US3839107A - Calcium nitrate explosive composition - Google Patents

Abstract

An explosive composition is provided containing calcium nitrate, a water miscible organic fuel and water.

Description

United States Patent Clark et a1.

[11] 3,839,107 Oct. 1,1974

CALCIUM NITRATE EXPLOSIVE COMPOSITION Inventors: Willard F. Clark; Thomas E.

Slykhouse, both of Midland, Mich.

Assignee: The Dow Chemical Company,

Midland, Mich.

Filed: Dec. 29, 1972 App]. No.: 319,899

Related U.S. Application Data Continuation of Ser. No. 34,183, May 4, 1970, abandoned.

U.S. Cl 149/22, 149/41, 149/46, 149/61 Int. Cl C06b 1/04 Field of Search... 149/22, 41, 43, 44, 46,149/61 Primary Examiner-Stephen J. Lechert, Jr. Attorney, Agent, or FirmBruce M. Kanuch ABSTRACT An explosive composition is provided containing calcium nitrate, a water miscible organic fuel and water.

42 Claims, 12 Drawing Figures CALCIUM NITRATE EXPLOSIVE COMPOSITION This is a continuation, of application Ser. No. 34,183- filed May 4, 1970, now abandoned.

BACKGROUND OF THE INVENTION Inorganic oxidizing salt based explosive compositions are well known in the art. Most of these compositions contain ammonium nitrate as the major inorganic oxidizing salt constituent. Certain other inorganic oxidiz' ing salts have been thought of as less potent or so sensitive and unstable as to be dangerous. Although, in some compositions a portion of the ammonium nitrate has been replaced by other inorganic oxidizing salts such as, for example, sodium nitrate, calcium nitrate, certain, perchlorates and other inorganic oxidizing salts. These optional inorganic oxidizing salts have been employed for various purposes, such as economy, fluidizing properties, sensitivity enhancement and the like. These inorganic oxidizing salt based explosive compositions vary from dry to slurry mixtures containing water and- /or other liquids, such as glycols, fuel oils and the like. A typical dry mix known in the art is ANFO which contains ammonium nitrate and fuel oil. Typical slurry explosive compositions contain inorganic oxidizing salts, normally a major portion comprising ammonium nitrate, water, a fuel and/or sensitizer and a thickening. agent.

It has also been proposed to employ various liquid organic solvents in amounts up to about 16 per cent by weight of these explosive compositions as supplemental fuels and fluidizing agents, e.g., formaldehyde, ethylene glycol and the like. Waterless slurries containing a liquid organic fuel as a solvent for ammonium nitrate or ammonium perchlorate and having a density greater than 1.8 grams per cubic centimeter have also been suggested.

Specifically, in the past calcium nitrate has been considered as a less potent minor substitute for a portion of the ammonium nitrate in certain inorganic oxidizing salt based compositions.

smaller diameters than prior ammonium nitrate based explosives.

SUMMARY OF THE INVENTION The present invention concerns a blasting agent comprising at least about 40 per cent by weight of a mixture of calcium nitrate, water, a second inorganic oxidizing salt, and a water miscible organic fuel. These four components are provided in proportions to each other so as to provide an effective blasting agent. Optionally up to 60 per cent of additives well known in the explosives art, e.g., organic and inorganic fuels, sensitizers, density control agents, thickeners and gelling agents, inorganic nitrate based explosive compositions can be incorporated into the blasting agent to provide certain desired characteristics.

BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1-4 are three dimensional diagrams encompassing compositions within the scope of the present invention.

FIG. 5 graphically illustrates certain data taken from Example 7.

FIG. 6 graphically illustrates certain data taken from 5 Example 10.

FIGS. 7-9 graphically illustrate certain data taken from Example 11.

FIGS. l0-12 graphically illustrate certain data taken from Example 12.

DETAILED DESCRIPTION OF THE INVENTION TABLE I Compositions Defined by Points of Geometric Shape as Per cent by Weight An explosive composition has now been discovered comprising calcium nitrate, a water miscible organic fuel component and water. The unique composition can be employed as an explosive, as an explosive additive, and as a base for preparing other explosives. These novel compositions have certain unique favorable char-, acteristics over other inorganic oxidizing salt based ex-= plosive compositions known in the art. Of the more important characteristics is better sensitivity and fluidity at lower temperatures even without the presence of additional sensitizers and fuels such as self-explosives, metals and the like. Also, the compositions are characterized as being detonable at higher densities and in cent. The volumes encompassed by the geometric.

shapes within each tetrahedron represent certain compositions within the scope of the present invention. In each Figure the corners of the geometric shapes will be defined thus defining a volume representing compositions of this invention.

The present invention comprises a blasting agent comprising from about 40 per cent to per cent by weight of a composition encompassed by the geometric shape defined by planes ABCDEF and A'B'C'D'E'F and the connecting planes in the regular tetrahedron of FIG. 1. The compositions defined by the points of the geometric shape are set forth in the following Table I.

Preferably the composition defined by FIG. 1 comprises at least 50 per cent by weight, more preferably 60 per cent by weight of the blasting agent of the present invention.

Preferably the compositions defined in FIG. 3 comprise at least about 50 per cent by weight, more preferably at least about 60 per cent by weight of the blasting agent of the present invention.

TABLE III Compositions Defined by Points of Geometric Shape as Per cent by Weight Another embodiment of the present invention is a blasting agent comprising from about 40 to about 100 per cent by weight of the composition encompassed by the geometric shape defined by planes ABCDE and ABCDE and the connecting planes in the regular tetrahedron of FIG. 2. The compositions defined by the points of the geometric shape are set forth in the following TABLE II. Preferably the compositions defined in FIG. 2 comprise at least 50 per cent by weight, more preferably at least 60 per cent by weight of the blasting agent of the present invention. 7

TABLE II Another blasting agent, which is especially effective at lower temperatures (less than about 32F) comprises at least about 60 per cent by weight of the composition encompassed by the geometric shape defined by planes ABCD and A'BCD and the connecting planes in the regular tetrahedron of FIG. 4. The compositions defined by the points of the geometric shape are set forth i the f l v aTa s iv.

