WATER-IN-OIL EMULSION EXPLOSIVE CONTAINING ENTRAPPED GAS
United States Patent 3715247
A water-in-oil emulsion explosive composition comprising a carbonaceous fuel, an inorganic oxidizer, a detonation sensitizer, water, an emulsifier, and a gas. The detonation catalyst is an inorganic metal compound of atomic number 13 or greater, other than Groups Ia and IIa and other than dioxides. The detonation sensitizer greatly enhances the sensitivity of the compositions so that they are cap-sensitive, the preferred compositions being cap-sensitive in a 1-inch diameter cartridge.
US Patent References:
Plastic explosive and method of making it
De Wilde - August 1962 - 3049453
Ammonium nitrate-fuel oil blasting agent containing triethylene glycol dinitrate
Cooley - December 1963 - 3113060
Ammonium nitrate-containing emulsion sensitizers for blasting agents
Egly et al. - December 1964 - 3161551
Production of detonatable explosive emulsion preparations
Berthmann et al. - October 1965 - 3212945
Water-in-oil explosive emulsion containing organic nitro compound and solid explosive adjuvant
Berthmann et al. - December 1967 - 3356547
Plastic explosive and method of making it
De Wilde - August 1962 - 3049453
Ammonium nitrate-fuel oil blasting agent containing triethylene glycol dinitrate
Cooley - December 1963 - 3113060
Ammonium nitrate-containing emulsion sensitizers for blasting agents
Egly et al. - December 1964 - 3161551
Production of detonatable explosive emulsion preparations
Berthmann et al. - October 1965 - 3212945
Water-in-oil explosive emulsion containing organic nitro compound and solid explosive adjuvant
Berthmann et al. - December 1967 - 3356547
Application Number:
05/069433
Publication Date:
02/06/1973
Filing Date:
09/03/1970
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Export Citation:
Assignee:
ICI America Inc. (Wilmington, DE)
Primary Class:
Other Classes:
149/82, 149/40, 149/44, 149/47, 149/78, 149/38, 149/92, 149/85, 149/62, 149/76, 149/70, 149/71
International Classes:
C06B47/14; C06B47/00; C06B1/04
Field of Search:
149/47,92,38,40,41,42,44,43,62,70,71,76,78,82,85
Primary Examiner:
Padgett, Benjamin R.
Assistant Examiner:
Lechert Jr., Stephen J.
Claims:
What is claimed is
1. A cap-sensitive water-in-oil emulsion explosive composition comprising:
2. The composition of claim 1 wherein said other inorganic nitrate is sodium nitrate.
3. The composition of claim 1 wherein said oxidizer comprises about 55 to about 80 percent ammonium nitrate, about 5 to about 15 percent sodium nitrate, about 10 to about 35 percent ethylene diamine dinitrate, and about 5 to about 10 percent ammonium perchlorate.
4. The composition of claim 1 wherein up to about 10 percent of an auxiliary fuel is included.
5. The composition of claim 4 wherein said auxiliary fuel is aluminum or sulfur.
6. The composition of claim 1 wherein about 0.25 to about 2.0 percent of a gelling agent is included.
7. The composition of claim 6 wherein said gelling agent is guar gum.
8. A cap-sensitive water-in-oil emulsion explosive composition comprising:
9. The composition of claim 8 wherein said oxidizer comprises about 55 to about 80 percent ammonium nitrate, about 5 to about 15 percent sodium nitrate, about 10 to about 35 percent ethylene diamine dinitrate, and about 5 to about 10 percent ammonium perchlorate.
10. The composition of claim 8 wherein said gas is in the form of occluded air bubbles.
11. The composition of claim 8 wherein said gas is in a gas-entrapping material.
12. The composition of claim 8 wherein said composition includes up to about 10 percent auxiliary fuel.
13. The composition of claim 12 wherein said auxiliary fuel is aluminum or sulfur.
14. The composition of claim 13 wherein about 0.25 percent to about 2.0 percent of a gelling agent is included.
15. The composition of claim 14 wherein said gelling agent is guar gum.
16. A composition of claim 1 wherein said gas-entrapping material is selected from the group consisting of expanded perlite and hollow microspheres of phenol-formaldehyde, urea-formaldehyde, and glass.
