AU635335B2 - Rheology controlled emulsion - Google Patents

Abstract

The present invention relates to an emulsion composition with a polymerizing and/or crosslinking agent and methods for its use in improving the manufacturing, packaging, transporting, storage placement and blasting characteristics of explosives containing an emulsion. The present invention is directed to controlling the rheology of an emulsion or explosive containing an emulsion by polymerizing and/or crosslinking the continuous phase of the emulsion by employing hydroxy-terminated polybutadiene and polymerizing agents and/or maleic anhydride adducted polybutadiene and crosslinking agents. The present invention provides compositions and methods of polymerizing and crosslinking emulsion compositions which result in an emulsion whose rheology may be controllably selected, without compromising the integrity of the explosive reaction. The composition of the present invention is comprised of a water-in-oil emulsion containing a continuous external carbonaceous fuel phase, the fuel phase being at least partially polymerized and/or crosslinked.

Description

WO 91/01800 PCT/US90/04261

-I-

RHEOLOGY CONTROLLED EMULSION

BACKGROUND

1. The Field of the Invention The present invention relates to methods and compositions for controlling the theology of emulsion compounds and explosives containing an emulsion. More particularly, the present invention is related to an emulsion with a polymerizing and/or crosslinking agent which permits the preselection of a desired rheology of the subject emulsion compound.

2. Backaround of the Invention Explosive compositions are frequently used in construction and mining related enterprises. The physical characteristics of explosive compounds vary with the intended use. In some circumstances it is desirable to utilize an explosive composition whose viscosity is so low that the explosive composition may be pumped into its intended site. On the other hand, it may be desirable to utilize an explosive composition which alone is rigid enough to withstand the weight of stacking in storage or as packaged material, when stacked vertically in a borehole.

In the last few decades, developments in mining explosive technology have produced explosives far different fr6m nitroglycerine-based explosives used in the past.

Explosives are now made from components which are much less expensive, less dangerous to prepare, transport and use.

These developments have resulted in slurries and explosives containing an emulsion.

The development of slurries has resulted in the use of thickening agents such as water-soluble gums, especially guar gum, allowing control of the rheology of continuous phase of the slurry and, hence, the slurry matrix.

Slurries continue, however, to be plagued with crystallization of the discontinuous phase. Slurries are prone to WO 91/01800 PCT/US90/04261 -2- 1 crystallization at low temperatures. This compromises the intimacy of the mixing of the oxidizers and fuels and results in a loss of sensitivity. This problem is particularly acute in small diameter applications. Loss of sensitivity is overcome by employing expensive ingredients such as paint grade aluminum, TNT, monoethanolamine nitrate, hexamethylene tetramine nitrate, ethyleneglycol mononitrate, and the like. What is needed is an explosive composition whose sensitivity is not compromised by crystallization, but which retains the versatility of theology control exhibited by slurries or water-gel explosives.

Explosives containing an emulsion are now well known and overcome many of the problems encountered with previous explosive formulations. The discovery of water-in-oil emulsions has resulted in pumpable fluid like explosives containing an emulsion which prove superior to slurries for many uses. Generally, emulsions include two separate phases. These phases comprise a discontinuous internal phase of an aqueous solution of oxidizers and a continuous external phase of a carbonaceous fuel, such as oils and waxes, and an emulsifier. The typical explosive containing an emulsion also contains sensitizers in order to render them detonable. One of the favorable features of explosives containing an emulsion is the fact that the surface area of contact between the fuel phase and the oxidizing phase is increased such that the fuel phase and the oxidizing phase are more intimately interspersed and, hence, more sensitive and faster reacting upon detonation.

30 Emulsions have provided some solutions to problems of 3O water resistance, separation of components, and loss of detonability at low temperatures. Explosives containing water-in-oil emulsions also have other advantages. They are safer because they are less sensitive to mechanical shock, and less expensive because the principal component WO 91/01800 PCr/US90/04261 -3- 1 ingredients of water, oil, ammonium nitrate, emulsifying agents, and sensitizers are available at relatively lower cost.

When emulsions are properly prepared, the interspersed oxidizer droplets of the oxidizing phase are so small that they are able to be supercooled. As a result, a highly concentrated aqueous solution with a crystallization temperature well above room temperature can be obtained and incorporated into the discontinuous oxidizing phase. Such an aqueous solution will not experience crystallization upon cooling to even well below the crystallization temperature. This preserves the intimacy of the mixing and the desired sensitivity. However, currently available emulsions have limited shelf life because of the tendency of the aqueous phase to crystallize and for such crystals, by rupturing the barriers between droplets, to grow. The emulsion then loses sensitivity.

