Patent Publication Number: US-4548659-A

Title: Cast emulsion explosive composition

Description:
The present invention relates to an explosive composition. More particularly, the invention relates to a cast explosive composition having a relatively high density, energy and critical diameter. By &#34;cast&#34; is meant an unflowable or unextrudable mass which is fluid when formulated at an elevated temperature but which sets or hardens upon cooling to ambient temperature. This allows the composition to be &#34;poured&#34; or &#34;cast&#34; while fluid into a container of desired form for hardening in that form. The compositions of the present invention, although hardened, also remain machinable into further desired shapes. 
     The compositions of the present invention are formulated at an elevated temperature by forming a water-in-oil emulsion, which, when allowed to cool, forms a cast composition. The composition comprises inorganic oxidizer salt consisting primarily of ammonium nitrate, a water-immiscible organic liquid fuel, less than about 5% water, optional fuels or sensitizers, and an emulsifier of a particular type which allows formation of a water-in-oil emulsion at the elevated formulation temperature but which also allows the emulsion to weaken and the inorganic oxidizer salt to crystallize at lower or ambient temperatures to produce a cast composition. 
     Water-in-oil emulsion explosives are well known in the art. See, for example, U.S. Pat. Nos. 4,356,044; 4,322,258; and 4,141,767. Such explosives contain a continuous phase of a water-immiscible organic liquid fuel and a discontinuous phase of an emulsified aqueous inorganic oxidizer salt solution. Normally, these explosive compositions contain a density reducing agent for sensitivity purposes. These compositions have a grease-like consistency which renders them water-resistant and generally easily extrudable. 
     Past efforts have focused upon preparing a stable emulsion explosive composition and thus upon preventing or minimizing breakdown, or weakening, of the emulsion and resulting crystallization of the inorganic oxidizer salt solution which is initially dispersed throughout the continuous fuel phase. This was accomplished by employing generally about 8% or more water, to reduce the crystallization temperature of the oxidizer salt solution, and emulsifiers that are particularly stable against emulsion breakdown. In contrast, the present invention employs less than about 5% water and a type of emulsifier that does not form a particularly stable emulsion and thus will allow weakening of the emulsion and resulting crystallization of the oxidizer salt to occur so that the composition becomes cast in form. 
     Low water emulsions are known from U.S. Pat. No. 4,248,644, which discloses an emulsion explosive composition in the form of a &#34;melt-in-fuel&#34; wherein the melt comprises ammonium nitrate as the discontinuous phase and the composition is substantially water-free. The composition, however, includes an emulsifying agent of the type which imparts to it a &#34;greasy consistency&#34; even after cooling to ambient temperature. Thus low water by itself does not insure the formation of a cast composition. The cast compositions of the present invention require the combination of low water and the particular emulsifiers described herein. 
     The compositions of the present invention have advantageous properties. A need exists for a relatively inexpensive but castable explosive composition which can be poured while hot into containers of various forms, but which when allowed to cool, becomes cast or hardened in the form of the container. Heretofore, such types of explosives were formed from cast self-explosives such as TNT, Composition B, pentolite, etc. These compositions, however, are relatively expensive. The cast compositions of the present invention have similar physical properties to these cast self-explosives, including high density and energy; however, the ingredient costs are considerably less. Thus a major advantage of the present invention is to provide a castable explosive composition comprising relatively inexpensive ingredients. In addition, even though the composition loses its grease-like consistency upon cooling and crystallization of the oxidizer salt, it retains adequate water resistance due to the hardened characteristic of its surface. For ease of handling, the compositions remain fluid for a period of time even after cooling to below the salt crystallization temperature. 