1. A cap-sensitive water-in-oil emulsion explosive composition comprising:
2. The composition of claim 1 wherein said other inorganic nitrate is sodium nitrate.
3. The composition of claim 1 wherein said oxidizer comprises about 55 to about 80 percent ammonium nitrate, about 5 to about 15 percent sodium nitrate, about 10 to about 35 percent ethylene diamine dinitrate, and about 5 to about 10 percent ammonium perchlorate.
4. The composition of claim 1 wherein up to about 10 percent of an auxiliary fuel is included.
5. The composition of claim 4 wherein said auxiliary fuel is aluminum or sulfur.
6. The composition of claim 1 wherein about 0.25 to about 2.0 percent of a gelling agent is included.
7. The composition of claim 6 wherein said gelling agent is guar gum.
8. A cap-sensitive water-in-oil emulsion explosive composition comprising:
9. The composition of claim 8 wherein said oxidizer comprises about 55 to about 80 percent ammonium nitrate, about 5 to about 15 percent sodium nitrate, about 10 to about 35 percent ethylene diamine dinitrate, and about 5 to about 10 percent ammonium perchlorate.
10. The composition of claim 8 wherein said gas is in the form of occluded air bubbles.
11. The composition of claim 8 wherein said gas is in a gas-entrapping material.
12. The composition of claim 8 wherein said composition includes up to about 10 percent auxiliary fuel.
13. The composition of claim 12 wherein said auxiliary fuel is aluminum or sulfur.
14. The composition of claim 13 wherein about 0.25 percent to about 2.0 percent of a gelling agent is included.
15. The composition of claim 14 wherein said gelling agent is guar gum.
16. A composition of claim 1 wherein said gas-entrapping material is selected from the group consisting of expanded perlite and hollow microspheres of phenol-formaldehyde, urea-formaldehyde, and glass.
Description:
This invention relates to a water-in-oil emulsion explosive composition containing a detonation sensitizer.
Bluhm U.S. Pat. No. 3,447,978 discloses ammonium nitrate blasting compositions in the form of water-in-oil emulsions. While the compositions described in that patent have many advantages over conventional slurry blasting compositions, they are typically not cap-sensitive. Therefore, it is necessary to employ a booster in order to detonate them.
It has now been found that water-in-oil emulsion explosive compositions can be prepared which retain all of the advantages of the emulsion blasting agents described in the Bluhm patent but which, in addition, are cap-sensitive without the use of an explosive ingredient, the preferred compositions being cap-sensitive in diameters of 1 inch or even less, and this sensitivity is maintained at low temperatures (less than 20° F.) and over extended storage periods (at least three months). Thus, it is not necessary to employ a booster to detonate the compositions of this invention. The compositions of this invention have excellent water resistance and safety characteristics in that they have high resistance to burning, impact, friction, rifle bullets, and static. They do not cause headaches, as do compositions employing nitroglycerin, and they have unexpectedly high velocities (typically, 17,000 ft./sec.) in 1-inch diameters and unexpectedly high detonation pressures (typically, 90 to 110 kilobars).
Moreover, the greatly enhanced sensitivity of the compositions of this invention was brought about without the addition of any ingredient which is cap-sensitive in itself. The detonation sensitizers which are responsible for the increased sensitivity of the compositions of this invention need not be explosive at all, and, in fact, it is really quite amazing that such explosively inert compounds as copper chloride and iron oxide would function to increase the sensitivity of an emulsion explosive.
The cap-sensitive compositions of this invention comprise about 1 to about 10 percent (all percentages herein are by weight) carbonaceous fuel, about 55 to about 87 percent oxidizer, about 0.1 to about 15 percent detonation sensitizer, about 10 to about 25 percent water, about one-half to about 2 percent emulsifier, and sufficient gas to give the composition a density of about 0.9 to about 1.40 gms./cc. The preferred compositions which are cap-sensitive in 1-inch diameters comprise about 2 to about 6 percent carbonaceous fuel, about 75 to about 85 percent oxidizer, about 2 to about 6 percent detonation sensitizer, about 15 to about 20 percent water, about three-fourths to 1 1/4 percent emulsifier, and sufficient gas to give the composition a density of about 1.05 to about 1.25 gms./cc.