Compositions Defined by Points of Geometric Shape as Per Cent by Weight Point in Water Miscible Inorganic Oxidizing Salt Tetrahedron H O Ca(NO Organic Fuel Other than Ca(NO;,)

A 4 23 23 50 B 4 55 41 C 4 73 23 O D 4 57 I5 24 E 4 27 I4 55 A 24 l8 I9 39 B 24 44 32 0 C 24 58 I8 0 D 24 45 l2 19 E 24 22 l l 43 TABLE IV Compositions Defined by Points of Geometric Shape as Per Cent by Weight Point in Water Miscible I Tetrahedron H 0 Cii(NO Organic Fuel 2nd Inorganic OXldlZll'tg Salt Still another embodiment of the present invention is 0 a blasting agent comprising from about 40 to about 100 per cent by weight of the composition encompassed by the geometric shape defined by planes ABCDE and ABCD'E and the connecting planes in the regular te tetrahedron of FIG. 3. The compositions defined by the points of the geometric shape are set forth in thsf l qwia Tab e J1 :v t

group consisting of =0, OH,-=NI-l,' or -NI-I I N, 8 and SH. Examples of groups of organic compounds which can be employed include certain compound amides; alcohols including both monoand polyhydric alcohols; alcohol ethers; carbohydrates (saccharides and polysaccharides); compounds which are hydroxy or polyhydroxy oxy derivative hydrocarbons including monosaccharides and disaccharides; sulpho compounds including sulphoamino and sulphoamido compounds; aldehydes and various salts of such compounds. Specific compounds include, for example, n-octylamine; sodium alkyl aryl polyether; alcohol sulfonates such as the i S OaNa (OCH CH ),OH in which x has an average value of about N,N-dimethyl formamide, l-hydroxy-2-. methoxy-4-allyl benzene; formamide; dimethyl sulfoxide; ethylene carbonate; glycerol; acetonitrile; acetic acid, glycolonitrile; ethylene glycol monomethyl ether; methanol; ethanol; furfuryl alcohol; diethylene glycol; sodium acetate; hexamethylene tetramine; hexamethylene tetramine monoand dinitrate; acrylonitrile, acetamide, glycine, ammonium gluconate; acrylamide; N,Ndimethyl acetamide; ethylene glycol; propylene glycol; urea; thiourea; formaldehyde; acetadehyde ammonia; methylacetyl carbinol; acetone cyanohydrin; Z-hydroxybutyraldehyde; pentylene glycol; benzylamine; butylamine, butyldiethanolamine; diacetone alcohol; diethylene-di-imide oxide ethanol hexylene glycol; methyl glycerinate; S-methyl-pyridine; thio diglycol; triethanol amine; benzyl hydrazine; synthetic sugar like materials; sugar, molasses, and mixtures of compatible compounds. Water soluble polymers may also be employed as fuels and in some instances also serve as thickening agents. Such polymers include, for example, polyamides, celluloses, guar, polyols, polyalkylamines, polyethyleneimines and other water miscible polymers containing at least one of the previously defined functional groups.

Preferred water miscible organic fuels include lower organic fuels containing from 1 to about 6 carbon atoms including, for example, alcohols, glycols, saccharides, amines or amides including as specific examples methanol, ethanol, ethylene glycol, propylene glycol, glycerol, formamide sorbitol, mannitol, isopropanol and mixtures thereof.

By miscible it is meant that the quantity of defined fuel in said mixtures is substantially completely mixable in the quantity of aqueous calcium nitrate solution present in said mixtures without separation of two phases. Organic fuel solvents which are solid at room temperature will normally produce a thicker, less fluid blasting agent than those organic fuel solvents which are fluid at about room temperature (e.g., 68-74F). By miscible it is meant that the defined fuel is preferably soluble in the liquid phase of the mixture to the extent of at least 2 percent by weight.

Inorganic oxidizing salts other than calcium nitrate which can be employed include. for example. alkaline earth metal and alkali metal nitrates, sulfates, chlorates, and perchlorates, and specifically ammonium nitrate, sodium nitrate, ammonium perchlorate, barium nitrate, ammonium sulfate, sodium sulfate, sodium perchlorate, potassium perchlorate and the like. It has been found that certain of these inorganic oxidizing salts enhance certain explosive characteristics of the calcium nitrate mixture while others may hamper certain explosive characteristics but are advantageous for other reasons. For example, some salts may be employed to balance oxygen at the expense of some other feature such as sensitivity. lt has been found that ammonium nitrate tends to increase the sensitivity of the calcium nitrate explosive to a certain degree while sodium nitrate tends to desensitize the calcium nitrate explosive when employed in amounts greater than about 30 percent byweight of the total composition but may be employed to adjust the oxygen balance of the compositions. Thus when additional inorganic oxidizing salts are employed it should be determined before hand what effect the salt will have on the final explosive. The inorganic oxidizing salts may be employed in particulate form, in solution or both. Ammonium nitrate is preferred as the additional inorganic oxidizing salt.

Supplemental sensitizers and/or fuels in addition to those previously described can also be employed in the present composition to alter or improve certain explosive characteristics of the composition. Those sensitizers and/or fuels normally employed in inorganic oxidizing salt based explosive compositions known in the art can be employed in the present invention. These fuels and sensitizers comprise, for example, metals. selfexplosives and non-explosive water insoluble carbonaceous or other fuels such as sulfur and mixtures of two or more of these materials. They are employed in amounts sufficient to enhance the base explosive compositions in the manner desired. For example, metal may be employed in an amount to provide a weight ratio of metal to the base composition of up to l l and more. The particle size distribution of the metal particles will effect certain characteristics of the blasting agent in a manner well known in the art. Finer metal, e.g., minus 200 mesh tends to sensitize the explosive composition to detonation while coarser metal tends to increase the power of the composition when exploded, but with less sensitizing effect. The use of such specific size metals are taught in US. Pat. Nos. 3,307,989 and 3,432,371, the teachings thereof being specifically incorporated herein by reference.

Particulate metals which can be employed include, for example, aluminum, magnesium, iron, silicon, titanium, aluminum alloys, magnesium alloys, ferrosilicon, silicon carbide, ferrophosphorous zinc, boron, and other like particulate metals which sensitize and/or function as a fuel in the explosive. Of particular importance are the light metals, e.g., aluminum, magnesium, beryllium alloys thereof and the like. Generally the metals range in size from about 4 to about +325 mesh US. Standard Sieve Series. For metals which might react with the composition certain inhibitors known in the explosives art may be employed to stabilize the compositions, e.g., mannitol, certain phosphorous containing compounds and the like may be employed.

Self-explosives as used herein refer to those nitrated organic substances which, by themselves are generally recognized in the art as an explosive and which can usually be detonated with a standard blasting cap. Examples of self-explosives which can be employed include organic nitrates. nitro compounds and nitroamines, such as TNT, pentaerythritoltetranitrate (PETN), cyclotrimethylenetrinitramine (RDX), cyclotetramethylenetetranitramine (RMX), tetryl, nitrostarch, and explosive grade nitrocellulose as well as mixtures of the aforesaid and other self-explosives. The selfexplosives can be in any of the conventional forms such as flake, pelleted or crystalline.