     SUMMARY OF THE INVENTION 
     The invention comprises a cast explosive composition comprising inorganic oxidizer salt consisting primarily of ammonium nitrate; a water-immiscible organic liquid fuel; less than about 5% water; optional liquid or particulate fuels or sensitizers and an emulsifier which allows formation of a water-in-oil emulsion at an elevated formulation temperature but also allows the emulsion to weaken and the inorganic oxidizer salt to crystallize at ambient temperatures to produce a cast composition. The composition is formulated by first forming a water-in-oil emulsion at a temperature above the crystallization temperature of the inorganic oxidizer salt and then allowing the emulsion to cool into a cast form. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     When initially formulated at an elevated temperature, the compositions of the present invention have a grease-like consistency and are in the form of a water-in-oil emulsion. This is advantageous for a number of reasons. The emulsion form allows the oxidizer salts to be finely and intimately dispersed throughout the continuous fuel phase to enhance ease of reaction of oxidizer and fuel. The oxidizer salt is dispersed throughout the fuel phase initially as droplets of solution at an elevated temperature, and as the composition cools, the precipitation of the salts within the droplets is physically inhibited resulting in the formation of fine salt crystals which enhance intimacy between oxidizer and fuel. Another advantage is that a grease-like emulsion is fluid and can be pumped or extruded as desired. As the emulsion cools, the grease-like nature is not lost immediately since crystallization of the salts occurs slowly, and thus the composition retains its emulsion-like handling characteristics for some period of time after cooling below the salt crystallization temperature. This allows the composition to be handled initially as an emulsion even at lower temperatures. Thus the addition of other ingredients, such as solid sensitizers or density reducing agents, can be accomplished at lower temperatures; shrinkage and/or cavity formation after placement into a container can be minimized; and risks to personnel of handling high temperature material can be reduced. A non-emulsion composition, when cooled below the ingredient crystallization or melting temperature, would rapidly harden. 
     The inorganic oxidizer salt is employed in an amount of from about 45% to about 92% by weight of the total composition. The oxidizer salt is primarily ammonium nitrate but minor amounts of other salts may be employed preferably in an amount of up to about 20%. The other oxidizer salts are selected from the group consisting of ammonium, alkali and alkaline earth metal nitrates, chlorates and perchlorates. Of these, sodium nitrate and potassium nitrate are preferred. Perchlorates may be employed in amounts up to 40%. Preferably from about 10% to about 65% of the total oxidizer salt is added in particle or prill form. 
     The immiscible organic liquid fuel forming the continuous phase of the composition at the time of its formulation at an elevated temperature is present generally in an amount of from about 2% to about 15% by weight of the total composition. The actual amount used can be varied depending upon the particular immiscible fuel(s) used and upon the presence of other fuels, if any. The immiscible organic liquid fuels can be aliphatic, alicylic and/or aromatic and can be saturated and/or unsaturated, so long as they are liquid at the formulation temperature. Preferred fuels include mineral oil, waxes, paraffin oils, benzene, toluene, xylenes and mixtures of liquid hydrocarbons generally referred to as petroleum distillates such as gasoline, kerosene and diesel fuel. Particularly preferred liquid fuels are mineral oil, No. 2 fuel oil, paraffin waxes, microcrystalline waxes and mixtures thereof. Aliphatin and aromatic nitro-compounds also can be used. Halogenated organic liquids can be used in amounts up to about 25%. Mixtures of the above can be used. 
     Water is employed in an amount of about 5% or less of the total composition. Water miscible organic liquids can partially replace water as a solvent for the salts, and such liquids also function as a fuel for the composition. Miscible liquid fuels can include alcohols such as methyl alcohol, glycols such as ethylene glycol, amides such as formamide, and analogous nitrogen-containing liquids. The use of low amounts of water is an important aspect of this invention. 
     Optionally, and in addition to the immiscible liquid organic fuel, solid or other liquid fuels or both can be employed in selected amounts. Examples of solid fuels which can be used are finely divided aluminum particles; finely divided carbonaceous materials such as gilsonite or coal; finely divided vegetable grain such as wheat; and sulfur. Liquid fuels include those water-miscible fuels described above. A particularly preferred solid fuel is particulate aluminum which can be employed in amounts up to about 50% by weight to increase the density and energy of the composition. Although granular, atomized or paint grade aluminum can be used, atomized is preferred. 