The compositions preferably contain a gelling agent which greatly increases storage stability. The preferred amount of gelling agent is about 0.25 to about 2.0 percent. Examples of suitable gelling agents include polyacrylamide, interpolymers of methyl vinyl ether and maleic anhydride and their salts, guar gum, etc.; guar gum is preferred.
The compositions may also contain up to about 10 percent auxiliary fuel, such as sulfur, sugar, urea, formamide, dimethyl formamide, carbon, aluminum, or magnesium, preferably aluminum, aluminum alloys, or sulfur for greatest sensitivity. Up to about one-third of the water may be replaced with a water-soluble fuel such as ethylene glycol, low molecular-weight alcohols such as methanol, ethanol, or propanol; however, water is preferred because of its economy and because it is a better solvent for the oxidizing salts. Other optional ingredients include glycerine, formamide, dimethyl formamide, sugar, and water-soluble alkylamines such as ethylene diamine and methylamine.
The carbonaceous fuel is a water-immiscible, emulsifiable fuel which is liquifiable at a temperature up to about 200° F. and preferably between about 110° F. and about 160° F. to facilitate aeration and packaging. Waxes having melting points of at least 80° F. and preferably in the range of about 110° F. to about 200° F. are usually suitable; examples include waxes derived from petroleums such as petrolatum wax, microcrystalline wax, and paraffin wax, mineral waxes such as ozocerite and montan wax, animal waxes such as spermacetic wax, and insect waxes such as beeswax and Chinese wax. A modified, highly cohesive micro-crystalline wax having a melting point of about 114°-119° F. and identified by the trademark "Indra 2119" sold by Industrial Raw Materials Corp. and a similar wax sold by the same company under the trademark "Indra 1153" having a melting point of about 150°-155° F. are preferred as they give good sensitivity and stability.
While greatest sensitivity is achieved if the carbonaceous fuel is 100 percent wax and this is preferred, up to about 60 percent of the wax may be replaced with an oil to increase long-term storage stability. Examples of suitable oils include the various petroleum oils, DNT, and various vegetable oils; a highly refined mineral oil sold by Atlantic Refining Co. under the trademark "Atreol 34 " is preferred if an oil is used as it gives good stability.
The oxidizer may be about 20 to about 95 percent ammonium nitrate (AN), about 5 to about 40 percent other inorganic nitrate, up to about 60 percent ethylene diamine dinitrate (EDDN), up to about 40 percent alkylamine nitrate or alkanolamine nitrate, and up to about 30 percent inorganic chlorate or inorganic perchlorate. The oxidizer which is preferred for greatest sensitivity comprises about 55 to about 80 percent (AN), about 5 to about 15 percent sodium nitrate (SN), about 10 to about 20percent EDDN, and about 5 to about 10 percent ammonium perchlorate (AP). Examples of suitable other inorganic nitrates include sodium nitrate, which is preferred for greatest sensitivity, potassium nitrate, lithium nitrate, calcium nitrate, magnesium nitrate, barium nitrate, zinc nitrate; examples of suitable alkylamine nitrates include methylamine nitrate, ethylamine nitrate, and propylamine nitrate; examples of suitable alkanolamine nitrates include ethanolamine nitrate, propanolamine nitrate, and isopropanolamine nitrate; examples of suitable chlorates include sodium chlorate, potassium chlorate, calcium chlorate, and lithium chlorate; examples of suitable perchlorates include ammonium perchlorate which is preferred for greatest sensitivity, sodium perchlorate, calcium perchlorate, potassium perchlorate, lithium perchlorate, magnesium perchlorate, barium perchlorate, and zinc perchlorate.
The detonation sensitizer is an inorganic metal compound of atomic number 13 or greater other than groups Ia and IIa of the periodic table and other than dioxides. The detonation sensitizer is preferably a compound of copper, zinc, iron, or chromium as they produce greatest sensitivity. Compounds of aluminum, manganese, cobalt, nickel, lead, silver and mercury are also suitable. For the purpose of this invention, silicon and arsenic are not considered to be metals. Nitrates, halides, chromates, dichromates, and sulfates are preferred for their sensitivity and solubility. Oxides may also be used but oxides are not as convenient as the other compounds because of their low solubility. Mixtures of various detonation sensitizers are also contemplated. If the detonation sensitizer is also an oxidizer, it is calculated as an oxidizer for the purpose of determining if the total amount of oxidizer present falls within the percentage ranges given for this invention.