The rheology of currently available explosives containing an emulsion is dependent largely upon the physical consistency of the continuous fuel phase and on the volume ratio of oxidizer to fuel phases. Rheology control manipulates the phase volume ratio of the oxidizer solution of the discontinuous phase to the continuous fuel phase, and/or selectively varies the size of the droplets of the oxidizer solution, and/or selectively varies the viscosity of the continuous fuel phase. The choice of phase volume ratio dictates the rheology of the emulsions and explosives containing an emulsion. For example, if the ratio of oxidizer solution to fuel is large the resulting emulsions are stiff. Similarly, if the solution droplets are small the resulting emulsions are stiff. Furthermore, if the fuel phase comprises a thick oil the resulting emulsions are highly viscous, or if the fuel phase comprises a wax the resulting emulsions have a high degree S of plasticity.

WO 91/01800 PCT/US90/04261 -4- 1 The ability to control the rheology of the emulsion or explosive containing an emulsion becomes very apparent when considering the manufacturing of explosives containing an emulsion. As stated, oils and waxes are selectively chosen to obtain the desired theology of an emulsion or explosive containing an emulsion. If, for example, it is desirable to cartridge the explosive containing an emulsion, or to assure that air bubbles or other discontinuous phases are held in place, the oils or waxes must be fluid at the temperature of manufacture in order to form and refine, and then pour or pump the emulsion. As a result, the rheology of the final composition is then dependent on temperature.

Even emulsions and explosives containing an emulsion containing waxes which are relatively stiff at the lower temperatures of use are relatively and often undesirably soft at higher temperatures of use. Change in the rheology with temperature is contrary to the constant environment needed to effectively disperse or maintain in dispersion a discontinuous oxidizing phase or sensitizing agent. In other words, temperature changes work not only a change in the rigidity of the composition itself, but also detrimentally influence the ability of the emulsion or explosive containing an emulsion to hold or lock the discontinuous oxidizing phase and/or sensitizers in place.

An explosive containing an emulsion whose composition permitted the user to select the rheology of the ultimate explosive containing an emulsion, much as is possible with water-gel explosives, would be much more desirable. Such a composition would provide an explosive containing an emulsion which is capable of effectively stabilizing the continuous and discontinuous phases over a wide range of temperatnres such that the explosive containing an emulsion would be less sensitive to temperature changes. Similarly, it would be an advancement in the art if the rheology of a given emulsion or explosive containing an emulsion would WO 91/01800 PCT/US90/04261 1 permit the control of other significant characteristics of the composition, such as waterproofing, surface adhesion, and wetness. Indeed, what is needed is a polymerizing agent or crosslinker which permits the user to select the desired rheology.

Therefore, it would be a further advantage and improvement in the art if the rheology of an emulsion or explosive containing an emulsion could be controlled to produce an emulsion or explosive containing an emulsion which is more stable, less prone to crystallization of the oxidizer salts in the solution of the discontinuous phase and to subsequent growth of the crystals.

Such an emulsion and explosive containing an emulsion are disclosed and claimed below.

BRIEF SUMMARY OF THE INVENTION The present invention relates to emulsion compositions with a polymerizing and/or crosslinking agent and methods for use in improving the manufacturing, packaging, transporting, storage and placement of emulsions and explosives containing an emulsion. More particularly, the present invention is directed to controlling the rheology of an emulsion or explosive containing an emulsion by polymerizing and/or crosslinking the continuous phase of the emulsion. The present invention provides compositions and methods of polymerizing and/or crosslinking emulsion compositions which result in an emulsion or explosive containing an emulsion whose rheology may be controllably selected, without compromising the integrity of the explosive reaction.

The present invention is directed to an emulsion comprising a fuel phase, an oxidizing phase, an emulsifier, a selected amount of polymerizable and/or crosslinkable material, and a coreactant to effect polymerization or crosslinking reaction in situ.

WO 91/01800 PCT/US90/04261 -6- 1 The present invention is also directed to an explosive containing an emulsion comprising a fuel phase, an oxidizing phase, an emulsifier, a selected amount of polymerizable and/or crosslinkable material, a coreactant to effect polymerization or crosslinking reaction in situ, a sensitizer, and optional additional fuels or oxidizers.