     The emulsifier is a key ingredient in the compositions of the present invention. The emulsifier must be capable of forming a water-in-oil emulsion at an elevated formulation temperature. In addition, the emulsifier must allow the emulsion to weaken upon cooling and the inorganic oxidizer salt in solution to crystallize at temperatures below the solution crystallization temperature. Thus the emulsion should be inherently unstable in the present compositions to allow salt crystallization to occur so that the composition becomes cast in form. Emulsifiers which have been found to produce compositions with these properties include a fatty amine having the following formula: RNH 2 , wherein R has a chain length ranging from 12 to 22 carbon atoms; an acid salt of such fatty amine; disodium ethoxylated nonyl phenal half ester of sulfossucinic acid; complex organic phosphate ester (Syn Fac 9214); and sucrose stearate. These examples represent the anionic, cationic, and nonionic emulsifier classes. The emulsifier allows the formation of a water-in-oil emulsion at an elevated formulation temperature but also allows the emulsion to weaken and the inorganic oxidizer salt to crystallize at ambient temperatures to produce a cast composition. The emulsifier is employed in an amount of from about 0.2% to about 5% by weight. Preferably the emulsifier contains a saturated hydrocarbon chain as its lipophilic portion, although the unsaturated form can be used even though it tends to form a more stable emulsion than the saturated form and thus may not form a cast as easily or as quickly. Preferably, the fatty amine or salt thereof emulsifier has a chain length of from 14 to 18 carbon atoms, and more preferably, the fatty amine is an alkylammonium salt composed of saturated molecules having a chain length of from 14 to 18 carbon atoms. The fatty amine emulsifiers of the present invention may also function as crystal habit modifiers in that they control oxidizer salt crystal growth and prevent the formation of larger desensitizing crystals. 
     Although it is desirable that the compositions of the present invention have a high density, the compositions can be reduced from their natural densities by addition of a density reducing agent, such as small hollow particles of which plastic or glass spheres and perlite are examples. In addition, gas bubbles can be entrained into the composition during formulation or can be introduced by a small amount of a chemical gassing agent, such as sodium nitrite, which decomposes chemically in the composition to produce gas bubbles. The use of density reducing agents to increase sensitivity is well known in the art. 
     The compositions of the present invention are formulated by first forming a melt, or a solution if water is present, of the oxidizer salt(s) at an elevated temperature above the salt crystallization or solidification temperatures. This melt or solution then is added to a solution of the emulsifier and the immiscible organic liquid fuel, which can at be at ambient or an elevated temperature, with sufficient vigor to produce an emulsion of the oxidizer salt melt or solution in a continuous organic liquid fuel phase. Usually this can be accomplished essentially instantaneously with rapid stirring. Stirring should be continued until the formulation is uniform. Any solid, particulate fuels and/or oxidizer salt and other ingredients, if any, then are added and stirred throughout the formulation by conventional means. The formulation process also can be accomplished in a continuous manner as is known in the art. Any particulate oxidizer salt or any solid, particulate fuels, such as aluminum particles, preferably are added at ambient temperature which results in a cooling of the overall formulation to a temperature below the freezing or crystallization temperature of the oxidizer salt. As previously mentioned, crystallization of the oxidizer salt occurs over some period of time, even at temperatures below the crystallization temperature, allowing the resulting composition to remain fluid for ease in handling, even when containing up to 60% solids. The rate of hardening is dependent upon the degree of refinement of the original emulsion, and the amount and intensity of shear it receives during handling while it is below the crystallization temperature. The type of emulsifier and organic liquid fuel also influence the hardening rate. It is advantageous to predissolve the emulsifier in the organic liquid fuel prior to adding the organic liquid fuel to the oxidizer salt melt or solution. This method allows the emulsion to form quickly and with minimum agitation. The emulsifier can be added separately and just prior to emulsification, however, if desired or if, for example, the emulsifier would degrade at the elevated temperature of the fuel. 