The emulsifier is a water-in-oil emulsifier. Examples include emulsifiers derivable from sorbitol by esterification with removal of one molecule of water such as sorbitan fatty acid esters, for example, sorbitan monolaurate, sorbitan monooleate, sorbitan monopalmitate, sorbitan monostearate, and sorbitan tristearate. The mono- and diglycerides of fat-forming fatty acids are also useful. Further examples include polyoxyethylene sorbitol esters such as the polyoxyethylene sorbitol beeswax derivative materials and polyoxyethylene (4) lauryl ether, polyoxyethylene(2)-ether, polyoxyethylene(2)stearyl ether, polyoxyalkylene oleyl/laurate, oleyl acid phosphate, substituted oxazolines and phosphate esters. Mixtures of various emulsifiers may also be used.
The gas may be in the form of occluded air or in a gas-entrapping material such as, for example, phenol-formaldehyde or urea-formaldehyde hollow microspheres, expanded perlite, or hollow glass microspheres; if a combustible gas-entrapping material is used, it should be included as an auxiliary fuel for calculation purposes.
The compositions of this invention are preferably prepared by making a premix of the water, the inorganic oxidizer, and the detonation sensitizer and a second premix of the carbonaceous fuel and the emulsifier. The two premixes are heated, the first until the salts are in solution (about 120°-205° F.) and the second until the carbonaceous fuel has liquified (about 120° F. or more). They are then blended together and emulsified which incorporates occluded air into the composition (or gas-entrapping material is added at this point). Further details of the preparation of emulsion blasting agents may be obtained from Bluhm U.S. Pat. No. 3,447,978 which is herein incorporated by reference.
The following compositions were prepared by making a premix of the water, the inorganic oxidizer, and the detonation sensitizer at 160° F. and a second premix of the carbonaceous fuel and the emulsifier at 130° F. The first premix was then slowly added to the second premix with vigorous agitation to obtain a water-in-oil emulsion. The agitation was continued with cooling to occlude air (or air-entrapping material was dispersed) into the emulsion. The compositions were then extruded or tamped into high-density polyethylene tubes which were sealed with plastic caps and detonated.
The tables below give the compositions and the diameter and cap size with which they were detonated. Water of hydration is included as "water" and not as part of the detonation sensitizer. The density is the density when made except for compositions 6 and 20 where it is the density when detonated; these two compositions were detonated in 4-inch diameter cartridges in order that the velocity and detonation pressure could be determined. Velocity was determined by the electronic counter method in 1-inch diameter or greater and detonation pressure by the Aquarium method in 4-inch diameter. Examples 26, 27, and 44 are preferred, example 26 because of its storage stability and low temperature sensitivity and examples 27 and 44 because they are almost as good as examples 26 but are more economical. ##SPC1## ##SPC2## ##SPC3##
The wax used in composition 41 was a hydrocarbon wax having a small oil content sold by Arco Chemical Co. under the trademark "Amprol 5." The waxes used in the remaining compositions were microcrystalline waxes having melting points of 114°-119° F., 133° F., 142° F., and 153° F. sold under the respective trademarks "Indra 2119," (compositions 1-7, 10-17, 20, 22-26, 28, 30, 31, 33-40, 42, and 45) "Indra 1133-S," (compositions 8 and 9) "Indra 1142-S," (composition 21) and "Indra 1153" (compositions 18, 19, 27, 29, 32, 43, and 44) by Industrial Raw Materials Corp.
The oil in compositions 10, 11, 18, 19, 27, 29, 32, 43, and 44 was a highly refined mineral oil sold by Atlantic Refining Co. under the trademark "Atreol 34." The oil in composition 8 was a mineral oil sold by Industrial Raw Materials Corp. under the trademark "Indrol 34-53BE." The oil in composition 9 was an oxygenated olefinic oil sold by Alox Corp. under the trademark "Alox 600."
The emulsifier in compositions 15, 20, 25, 26, 33, 36, 37, 39-42, and 45 was sorbitan monooleate sold by Atlas Chemical Industries, Inc., under the trademark "Span 80." The emulsifier used in the remaining compositions was mono- and diglycerides of fat-forming fatty acids sold by Atlas Chemical Industries, Inc., under the trademark "Atmos 300."