Examples of water insoluble carbonaceous nonexplosive fuels and sensitizers include finely divided coal and carbon, solid carbonaceous vegetable products such as corn starch, wood pulp, ivory nut meal and bagasse, organic liquids such as hydrocarbon oils, fuel oils, fatty oils, vegetable oils, and mixtures of two or more of these water insoluble carbonaceous nonexplosive fuels. These fuels may be blended into the water based mix with, for example, a suitable emulsifying agent to produce a water-in-oil or oil-in-water emulsion. They can also be used as a coating for nonsoluble fuels and other additives such as TNT, particulate metals and the like.

Any grade of calcium nitrate, e.g., anhydrous or hydrated may be employed in the present invention. Anhydrous grade, i.e., substantially free from water of hydration or absorbed water, or mono, di, tri, tetra or any other of the hydrated forms may be employed as well as water or organic liquid solutions of the hydrated calcium nitrate. When hydrated calcium nitrate is employed the water of hydration is considered in calculating the water content of the explosive. Thus the water present in the explosive may come from water of hydration, water may be added separately or a combination of the two can be employed.

Thickening and/or gelling agents can also be employed in the present compositions. These agents are employed in amounts to provide thickened, freeflowing pumpable to very stiff practically immobile compositions. The physical characteristics desired depend mainly on the ultimate use of the explosive. For example, in water-containing boreholes very strong gels are desired to prevent a leaching out and erosion of the explosive composition. Gelling and/or thickening agents are employed which will swell and/or can be crosslinked in the liquid system containing dissolved Ca(NO water, and the water soluble organic fuel. Examples of suitable gelling agents include synthetic polymers, e.g., polyethers, polyesters, polyacrylamide, polyamines; starches, metal alcoholates; polysaccharides; wheat flour; galactomannan gums, such as guar, karaya and the like. Specific thickening agents which may be employed include cellulose acetate, polyalkylene glycol, hydroxyalkyl cellulose, potato starch, wheat starch, corn starch, carboxymethyl hydroxyethyl cellulose, methyl cellulose, polyethyleneimine, carboxymethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, sodium polystyrene sulfontate, and the like. It has been found that cellulosic materials, e.g., carboxymethyl hydroxyethyl cellulose, methyl and ethyl cellulose, and the like are preferred in the present invention. Examples of thickeners which provide thickening and suspending characteristics by physical form include magnesium oxides, asbestos fibers, cotton fibers, glass fibers, wood fibers, and the like.

Various density control agents can also be employed in the present invention. These materials can be employed to decrease the density of the explosive, to sensitize the composition, to alter the energy release of the explosive composition and/or to provide compositions which can be more readily exploded under elevated pressures and/or low temperatures. Suitable density control agents include void-containing materials, for example, hollow spheres prepared from metals, clays, glass, thermoplastics, resins and other like materials. Specific examples of void-containing materials can be found in U.S. Pat. No. 3,456,589 and 3,ll,288 the teaching of these patents'being incorporated herein by reference. Also naturally occurring void-containing materials such as ground corn cobs, bagasse, walnut shells and other like materials known in the art can be employed in the explosive. The carbonaceous thickening, gelling and density control agents also provide additional fuel for the explosive composition. Also void generating chemicals may be employed to form gaseous voids in situ. Examples of such chemicals include certain nitrites alone or in combination with sulfamic acid, certain sulfamates, carbonates or bicarbonates. Other such void generating compounds include, for example, combinations of carbonates or bicarbonates and acids, e.g., HCl and the like.

The compositions of the present invention range from watery clear fluid substances to very thick masses containing particulates, e.g., particulate inorganic oxidizing salts and/or sensitizers, and/or fuels.

The explosive compositions of the present invention may be prepared in the following manner. The requisite amount of water soluble organic fuel and water are mixed together. Any density control agents which may be employed are then added to this mixture. Particulate materials, e.g., calcium nitrate, inorganic oxidizing salts, metals, etc. are then blended into the liquid mixtures and stirred until a uniform mixture is formed. The thickening agent, preferably dispersed in a dispersing agent, e.g., particulate salts or a water soluble liquid in which the polymer does not swell or swells very slowly, e.g., propylene glycol, is then blended in and the composition stirred until the viscosity becomes sufficient to hold the particulate constituents in suspension.

The compositions are unique in that they are more sensitive to detonation at low temperatures, maintain better fluidity at low temperatures, and can be detonated at higher densities at low temperatures than similar explosives which contain ammonium nitrate as the major inorganic oxidizing salt. Likewise, in addition to all of these favorable characteristics certain of the compositions normally release energy upon explosion thereof, which is equal to and even in some instances greater than similar types of known ammonium nitrate based explosives compositions.

The following examples will facilitate a more complete understanding of the present invention.

In the following examples a thin walled cylindrical polyethylene container about 1 /8 inches in diameter and having a volume capacity of about 167 cc was filled with a test composition having a known density and temperature. The filled container was centered on a cylindrical steel driving plate about 4 inches in diameter and five-eighths inch thick (except as otherwise noted herein). The driving plate in turn was centered on the top of a l 1% inch diameter by 3 inch long cylindrical cast lead block. The lead block was placed on top of a 6 inch diameter by l /2 inch thick cylindrical steel base plate which was placed on the ground. A detonator and high explosive booster charge was placed on top of the polyethylene container and the test composition detonated. The decrease in the height of the lead block was then measured.

Example 1 26 compositions (Table V) were prepared containing in different proportions either formamide, ethylene glycol, or 50/50 weight ratio formamide/ethylene glycol mixture as the water soluble organic fuel, ammonium nitrate, fertilizer grade calcium nitrate and water. Each of these compositions was tested in the standard lead block detonation test, as previously defined, employing a 37 gram 50/50 pentolite booster (a cast mixture of equal parts of pentaerythritol tetranitrate and trinitrotoluene) and a No. 6 blasting cap as a detonator. The densities of the compositions were controlled by the addition of plastic microballoons which had a bulk density of about 0.03 gm/cc.

The samples to be tested were prepared by blending the water, fuel, plastic balloons and ground I IH,,NO and Ca( NO with stirring for from 6 to8 hours. The plastic balloons were added in an amount to provide the density desired in each test. About 1.5 parts by weight (per 100 parts of total mix) of carboxymethyl hydroxyethyl cellulose gelling agent was blended with about 3 parts by weight of propylene glycol and this blended into the slurry. The thickening agent and propylene glycol which were added are characteristic of water soluble organic fuels which can be employed in the present invention. The amount of such additional fuel was taken into consideration when determining the scope of the present invention as definedherein. The

H 0, and Series 3 and 5, 10 percent additive H O).