     Reference to the following Table further illustrates the invention. 
     Examples A and B were prepared in accordance with the above-described procedure and are representative compositions of the present invention. Example A contained a high amount of dry AN prills (50%) and no aluminum, whereas Example B contained a smaller amount of prills but 39% atomized aluminum, which gave Example B a much higher density and considerably more energy. The remaining examples show variations in ingredients. Examples G-L and O contained glass microballoons and thus had relatively lower densities but higher sensitivities. Example L contained 40% dry potassium perchlorate. Examples of other emulsifiers which are found to produce cast compositions in accordance with the invention include disodium ethoxylated nonyl phenol half ester of sulfossucinic acid, complex organic phosphate ester (Syn Fac 9214) and sucrose stearate. 
     The compositions of the present invention can be used in explosives applications requiring relatively insensitive blasting agents in large diameters or bulk configurations. Because the compositions are extrudable and/or pumpable when initially formulated, they can be loaded into containers of various forms for various applications. 
     While the present invention has been described with reference to certain illustrative examples and preferred embodiments, various modifications will be apparent to those skilled in the art. In any such modifications are intended to be within the scope of the invention as set forth in the appended claims. 
     
                                           TABLE                                   
__________________________________________________________________________
Composition Ingredients                                                   
(Parts by Weight)                                                         
               A  B  C  D   E  F  G  H   I  J  K  L   M  N  O             
__________________________________________________________________________
AN             40.0                                                       
                  40.0                                                    
                     37.4                                                 
                        40.0                                              
                            40.0                                          
                               40.0                                       
                                  39.8                                    
                                     39.6                                 
                                         39.4                             
                                            61.8                          
                                               50.0                       
                                                  38.4                    
                                                      37.9                
                                                         40.0             
                                                            32.0          
SN             -- -- 4.4                                                  
                        --  -- -- -- --  -- -- -- --  -- -- 8.3           
KN             -- -- -- --  -- -- -- --  -- -- 10.0                       
                                                  7.7 -- -- 3.3           
CN             -- -- -- --  -- -- -- --  -- 23.7                          
                                               -- --  -- -- --            
H.sub.2 O      4.0                                                        
                  4.0                                                     
                      2.2                                                 
                        4.0 4.0                                           
                               4.0                                        
                                  4.0                                     
                                     4.0 3.9                              
                                            4.5                           
                                               5.0                        
                                                  3.8 3.8                 
                                                         4.0              
                                                            --            
Emulsifier     1.0.sup.a                                                  
                  0.7.sup.a                                               
                     1.0.sup.a                                            
                        1.0.sup.c                                         
                            1.0.sup.d                                     
                               1.0.sup.e                                  
                                  1.0.sup.a                               
                                     1.0.sup.a                            
                                         1.0.sup.a                        
                                            4.0.sup.a                     
                                               0.4.sup.a                  
                                                  1.1.sup.a               
                                                      .9.sup.a            
                                                         1.0.sup.f        
                                                            1.1.sup.a     
Fuel Oil       5.0                                                        
                  3.3                                                     
                     5.0                                                  
                        5.0 5.0                                           
                               5.0                                        
                                  5.0                                     
                                     5.0 4.9                              
                                            4.0                           
                                               2.6                        
                                                  6.9 10.0                
                                                         5.0              
                                                            5.5           
Dry AN Prill   50.0                                                       
                  13.0                                                    
                     50.0                                                 
                        50.0                                              
                            50.0                                          
                               50.0                                       
                                  49.7                                    
                                     49.5                                 
                                         49.3                             
                                            -- -- --  47.4                
                                                         50.0             
                                                            47.8          
Dry KC10.sub.4 -- -- -- --  -- -- -- --  -- -- -- 40.0                    
                                                      -- -- --            
Atomized Aluminum                                                         
               -- 39.0                                                    
                     -- --  -- -- -- --  -- -- 30.0                       
                                                  --  -- -- --            
Glass Microballoons                                                       
               -- -- -- --  -- -- 0.5                                     