The gelling agents in compositions 20 and 33 and in 25, 26, 41, and 42 were guar gum sold by Stein Hall Co. under the respective trademarks "Jaquar AC-1" and "Jaguar AC-4." In compositions 21 and 22 it was a gelling agent sold by Oil Center Research, Inc., under the trademark "TX-150" and determined by analysis to be about 33.5 percent boric acid, about 35.8 percent guar gum, about 22.9 percent water, about 6.7 percent polyacrylamide, and about 1.1 percent ester, probably triglyceride. In composition 23 the gelling agent was a high molecular weight interpolymer of methyl vinyl ethyl and maleic anhydride sold by GAF Corp. under the trademark "Gantrez AN169." The gelling agent in composition 24 was a half amide-half ammonia salt of an interpolymer of methyl vinyl ether and maleic anhydrate sold by GAF Corp. under the trademark "Gantrez AN4651."
Bluhm U.S. Pat. No. 3,447,978 discloses ammonium nitrate blasting compositions in the form of water-in-oil emulsions. While the compositions described in that patent have many advantages over conventional slurry blasting compositions, they are typically not cap-sensitive. Therefore, it is necessary to employ a booster in order to detonate them.
It has now been found that water-in-oil emulsion explosive compositions can be prepared which retain all of the advantages of the emulsion blasting agents described in the Bluhm patent but which, in addition, are cap-sensitive without the use of an explosive ingredient, the preferred compositions being cap-sensitive in diameters of 1 inch or even less, and this sensitivity is maintained at low temperatures (less than 20° F.) and over extended storage periods (at least three months). Thus, it is not necessary to employ a booster to detonate the compositions of this invention. The compositions of this invention have excellent water resistance and safety characteristics in that they have high resistance to burning, impact, friction, rifle bullets, and static. They do not cause headaches, as do compositions employing nitroglycerin, and they have unexpectedly high velocities (typically, 17,000 ft./sec.) in 1-inch diameters and unexpectedly high detonation pressures (typically, 90 to 110 kilobars).
Moreover, the greatly enhanced sensitivity of the compositions of this invention was brought about without the addition of any ingredient which is cap-sensitive in itself. The detonation sensitizers which are responsible for the increased sensitivity of the compositions of this invention need not be explosive at all, and, in fact, it is really quite amazing that such explosively inert compounds as copper chloride and iron oxide would function to increase the sensitivity of an emulsion explosive.
The cap-sensitive compositions of this invention comprise about 1 to about 10 percent (all percentages herein are by weight) carbonaceous fuel, about 55 to about 87 percent oxidizer, about 0.1 to about 15 percent detonation sensitizer, about 10 to about 25 percent water, about one-half to about 2 percent emulsifier, and sufficient gas to give the composition a density of about 0.9 to about 1.40 gms./cc. The preferred compositions which are cap-sensitive in 1-inch diameters comprise about 2 to about 6 percent carbonaceous fuel, about 75 to about 85 percent oxidizer, about 2 to about 6 percent detonation sensitizer, about 15 to about 20 percent water, about three-fourths to 1 1/4 percent emulsifier, and sufficient gas to give the composition a density of about 1.05 to about 1.25 gms./cc.
The compositions preferably contain a gelling agent which greatly increases storage stability. The preferred amount of gelling agent is about 0.25 to about 2.0 percent. Examples of suitable gelling agents include polyacrylamide, interpolymers of methyl vinyl ether and maleic anhydride and their salts, guar gum, etc.; guar gum is preferred.
The compositions may also contain up to about 10 percent auxiliary fuel, such as sulfur, sugar, urea, formamide, dimethyl formamide, carbon, aluminum, or magnesium, preferably aluminum, aluminum alloys, or sulfur for greatest sensitivity. Up to about one-third of the water may be replaced with a water-soluble fuel such as ethylene glycol, low molecular-weight alcohols such as methanol, ethanol, or propanol; however, water is preferred because of its economy and because it is a better solvent for the oxidizing salts. Other optional ingredients include glycerine, formamide, dimethyl formamide, sugar, and water-soluble alkylamines such as ethylene diamine and methylamine.