Table V shows the constituents contained in base compositions Nos. l26 as percent by weight. In each series fertilizer grade calcium nitrate prills (CNF) were employed. A chemical analysis of CNF showed 4.5 percent ammonium nitrate, -l4.4 percent water. -80.5 percent calcium nitrate with the balance being inert.

Tables VI XI show the results of the lead block tests in Series l6 as defined above. AH represents the deformation (inches) of the lead block for each shot. X represents the lead block deformation divided by the density of the composition tested. This factor allows for the comparison of AH values where the compositions being compared did not have equal densities, since for fully propagating explosives the deformation for like volumes of explosive is proportional to the densities of the explosives.

TABLE v Basic Compositions Tested. as Per Cent by Weight Water Soluble compositions were allowed to thicken to a rubbery con- Organic NO. Fuel nil-1.190 CNF slstency and then placed 1n the lead block contamers.

An attempt was first made to detonate each composi- 1 tion at a temperature of 45F. If the lead block was not g 35 5 deformed more than about 0.5 inch at that temperature 4 20 o 30 5 35 10 a l1ke composltlon was then usually tested at F. If, 6 35 0 however, the lead block was deformed more than about 7 0.5 inch at 45F, a like composition was then tested at g 5; $3 52 32F and if a deformation occurred there, a like com- 9 27 2g position was then tested at 10F. The 0.5 inch deforma- 5 i; 64 tion was an arbitrarily chosen cut off point based on 12 27 0 73 previous observations that when a composition failed [3 T; g; to give such a deformation it also usually failed at a 14 19 48 33 lower temperature. Six Series of tests were run; em- :2 :8 3g ploying 26 different base compositions. The Series dif- 40 17 19 18 63 fered from each other first, in that in Series 1, 2 and 3 :8 {g g g] formamide was employed as the fuel and in Series 4, 5 and 6 ethylene glycol was employed as the fuel. Seg? {8 28 condly, Series 2, and 3, 5 and 6 differed from Series I 12 10 40 50 and 4 in that an additional amount of water above that 45 52 :8 38 38 present as hydration of the calcium nitrate was added 25 0 10 30 to the compositions (Series 2 and 5, 5 percentadditive 26 u TABLE VI Series No. l. Formamide Fuel Base Composition 10"F 32"1= 45F 60F No. AH Density X AH Density X AH Density X AH Density X 1 0 1.12 0 0 1.13 0 2 0 1.16 0 0 1.16 0 3 0 1.14 0 0 1.14 0 4 0 1.15 0 .14 1.13 .123 5 0 1.19 0 .98 1.19 .823 6 0 1.23 0 0 1.25 0 7 0 1.20 0 0 1.20 0 g 0 1.18 0 0 1.18 9 0 1.22 0 .79 1.22 .647 9A .11 1.17 10 .61 1.18 .52 .85 1.20 .708 1.08 1.19 .907 11 .73 1.25 .58 .85 1.21 .702 .95 1.25 .759 12 0 1.22 0 .72 1.25 .575 .86 1.23 .699 13 0 1.16 0 0 1.17 0 14 0 1.18 v 0 .83 1.17 .709 1 4A 0 1.17 15 .55 1.19 .462 .86 1.20 .716 16 .52 1.24 .42 .83 1.27 .653 .94 1.23 .764- 17 .40 1.27 .32 .48 1.27 .377 .77 1.27 .606 18 .35 1.29 V .271 .73 g 1.27 .574

TABLE VI -Continued Series No. 1, Formamide Fuel Base Composition 10F 32F 45F 60F No. AH Density X AH Density X AH Density X AH Density X 19 .31 1.24 .250 .48 1.24 .387 20 .64 1.17 .54 .76 1.16 .655 .79 1.15 .686 21 .66 1.17 .564 .78 1.16 .672 21A .74 1.17 22 .08 1.26 .063 .65 1.21 .537 22A .18 1.2.3, 23 1.23 0 .58 1.24 .467 23A 0 1.23 24 O 1.24 0 0 1.26 0 25 .43 1.26 .341 .54 1.23 .439 25A .47 1.26 26 0 1.46 0 0 1.47 0

TABLE V11 Series No. 2 Formamide, by wt Additional H O Base Composition F 32F 45F 60F No. AH Density X AH Density X AH Density X AH Density X 19 .23 1.25 .18 .33 1.26 .26 20 0 1.22 .72 1.22 .59 21 .58 1.22 .49 .78 1.23 .63 21A .60 1.22 .48 22 0 1.28 0 23 O 1.25 0 .42 1.23 .34 24 0 1.29 0 25 0 1.27 0 0 1.28 0 25A 0 1.28 0 26 0 1.32 0

TABLE V111 Series No. 3 Formamide, 10% Additional H O Base Composition 10F 3 2F "F F No. AH Density X AH Density X AH Density X AH Density X 9 O 1.17 0 .89 1.18 .75 10 0 1.19 O .83 1.20 .69 .83 1.20 .69 11 0 .22 O .21 1.24 .17 .79 1.24 .64 12 0 1.23 0 13 0 1.20 0 14 0 1.26 0 0 1.26 0 l5 0 1.17 0 .82 1.18 .69 0 1.26 0 16 0 1.22 0 .92 1.24 .74 .97 1.24 .78 17 20 1.22 16 .73 1.24 .59 .82 1.23 .67 18 .08 1.27 .06 .13 1.27 .10 19 0 1.28 0 0 1.28 0 20 0 1.25 0 .13 1.22 .11 .65 1.22 .53 21 .08 1.26 .06 .63 1.24 .51 22 O 1.20 0 .38 1.20 .32 23 0 1.21 0 O 1.21 0 24 0 1.27 0 0 1.27 0 25 0 1.23 0 0 1.23 0 26 0 1.29 0

TABLE XI Continued Series No. 6 Ethylene Glycol 10% Additional H O Base Composition 10F 32F 45F 60F No. AH Density X AH Density X AH Density X AH Density X 17 .32 1.25 .26 .85 1.28 .664 18 .08 1.21 .06 .84 1.19 .71 19 .75 1.22 .62 20 .09 1.20 .075 .31 1.22 .25 21 .89 1.20 .74 22 O 1.23 0 .98 1.24 .79 .96 1.23 .78 23 .67 1.22 .55 24 0 1.32 0 25 0 1.26 0 .13 1.26 .10 26 0 1.29

As demonstrated by this series of tests many of the compositions exhibited excellent sensitivity and energy as evidenced by the deformation of the lead block even at temperatures as low as 10F. This is even more significant when it is noted that the compositions contained no auxiliary sensitizers and/or fuels, e.g., particulate metals, self-explosives and the like. The performance of these compositions and some of the poorer performing compositions, as to power and sensitivity, can be improved by the addition of such auxiliary materials as demonstrated in some of the following examples. However, these tests demonstrate the unique improvement offered by the novel composition because in many instances such costly and/or dangerous additives were unnecessary to obtain powerful explosives.

