sodium thiosulfate.
4. An aqueous slurried explosive in accordance with claim 1 wherein the sulfur compound is an organic sulfonate.
5. An aqueous slurried explosive in accordance with claim 4 in which the sulfonate is an organic hydrocarbon sulfonate.
6. An aqueous slurried explosive in accordance with claim 4 in which the sulfonate is an ester-substituted hydrocarbon sulfonate.
7. An aqueous slurried explosive in accordance with claim 6 in which the sulfonate is an alkyl ester of sodium sulfosuccinate.
8. An aqueous slurried explosive in accordance with claim 1 in which the inorganic nitrate is ammonium nitrate.
9. An aqueous slurried explosive in accordance with claim 1 in which the inorganic nitrate is a mixture of ammonium nitrate and another inorganic nitrate.
10. An aqueous slurried explosive in accordance with claim 1 containing sutficient water to impart to the composition a semi-solid consistency.
11. An aqueous slurried explosive in accordance with claim 1 comprising a thickening agent in an amount to increase the consistency of the composition.
12. An aqueous slurried explosive in accordance with claim 1 comprising an explosive sensitizer.
13. An aqueous slurried explosive in accordance with claim 1 in which the slurrying liquid is water.
14. An aqueous slurried explosive in accordance with claim 1 in which the slurrying liquid is water and oil.
15. A method of reducing the coefficient of thermal expansion of aqueous slurried explosive compositions comprising an inorganic nitrate oxidizer in an amount within the range from about 10 to about particulate aluminum in an amount within the range from about 0.5 to about 20%, and an aqueous liquid in an amount to form a slurry, which comprises incorporating therein a sulfur compound selected from the group consisting of inorganic thiosulfates and organic sulfonates in an amount sufiicient to inhibit thermal expansion.
References Cited by the Examiner The following references, cited by the Examiner, are of record in the patented file of this patent or the original patent.
UNITED STATES PATENTS 3,094,069 6/1963 Hradel 149-43 X 3,111,437 11/1963 Hino et a1. 14946 3,116,185 12/1963 Wilson et a] 14946 X 3,121,036 2/1964 Cook et al 149-41 3,147,163 9/1964 Griflith ct al 14939 CARL D. QUARFORTH, Primary Examiner. B. R. PADGETT, Assistant Examiner.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Reissue No. 26,115 November 22, 1966 William L. Schwoyer It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 1, line 43, for "portion" read proportion column 2, lines 33, the formula should appear as shown below instead of as in the patent:
line 48, for "ehther" read ether same line 48, for "culfuryl" read sulfuryl column 7, line 7, for "1.5" read 1.5% column 9, line 6, for "composition" read compositions column 10, line 69, for "ntirate" read nitrate Signed and sealed this 29th day of August 1967.
(SEAL) Attest:
ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3369944A (en) * | 1963-06-12 | 1968-02-20 | Dynamit Nobel Ag Patentabteilu | Thickened aqueous detonator composition containing a brisant explosive |
FR2361319A1 (en) * | 1976-08-11 | 1978-03-10 | Ireco Chemicals | PERFECTED AQUEOUS EXPLOSIVE COMPOSITION AND ITS OBTAINING |
EP0084766A1 (en) * | 1982-01-26 | 1983-08-03 | Prb Nobel Explosifs | Continuous process for the production of sirupeous explosive compositions that can be cartridged on a cutting machine, and products so obtained |
-
0
- US US26115D patent/USRE26115E/en not_active Expired
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3369944A (en) * | 1963-06-12 | 1968-02-20 | Dynamit Nobel Ag Patentabteilu | Thickened aqueous detonator composition containing a brisant explosive |
FR2361319A1 (en) * | 1976-08-11 | 1978-03-10 | Ireco Chemicals | PERFECTED AQUEOUS EXPLOSIVE COMPOSITION AND ITS OBTAINING |
EP0084766A1 (en) * | 1982-01-26 | 1983-08-03 | Prb Nobel Explosifs | Continuous process for the production of sirupeous explosive compositions that can be cartridged on a cutting machine, and products so obtained |
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