The carbonaceous fuel is a water-immiscible, emulsifiable fuel which is liquifiable at a temperature up to about 200° F. and preferably between about 110° F. and about 160° F. to facilitate aeration and packaging. Waxes having melting points of at least 80° F. and preferably in the range of about 110° F. to about 200° F. are usually suitable; examples include waxes derived from petroleums such as petrolatum wax, microcrystalline wax, and paraffin wax, mineral waxes such as ozocerite and montan wax, animal waxes such as spermacetic wax, and insect waxes such as beeswax and Chinese wax. A modified, highly cohesive micro-crystalline wax having a melting point of about 114°-119° F. and identified by the trademark "Indra 2119" sold by Industrial Raw Materials Corp. and a similar wax sold by the same company under the trademark "Indra 1153" having a melting point of about 150°-155° F. are preferred as they give good sensitivity and stability.
While greatest sensitivity is achieved if the carbonaceous fuel is 100 percent wax and this is preferred, up to about 60 percent of the wax may be replaced with an oil to increase long-term storage stability. Examples of suitable oils include the various petroleum oils, DNT, and various vegetable oils; a highly refined mineral oil sold by Atlantic Refining Co. under the trademark "Atreol 34 " is preferred if an oil is used as it gives good stability.
The oxidizer may be about 20 to about 95 percent ammonium nitrate (AN), about 5 to about 40 percent other inorganic nitrate, up to about 60 percent ethylene diamine dinitrate (EDDN), up to about 40 percent alkylamine nitrate or alkanolamine nitrate, and up to about 30 percent inorganic chlorate or inorganic perchlorate. The oxidizer which is preferred for greatest sensitivity comprises about 55 to about 80 percent (AN), about 5 to about 15 percent sodium nitrate (SN), about 10 to about 20percent EDDN, and about 5 to about 10 percent ammonium perchlorate (AP). Examples of suitable other inorganic nitrates include sodium nitrate, which is preferred for greatest sensitivity, potassium nitrate, lithium nitrate, calcium nitrate, magnesium nitrate, barium nitrate, zinc nitrate; examples of suitable alkylamine nitrates include methylamine nitrate, ethylamine nitrate, and propylamine nitrate; examples of suitable alkanolamine nitrates include ethanolamine nitrate, propanolamine nitrate, and isopropanolamine nitrate; examples of suitable chlorates include sodium chlorate, potassium chlorate, calcium chlorate, and lithium chlorate; examples of suitable perchlorates include ammonium perchlorate which is preferred for greatest sensitivity, sodium perchlorate, calcium perchlorate, potassium perchlorate, lithium perchlorate, magnesium perchlorate, barium perchlorate, and zinc perchlorate.
The detonation sensitizer is an inorganic metal compound of atomic number 13 or greater other than groups Ia and IIa of the periodic table and other than dioxides. The detonation sensitizer is preferably a compound of copper, zinc, iron, or chromium as they produce greatest sensitivity. Compounds of aluminum, manganese, cobalt, nickel, lead, silver and mercury are also suitable. For the purpose of this invention, silicon and arsenic are not considered to be metals. Nitrates, halides, chromates, dichromates, and sulfates are preferred for their sensitivity and solubility. Oxides may also be used but oxides are not as convenient as the other compounds because of their low solubility. Mixtures of various detonation sensitizers are also contemplated. If the detonation sensitizer is also an oxidizer, it is calculated as an oxidizer for the purpose of determining if the total amount of oxidizer present falls within the percentage ranges given for this invention.
The emulsifier is a water-in-oil emulsifier. Examples include emulsifiers derivable from sorbitol by esterification with removal of one molecule of water such as sorbitan fatty acid esters, for example, sorbitan monolaurate, sorbitan monooleate, sorbitan monopalmitate, sorbitan monostearate, and sorbitan tristearate. The mono- and diglycerides of fat-forming fatty acids are also useful. Further examples include polyoxyethylene sorbitol esters such as the polyoxyethylene sorbitol beeswax derivative materials and polyoxyethylene (4) lauryl ether, polyoxyethylene(2)-ether, polyoxyethylene(2)stearyl ether, polyoxyalkylene oleyl/laurate, oleyl acid phosphate, substituted oxazolines and phosphate esters. Mixtures of various emulsifiers may also be used.