Example 2 In this example certain compositions were tested in a standard underwater and a different lead block test than previously defined herein at normal and low temperatures. In the underwater tests the composition to be tested was placed in a two gallon pail along with a level a known horizontal distance from the explosive. The electrical impulses were recorded and converted -to the corresponding pressures and from this, peak one-third pound high density booster charge. The pail was sealed with a lid through which the detonating cord extended. Water resistance was assured by a gasket sealing assembly at the opening where the detonating cord came through the lid. 1n the testing, the detonating cord was connected to an initiator and firing line and the pail was suspended in a body of water at about half the depth of a lake (pail placed at about 42.5 feet beneath the surface of the water). The composition was exploded and the resulting pressure profile from the explosion was converted into electrical impulses by a piezoelectric gauge suspended in the water at the same pressure, shock energy, bubble energy and the total energy of the explosive was calculated by methods described in Underwater Explosives, R. H. Cole, Princeton University Press (1948). In this example and Table X11, peak pressure is designated as PK, the shock energy as ESN, the bubble energy as Y, and the total energy as ET.

The results of testing eight compositions in the underwater test and procedure are set forth in the following Table XII. The compositions listed in shot No. 4-8 fall within the scope of the present invention. Shot Nos. 5 1 and 2 demonstrate the results obtained where ammonium nitrate was the sole oxidizing salt. The composition in shot No. 3 is similar to a commercially available unmetallized slurry explosive formulation. As demonstrated by these tests certain of the compositions of the present invention showed superior energies over the other compositions tested and all showed superior peak pressures.

To demonstrate the unique low temperature sensitivity properties of the present invention compositions corresponding to those in shot Nos. 3 and 8 were tested in a standard lead block deformation test as describedhereinbefore. The composition of shot No. 8 detonated at 10F, at a density of 1.25 grams/cc with a deformation of 0.73 inch, while the composition of shot No. 3 failed to detonate in the lead block test even at a lower density of 0.93 gm/cc, at 73F. The lower density and higher temperature favor detonation of explosives.

This data shows the superior sensitivity properties of the present composition, for low temperature use.

TABLE X11 Parts by Weight Constituents As Shot Sug- Wt. No. CNF AN SN NH H O F EG P6 ar Gum Lbs ESN Y ET PK AN ammonium nitrate SN sodium nitrate F l'ormalnidc EG ethylene glycol PG propylene glycol Example 3 A TAB LEZY M As a further example of the superior low temperature sensitivity of compositions falling within the scope of Mix B the resent invention several com ositions were re- Mix B 30 parts by weight Formamide p l I p p b t N pared contammg CNF, formam1de, water and ammo- 3 C F nium nitrate. Five compositions were prepared conaggin i Parts/Wt. Density .511 H taining the constituents as parts by weight as set forth in the following Table XIII. The compositions were A M tested in the previously defined standard lead block test 52mg 5 25 333 at 45F, the primer consisting of a 37 gram 50/50 pen- NaNO: 11.1 I 0:7i 0.60 tohtc booster. The results of the tests are also tabulated {32:8 g2; in Table XIII. Each composition varied from com- 1100: 14 I 0:66 0:53 positlon of test No. 1 in that a quantity of calcium ni- $28 5-: 8-3; 8 :3 trate was replaced by a bite we1ght of ammonium 111- Npmti3 ,1 L15 1'08 094 trate. F1ve percent by we1ght of water was also em- S3 28 33-3 Hg 1.05 ployed over that present in the CNF. The uniqueness j g 6:82 of the compositions contaming greater proportions of g F 38? mg {-8} 8.3; calcium nitrate at lower temperatures is shown by the BadvOf). H11 1111 1.02 0:92 fact that 1n shots 3-5, containing at least 55 or more 32558 ig-g 83? parts by weight ammonium nitrate, no detectable lead block deformations were produced. 7

TABLE XIII Shot Specific Weight emp N0. Gravity G.M.S. "F Al-l FORM CAN AN H10 1 1.17 191 45 .96 I7 58 5 2 1.15 184 45 1.03 17 43 5 3 1.16 188 0 i7 28 5 4 1.15 186 45 0 17 13 5 5 1.16 188 45 0 17 0 s3 5 Example 4 TABLE xv1 In this example various compositions were prepared containing CNF, formamide, and water in amounts MiXC Mix C (25 parts by weight Formamide within the scope of the present mvent1on. To these 40 rts by weight CNF compos1t1ons were added var1ous morgamc salts, wh1le maintaining the ratio of CNF to formamide approxi- Additive Pam/W1 Density X mately the same. The compositions were tested at a Comm H8 My 077 temperature of about 70F in the previously defined NHiNo 11.1 1.5g 8.3g standard lead block test and AH and X as defined here- 45 1nbefore, tabulated for each. The base compos1t1ons $3.585 8.7 8.32 8.27% (Mixes A-D), as parts by welght, the add1t1ves (parts 150 by we1ght) and results of the lead block tests are set NaNO 11.1 1.11 0.74 0.67 forth in the following Tables -x1v xv i. 5 5g; 3;, Hg 3?; 3f};

' 50 61110903 66.7 1.21 0.03 0.025 iii 3'85 88% NaNO 150 TABLE V.., Ba(NO3) 11.1 1.07 0.80 0.75 Bfl(NO:i)2 25.0 1.13 0.3g .7g B8(N03) 42.8 1.1 0. .6

Mix A Base Comp (Mix A) (28 parts by weight Formamide 55 (57 parts by weight CNF (15 parts by weight Nl-nNo, TABLE XVII Additive Parts/Wt. Density AH X Mix D Control 1.14 1.0g 0.9g 60 Mix D g; g NaNO; 5.25 1.12 0.9 0.8

NaNO; l U "20 0'99 033 Additive Parts/Wt. Denslty AH X E 228: 3'31 Control 1 2 .3 :3

, NH NO 11.1 .1 M5 19111610: 25.0 1.15 0.96 0.83

NaNO 55.8 1.06 0.87 0.x:

NHINO, 42.8 1.14 1.06 0.93 CaSO 5.25 1.03 0.77 0.75 65 H l mg 0 77 O 74 Nl-LNO, 53.8 1.14 0.98 0.86 1 Nl-LNO, 1.18 0.73 0.62

TABLE XVII-Continued positions were tested in a standard lead block test at -densities ranging from about 1.00 gm/cc to about 1.24