                                     1.0 1.5                              
                                            2.0                           
                                               2.0                        
                                                   2.0                    
                                                      -- -- 2.0           
Density (g/cc) 1.42                                                       
                  1.70                                                    
                     1.45                                                 
                        1.40                                              
                            1.40                                          
                               1.40                                       
                                  1.30                                    
                                     1.19                                 
                                         1.15                             
                                            1.20                          
                                               1.43                       
                                                  1.17                    
                                                      -- -- 1.18          
Detonation Velocity (km/sec)                                              
at 12-15&#39;C                                                                
Diameter (cm)                                                             
40             3.2                                                        
                  4.2                                                     
                     -- 4.7 Det                                           
                               4.1                                        
                                  -- --  -- -- -- --  4.3                 
                                                         3.7              
                                                            --            
35             3.3                                                        
                  -- 3.9                                                  
                        4.6 3.5                                           
                               3.6                                        
                                  -- --  -- -- -- --  4.2                 
                                                         Det              
                                                            --            
30             3.1                                                        
                  4.0                                                     
                     3.1                                                  
                        4.5 3.0                                           
                               Fail                                       
                                  -- --  -- -- -- --  3.8                 
                                                         3.3              
                                                            --            
25             2.7                                                        
                  3.3                                                     
                     -- 4.1 Det                                           
                               -- 4.6                                     
                                     --  -- -- -- --  3.5                 
                                                         Det              
                                                            --            
20             Fail                                                       
                  Fail                                                    
                     Fail                                                 
                        Det -- -- 4.3                                     
                                     Det -- -- -- --  3.4                 
                                                         4.0              
                                                            --            
15             -- -- -- --  -- -- 3.9                                     
                                     4.7 4.7                              
                                            5.5                           
                                               3.9                        
                                                  --  -- -- 4.2           
12.5           -- -- -- --  -- -- 3.4                                     
                                     4.4 4.5                              
                                            5.5                           
                                               3.4                        
                                                  4.5 -- -- 3.9           
10             -- -- -- --  -- -- 2.1                                     
                                     4.2 4.2                              
                                            5.4                           
                                               4.9                        
                                                  4.5 -- -- 3.6           
 7.5           -- -- -- --  -- -- -- 3.0 3.6                              
                                            4.7                           
                                               4.9                        
                                                  4.5 -- -- 2.8           
Minimum Booster.sup.b, Det/Fail                                           
               3C/                                                        
                  3C/                                                     
                     3C/                                                  
                        8g/ 3C/                                           
                               2A/                                        
                                  15g/                                    
                                     8g/ 8g/                              
                                            15g/                          
                                               8g/                        
                                                  8g/ 2A/                 
                                                         3C/              
                                                            2A/           
               2A 2A -- #12 2A -- 8g #12 #12                              
                                            8g #12                        
                                                  #12 40g                 
                                                         2A 40g           
__________________________________________________________________________
 Key:                                                                     
 .sup.a Alkylammonium acetate compound of saturated molecules having a    
 chain length of from 12 to 18 carbon atoms.                              
 .sup.b &#34;3C&#34; represents an 340 gram pentolite booster, &#34;2A&#34; represents a  
 160 gram pentolite booster, &#34;-g&#34; represents pentolite booster of specifie
 grams, &#34;#12&#34; is a blasting cap having 12 grains of base charge.          
 .sup.c Alkylammonium acetate compound of unsaturated molecules primarily 
 having a chain length of 18 carbon atoms.                                
 .sup.d Aliphatic primary amine acetate of saturated molecules primarily  
 having a chain length of from 14 to 18 carbon atoms.                     
 .sup.e Alkylammonium acetate compound of saturated molecules primarily   
 having a chain length of 12-14 carbon atoms.                             
 .sup.f Alkylammonium acetate compound of unsaturated molecules having a  
 chain length of from 12 to 18 carbon atoms.