The gas may be in the form of occluded air or in a gas-entrapping material such as, for example, phenol-formaldehyde or urea-formaldehyde hollow microspheres, expanded perlite, or hollow glass microspheres; if a combustible gas-entrapping material is used, it should be included as an auxiliary fuel for calculation purposes.
The compositions of this invention are preferably prepared by making a premix of the water, the inorganic oxidizer, and the detonation sensitizer and a second premix of the carbonaceous fuel and the emulsifier. The two premixes are heated, the first until the salts are in solution (about 120°-205° F.) and the second until the carbonaceous fuel has liquified (about 120° F. or more). They are then blended together and emulsified which incorporates occluded air into the composition (or gas-entrapping material is added at this point). Further details of the preparation of emulsion blasting agents may be obtained from Bluhm U.S. Pat. No. 3,447,978 which is herein incorporated by reference.
The following compositions were prepared by making a premix of the water, the inorganic oxidizer, and the detonation sensitizer at 160° F. and a second premix of the carbonaceous fuel and the emulsifier at 130° F. The first premix was then slowly added to the second premix with vigorous agitation to obtain a water-in-oil emulsion. The agitation was continued with cooling to occlude air (or air-entrapping material was dispersed) into the emulsion. The compositions were then extruded or tamped into high-density polyethylene tubes which were sealed with plastic caps and detonated.
The tables below give the compositions and the diameter and cap size with which they were detonated. Water of hydration is included as "water" and not as part of the detonation sensitizer. The density is the density when made except for compositions 6 and 20 where it is the density when detonated; these two compositions were detonated in 4-inch diameter cartridges in order that the velocity and detonation pressure could be determined. Velocity was determined by the electronic counter method in 1-inch diameter or greater and detonation pressure by the Aquarium method in 4-inch diameter. Examples 26, 27, and 44 are preferred, example 26 because of its storage stability and low temperature sensitivity and examples 27 and 44 because they are almost as good as examples 26 but are more economical. ##SPC1## ##SPC2## ##SPC3##
The wax used in composition 41 was a hydrocarbon wax having a small oil content sold by Arco Chemical Co. under the trademark "Amprol 5." The waxes used in the remaining compositions were microcrystalline waxes having melting points of 114°-119° F., 133° F., 142° F., and 153° F. sold under the respective trademarks "Indra 2119," (compositions 1-7, 10-17, 20, 22-26, 28, 30, 31, 33-40, 42, and 45) "Indra 1133-S," (compositions 8 and 9) "Indra 1142-S," (composition 21) and "Indra 1153" (compositions 18, 19, 27, 29, 32, 43, and 44) by Industrial Raw Materials Corp.
The oil in compositions 10, 11, 18, 19, 27, 29, 32, 43, and 44 was a highly refined mineral oil sold by Atlantic Refining Co. under the trademark "Atreol 34." The oil in composition 8 was a mineral oil sold by Industrial Raw Materials Corp. under the trademark "Indrol 34-53BE." The oil in composition 9 was an oxygenated olefinic oil sold by Alox Corp. under the trademark "Alox 600."
The emulsifier in compositions 15, 20, 25, 26, 33, 36, 37, 39-42, and 45 was sorbitan monooleate sold by Atlas Chemical Industries, Inc., under the trademark "Span 80." The emulsifier used in the remaining compositions was mono- and diglycerides of fat-forming fatty acids sold by Atlas Chemical Industries, Inc., under the trademark "Atmos 300."
The gelling agents in compositions 20 and 33 and in 25, 26, 41, and 42 were guar gum sold by Stein Hall Co. under the respective trademarks "Jaquar AC-1" and "Jaguar AC-4." In compositions 21 and 22 it was a gelling agent sold by Oil Center Research, Inc., under the trademark "TX-150" and determined by analysis to be about 33.5 percent boric acid, about 35.8 percent guar gum, about 22.9 percent water, about 6.7 percent polyacrylamide, and about 1.1 percent ester, probably triglyceride. In composition 23 the gelling agent was a high molecular weight interpolymer of methyl vinyl ethyl and maleic anhydride sold by GAF Corp. under the trademark "Gantrez AN169." The gelling agent in composition 24 was a half amide-half ammonia salt of an interpolymer of methyl vinyl ether and maleic anhydrate sold by GAF Corp. under the trademark "Gantrez AN4651."