Mix D gm/cc. The constituents in these various compositions, Mix D P311533 ism 29:2 and lead block data is set forth in the following Tables parts yweig 5 Additive Parts/Wt. Density AH x and I NH NO 150.0 1.16 0.71 0.61 1861 10. 11.1 1.06 0.11 0.10 Example 6 NaNO; 25.0 1.04 0.07 0.067 NaNO, 42.8 1.14 0.04 0.035 In th1s example d1fierent water soluble organic fuels NaNO 53.8 1.16 0.03 0.025 NaNO; 2' 0.03 0025 10 were employed wh1le keep ng theweight ratio ofCNF, Eamon)! 1H 104 (mg 0019 fuel, water and ammomum mtrate approx1mately 3 8mg); ig-g g 8-83 equal. The compositions were tested in the aforemenm g g tioned lead block test at about 70F. The results of B3(NO;| 100 1.11 0.05 0.045 these tests are set forth 1n the followmg Table XX. The E l 15 results of these tests demonstrate the application of dif- Xamp e ferent water soluble organic fuels and mixtures of such In this example various additives and combinations of fuels in the preparation of compositions within the additives were added to a base CNI mixture. The co1fr 1 scope of the presentinwention MMM TABLE XVIII Composition No. Parts by Wt. Constituents l 2 3 4 S 6 7 8 9 l0 CNF 40 40 40 40 40 40 40 40 40 57 Ethylene Glycol 10 10 10 10 10 10 10 Formamide 28 NH,NO3 10 5 5 5 5 Urea l0 1(No 5 10 NaNO: 5 NaSO 5 10 a)2- 4 5 I0 11 0 5 5 5 5 5 5 5 5 Al 5.25 AH 0.02 0.73 0.06 0.08 0.13 0.80 0.44 0.78 0.12 0.92 Density 7 1.14 1.14 1.19 1.14 1.24 1.18 1.21 1.14 1.16 1.00 x 0.017 0.64 0.03 0.77 0.11 0.68 0.36 0.68 0.10 0.92

...L LE.. X, W

Composition No. Parts by Wt.

Constituents 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 13: 5 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 70 70 Formamide 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 30 30 N1-1..NOs 15 15 15 15 15 15 15 15 15 15 15 15 15 NaNG 15 15 M SO4 11.1 25.0 11.1 MgO 11.1 caso.1 5.25 11.1 Ferrophosphorous l 1.1 15 ulfur 11.1 11.1 Starch 11.1 Sand 11.1 Wood Fibers 5.25 Mg 11.1 Algflake) 11.1 11.1

AH 0.65 0.04 0.79 0.77 0.71 0.70 0.77 0.77 0.07 0.02 0.92 0.89 0.87. 0.31 1.86 1.06 0.65 Density 1.02 1.12 1.09 1.12 1.09 1.04 1.03 1.05 1.12 1.19 1.15 122 1.19 1.07 1.16 1.14 1.10 X 0.640.036 0.73 0.69 0.65 0.67 0.75 0.73 0.060.017 0.80 0.73 0.73 0.29 0.74 0.93 0.59

TABLE Parts by Weight Booster Density emp. Fuel Fuel CNF AN H2O "F gms/cc gms/cc AH X Propylene Glycol 15.4 61.6 15.4 7.7 37 gms 1.45 0.00 0.00

70 1.35 0.05 0.037 70 1.21 0.37 0.31 70 1.15 0.78 0.69 70 L08 0.75 0.69 Sorbitol 15.8 60.0 15.0 9.0 70 1.47 0.02 0.014

Booster Density Parts by Weight emp. F gms/cc gms/cc Fuel CNF Fuel Ethylene Glycol Propylene Glycol Ethylene Glycol Glycerine Ethylene Glycol Tripropylene Glycol Methyl- 4 6954 .5 00000 200300 0 000 0 274 7 A3 11111 7 5 1 6 J 7 r e h t F ormamide Ethylene Glycol Ethylene Glycol Example 7 Several compositions containing the constituents lead block eye? at a denslty of about'l's gm/cc' listed below were tested in the aforementioned lead block test at a temperature of about 70F in the manner as defined in the previous examples. Metal was added to some of these compositions and also different water TABLE XXII 40 Composition Density (gm/cc) H Inches lllllllllllllllllllllo A B C D E 5 O 5 4 5 5 V. m 4 4 400 t 1 3 .HD 4 974 40 me E 3 l Pm e p O 4 4 48 CS ujfi 9 mm .mn Imwnm M t TX w pGh m 4 4 Wm m QC Hm m x m E 2 so; am m a u. Emu aw A M T 1 .1 w A M N H M u e Cm m .1 a m .m mo w N rl t l ow m ala mmm u m .l e lS t nmn m w bu .U .w c k u k m .wm mo mmm l e 0 a. lh wmw C BMMCHAMAT Ca(NO 4H O was employed and the amount of water in the composition takes into account the 4 wa- To further Show the ffect of metal IWQFOmPOSmOnS ters of hydration. 60 were tested at approximately 32-33F in a standard The results of the lead block detonation tests are tablead block deformation test- The two compositions ulated in the following Table XXII.

were identical except that one composition contained 10 parts by weight of particulate aluminum. The compositions, and results of the tests are set forth in the folle XXIII and graphically illustrated in FIG.

As evidenced by this data the addition of particulate As shown by these data the employment of particulate aluminum greatly increases the sensitivity and power of the explosive composition as indicated by the lowing Tab greater deformations caused by compositions A, B, D

and E. With about 24 percent by weight of metal, com;

TABLE XXIII primer was detonated with an electric blasing cap. The detonation velocity was determined upondetonation Composition A Parts by Wtv Shot Specific Weight Ethylene Ca(NO emp No. Gravity Grams F AH X Glycol 41-1 Al Nl-LNO Thickener 1 1.37 223.0 32 0.06 .044 10 4O 10 1O 1 2 1.30 210.5 32 0.14 .11 10 4O 10 10 1 3 1.20 195.5 32 0.93 .78 10 40 l0 10 l 4 1.12 182.0 32 1.07 .96 1O 40 10 10 l 5 1.04 169.5 32 1.03 .99 40 10 10 1 Composition B Ethylene Glycol Ca! N01), 4H,O NHINO-t l 1.31 212.5 33 0.02 .015 10 40 10 2 1.20 195.5 33 0.09 .075 10 40 10 3 1.11 180.0 33 0.82 .74 10 40 10 4 1.01 164.1 33 0.80 .79 1O 40 10 5 0.91 147.5 33 0.74 .81 10 40 10 Example 8 by suitable timing instrumentation known to those Various explosive properties of the following compositions were compared.

Composition No. Constituent Parts by Weight Composition No. 1 falls within the scope of the present invention while compositions 2-4 consist of formulations of commercially available explosives.

The tests consisted of l) a plate dent test to determine average detonation velocity of a confined explosive and dent pressure; (2) a detonation velocity test of unconfined explosive and (3) a cone test to determine minimum critical diameter.

In the plate dent test the average detonation velocity of a confined explosive is determined. Both the detonation velocity and the plate dent relate to the peak pressure or brisance of the explosive. 1n the present exam-' ple a 2 inch inside diameter extra heavy open ended steel pipe 20 inches long was filled with an explosive composition to be tested. The pipe contained two ports through the wall thereof a known distance apart. Contactors were inserted through these ports and were employed to determine the velocity of detonation. One end of the pipe was centered on a cylindrical steel plate 3 inches in diameter and 4 inches thick. A 3-7 gram high pressure primer was centered on the opposite end of the pipe in contact with the explosive mixture. The

skilled in the art which measured the time for the detonation wave to progress from the first to second contacts. The plate dent pressure is determined from calculations known in the art based upon the dent produced by the explos iye the steel base plate.

In the second test the detonation velocity of unconfined explosive was determined. The unconfined detonation velocity test was determined by placing an explosive to be tested in a cardboard tube 16 inches long and of constant diameter over the length thereof. The diameter is any diameter which is greater than the critical diameter of the explosive being tested. The velocity was measured by employing contactors in the same manner as described for the plate dent test. A 37 gram high pressure booster was placed at one end of the tube in contact with the explosive and the booster armed and o ed. with an $1929 h st nesaizt..-

The third test consisted of a cone test to determine the minimum diameter column of explosive which will sustain propagation. In the cone test hollow tapered tubes constructed of cardboard 24 inches long were filled with the explosive to be tested. The explosives to be tested were firsttested in a tube which evenly tapered from 4 to 3 inches in diameter. If the entire column of explosive propagated a like composition was then placed in a tube which tapered evenly from 3 inches to 2 inches in diameter. The explosive was always detonated from the larger end of the tube. After the detonation the diameter of any remains of the tube were measured at the position where the explosive appeared to fail to propagate.

The results of the tests are set forth in the following Table XXlV.

As shown by the data metallized compositions of the present invention show superior performance when compared to other metallized and unmetallized explosive compositions when tested at normal and low temperatures.

TABLE XXIV chosen since the fluidity (and pumpability) of slurry ex- .s qsivss. desreases a me psc a y t ss t Composition No. 1 2 3 4 Plate Dent Test kbar kilo bar equals 1000 bars ee uals 14,700 psi Example 9 Explosive compositions were prepared from base mixes comprising; Mix A, 30 per cent formamide and 70 per cent CNF; and Mix B, 28 per cent formamide, 57 per cent CNF and 15 per cent Nl-l NO Plastic balloons were employed as a density control agent and carboxy methyl hydroxyethyl cellulose was employed as a thickener. Additional NH NO and particulate aluminum were premixed into some of these base mixes and they were tested in small diameter cardboard and metal tubes. The results, diameters, size of initiator and formulations are set forth in the following Table XXV.

All the compositions were shot at about 70F. The boosters consisted of 50/50 pentolite in an amount as shown or a blasting cap.

TABLE XXV Density of explosive (gm/cc) 1.25 1.23 1.20 1.27 Detonation velocity (ft/sec) 16,866 15,372 Failed 13,866 Dent pressure (kbar)* 29 33 26 Temperature (F) 75 75 1 75 75 Unconflned Detonation Velocity Test Diameter of tube (inches) 4 4 4 4 Temperature ("F) 75 75 75 75 Density of explosive (gm/cc) 1.25 1.25 1.20 1.27 Detonation velocity (ft/sec) 18,835 10,000 Failed Failed Cone Test Temperature (F) 75 75 Not Not Density of explosive (gm/cc) 1.20 1.21 Tested Tested Minimum diameter (inches) 1.5 3 b proaches the volume occupied by the total composition.

The ingredients were weighed into a clear, cylindrical plastic container. The mixture was then stirred for several hours at room temperature 75F) and allowed to settle overnight. The height of solid layer (HS) and the total mixture height (H) in the container were measured and the ratio obtained as:

Data were obtained in this way for mixture of fertilizer grade Nl-l NO and CNF in ethylene glycol, formamide and 50/50 (by weight ratio) formamide-ethylene glycol fueled mixtures, each with 0.5 and 10 percent by weight additional water. Methanol was also tested as a fuel for a 10 percent water level only. In the methanol tests, samples were stirred by hand two or three times daily for several days and then allowed to settle. They were not placed on mechanical stirrers due to possible evaporation loss. The methanol system was observed both at room (75F) and 6F temperatures.

' Paint Booster Tube Type Result Wt Wt Wt Grade Weight Diam. Length and Density Inches Mix A NH N0 Al Al grns Inches Inches Thickness gm/cc Left 90A 10 8 H16 cardboard 1.05 0 95A 5 5 it 8 l/16 cardboard 1.17 0 98A 2 5 8 1/16 cardboard 1.30 4 98A 2 No. 6 cap as 8 liqsteel 1.33 0 Wt MiK 50B 40 5 8 1/16 cardboard 1.17 4.5 5013 40 10 10 8 1/16 cardboard 1.17 4.5 5013 40 10 34 8 H16 cardboard 1.17 4.5 508 10 Engineers special A 8 ,iasteel 1.18 0 B 40 10 No. 6 cap Va 8 liisteel 1 l8 0 50B 40 10 Engineers special 1 8 liasteel 1 l8 0 50B 40 10 No. 6 cap 1 8 ,iasteel 1.18 0

Fluidity Examples ln examples 10 to 12 data was obtained to show the plasticity properties of compositions falling within the scope of the present invention.

Example 10 In this example an indication of the fluidity of a composition was determined by observing the proportion of a mixture occupied by undissolved solids when the system had reached equilibrium. This parameter was The R values for various compositions are listed in the following Tables XXVI and XXVII. in Table XXVll per cent by weight of CNF and Nl-l NO are shown with methanol comprising the balance. The solubility results for the ethylene glycol-l0 percent H O compositions are illustrated in FIG. 6. In this diagram the solid and broken lines representconstant R values of about 25 and 50 respectively for the different compositions tested. The points represent the composition tested and the numbers over the points represent the

Claims (42)

1. A BLASTING AGENT COMPRISING AT LEAST ABOUT 40 PER CENT BY WEIGHT OF A COMPOSITION CONTAINING CALCIUM NITRATE, WATER, A WATER MISCIBE ORGANIC FUEL AND AMMONIUM NITRATE WHEREIN THESE CONSITUTENTS ARE PRESENT IN AN AMOUNT RELATIE TO EACH OTHER AS DEFINED BY THE GEOMETRIC SHAPE DEFINED BY PLANES ABCDEF AND A''B''C''D''E''F'' AND THE CONNECTING PLANES IN THE REGULAR TETRAHEDROM OF FIG. 1.

2. The blasting agent as defined in claim 1 wherein the composition defined in FIG. 1 comprises at least about 50 per cent by weight of the blasting agent.

3. The blasting agent as defined in claim 1 wherein the composition defined in FIG. 1 comprises about 60 per cent by weight of the blasting agent.

4. The blasting agent as defined in claim 1 wherein the water miscible organic fuel comprises an organic compound containing at least one functional group of 0, -OH, NH, -NH2 N, S or -SH.

5. The blasting agent as defined in claim 4 wherein the water miscible organic fuel comprises an organic compound containing from about 1 to about 6 carbon atoms.

6. The blasting agent as defined in claim 1 wherein the water miscible organic fuel is at least one of ethylene glycol, formamide, propylene glycol, methanol, ethanol, glycerol, sorbitol, mannitol or isopropanol.

7. The blasting agent as defined in claim 1 including up to about 60 per cent by weight of at least one sensitizer or fuel in addition to the water miscible organic fuel.

8. The blasting agent as defined in claim 1 including in addition a metallic fuel.

9. The blasting agent as defined in claim 8 wherein the metallic fuel is at least one of particulate aluminum, magnesium, iron, silicon, titanium, an aluminum alloy, a magnesium alloy, ferrosilicon, silicon carbide, ferrophosphorous, zinc, boron or alloys thereof.

10. The blasting agent as defined in claim 1 including in addition at least one of a gelling or thickening agent.

11. The blasting agent as defined in claim 1 including in addition a cellulosic thickening agent.

12. The blasting agent as defined in claim 1 including in addition a density control agent.

13. A blasting agent comprising at least about 40 per cent by weight of a composition containing calcium nitrate, water, a water miscible organic fuel and ammonium nitrate wherein these constituents are present in an amount relative to each other as defined by the geometric shape defined by planes ABCDE and A''B''C''D''E'' and the connecting planes in the regular tetrahedron of FIG. 2.

14. The blasting agent as defined in claim 13 wherein the composition defined in FIG. 2 comprises at least about 50 per cent by weight of the blasting agent.

15. The blasting agent as defined in claim 13 wherein the composition defined in FIG. 2 comprises about 60 per cent by weight of the blasting agent.

16. The blasting agent as defined in claim 13 wherein the water miscible organic fuel is an organic compound containing at least one functional group of O, -OH, NH, -NH2, *N, -S or -SH.

17. The blasting agent as defined in claim 16 wherein the water miscible organic fuel comprises an organic compound containing from about 1 to about 6 carbon atoms.

18. The blasting agent as defined in claim 13 wherein the water miscible organic fuel is at least one of ethylene glycol, formamide propylene glycol, methanol, ethanol, glycerol, sorbitol, mannitol or isopropanol.

19. The blasting agent as defined in claim 13 including up to about 60 per cent by weight of at least one sensitizer or fuel in addition to the water miscible organic fuel.

20. The blasting agent as defined in claim 13 including in addition a metallic fuel.

21. The blasting agent as defined in claim 20 wherein the metallic fuel is at least one of particulate aluminum, magnesium, iron, silicon, titanium, aluminum alloy, magnesium alloy, ferrosilicon, silicon carbide, ferrophosphorous, zinc, boron or alloys thereof.

22. The blasting agent as defined in claim 13 including in addition at least one of a gelling or thickening agent.

23. The blasting agent as defined in claim 13 including in addition a cellulosic thickening agent.

24. The blasting agent as defined in claim 13 including in addition a density control agent.

25. A blasting agent which comprises at least about 40 per cent by weight of a composition containing calcium nitrate, water, a water miscible organic fuel and ammonium nitrate wherein these constituents are present in an amount relative to each other as defined by the geometric shape defined by planes ABCDE and A''B''C''D''E'' and the connecting planes in the regular tetrahedron of FIG. 3.

26. The blasting agent as defined in claim 25 wherein the composition defined in FIG. 3 comprises at least about 50 per cent by weight of the blasting agent.

27. The blasting agent as defined in claim 25 wherein the composition defined in FIG. 3 comprises about 60 per cent by weight of the blasting agent.

28. The blasting agent as defined in claim 25 wherein the water miscible organic fuel is an organic compound containing at least one functional group of O, -OH, NH, -NH2, *N, S or -SH.

29. The blasting agent as defined in claim 28 wherein the water miscible organic fuel comprises an organic compound containing from about 1 to about 6 carbon atoms.

30. The blasting agent as defined in claim 25 wherein the water miscible organic fuel is at least one of ethylene glycol, formamide propylene glycol, methanol, ethanol, glycerol, sorbitol, mannitol or isopropanol.

31. The blasting agent as defined in claim 25 including up to about 60 per cent by weight of at least one sensitizer or fuel in addition to the water miscible organic fuel.

32. The blasting agent as defined in claim 25 including in addition a metallic fuel.

33. The blasting agent as defined in claim 32 wherein the metallic fuel is at least one of particulate aluminum, magnesium, iron, silicon, titanium, aluminum alloy, magnesium alloy, ferrosilicon, silicon carbide, ferrophosphorous, zinc, boron or alloys thereof.

34. The blasting agent as defined in claim 25 including in addition at least one of a gelling or thickening agent.

35. The blasting agent as defined in claim 25 including in addition a cellulosic thickening agent.

36. The blasting agent as defined in claim 25 including in addition a density control agent.

37. A blasting agent which comprises at least 50 per cent by weight of the composition containing calcium nitrate, water, a water miscible organic fuel and ammonium nitrate wherein these constituents are present in an amount relative to each other as defined by the geometric shape defined by planes ABCD and A''B''C''D'' and the connecting planes in the regular tetrahedron of FIG. 4.

38. The blasting agent as defined in claim 37 wherein the water miscible organic fuel comprises an organic compound containing at least one functional group of O, -OH, NH, -NH2, *N, S or -SH.

39. The blasting agent as defined in claim 37 wherein the water miscible organic fuel comprises an organic compound containing from about 1 to about 6 carbon atoms.

40. The blasting agent as defined in claim 37 wherein the water miscible organic fuel is at least one of ethylene glycol, formamide, propylene glycol, methanol, Ethanol, glycerol, sorbitol, mannitol or isopropanol.

41. The blasting agent as defined in claim 37 including in addition at least one of a gelling or thickening agent.

42. The blasting agent as defined in claim 37 including in addition a cellulosic thickening agent.

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