The composition of the present invention comprises a water-in-oil emulsion containing a continuous external carbonaceous fuel phase. The fuel phase contains a polymerizable and/or crosslinkable polymer which is polymerized or crosslinked. Dependent upon the chemistry of the polymer or crosslinker, the amount used, temperature and pH, the polymerizing and crosslinking reaction adjusts the rheology of the selected emulsion to the desired rheology and stabilizes the emulsion composition. As a result, the coalescence, crystallization, agglomeration, or migration of the discontinuous oxidizing phase of the emulsion and/or sensitizing agents of the explosive containing an emulsion is reduced, and the final rheology of the emulsion or explosive containing an emulsion is optimal for its intended use.

The rheology control mechanism of the present invention is one that is not only influenced by the chemistry of the polymer or crosslinker, the amount used, temperature and pH, but also by the period of time over which the polymerization and/or crosslinking reaction occurs. That is, the rheology change of the continuous phase of the emulsion may be controlled over time as desired.

Included within the fuel phase of the present invention is a crosslinkable and/or polymerizable carbonaceous oil and/or wax. In one preferred embodiment, the polymerizable material is hydroxy-terminated polybutadiene (HTPB). In many cases the HTPB can be .c substituted by a butadiene-styrene copolymer, a polymer WO 91/01800 PCT/US90/04261 -7- 1 with hydroxy functional groups, or other carbonaceous, polymerizable materials with, for example, epoxy functional groups.

HTPB and similar polymerizable carbonaceous materials may be polymerized by reaction with multi-functional isocyanates. In most cases, a suitable polymerizing isocyanate may be chosen from the group of high molecular weight, 1 .j vapor pressure isocyanates. A preferred isocyanate is Isonate® 143L. In the case of HTPB and Isonate® 143L, they act as coreactants to effect the polymerization of some of the continuous phase of the emulsion.

The present invention is also directed to a crosslinkable carbonaceous material used in conjunction with or mutually exclusive of the polymerizable carbonaceous material. A preferred crosslinkable material is maleic anhydride adducted polybutadiene (131 MA). Other suitable redundant materials may also be used. The crosslinkable material is crosslinked employing a suitable crosslinking catalyst or coreactant. In the case of 131 MA, a basic reagent, or a multifunctional hydroxy group is an effective crosslinker. Examples of suitable crosslinkers include ammonia, ethyleneglycol, polyethylene glycol, tri- and monoethanolamine, and other alkaline materials. The presently preferred crosslinker is triethanolamine. Practice of the invention has revealed that other crosslinker coreactants aid the crosslinking process. Suitable crosslinking coreactants include metal organic compositions, and poly-hydroxy compounds or polyols.

The internal, discontinuous oxidizing phase of the emulsion comprises an aqueous solution oxygen-containing salts. Suitable salts include ammonium nitrate, calcium nitrate, sodium nitrate, or perchlorate. The salts are WO 91/01800 PCT/US90/04261 -8- 1 dispersed in the continuous phase so as to provide intimate contact with the continuous fuel phase.

The emulsifier required by the present invention comprises any effective water-in-oil emulsifier. Suitable water-in-oil emulsifiers include known compounds such as sorbitan monooleate, sorbitan tristearate, sorbitan sesquileate, polyisobutylene sulphonic acid, and the like.

An explosive containing an emulsion may be compounded by combining an emulsion as discussed above as a continuous phase, with undissolved, solid oxidizers such as ammonium nitrate or other nitrates or perchlorates, and solid fuels such as coal dust, hydrocarbon fuels or aluminum as discontinuous phases. A preferred embodiment of explosives containing an emulsion phase and a second reactive phase is the so-called heavy ANFO explosive which comprise an emulsion combined with porous ammonium nitrate or with

ANFO.

Sensitizers are typically used in conjunction with explosives containing an emulsion. Sensitizers and density-control agents used in conjunction with the present invention may include, for example, porous prill ammonium nitrate or ANFO, microballons or microspheres, polystyrene beads, self explosives such as TNT, gassing bubbles from nitrite or peroxide solutions, perlite, emulsified gassing agents, and the like. The amount of solid or chemical density-control agents is chosen to give the emulsion or explosive containing an emulsion a void volume in the range from about 4% to about 80% of the final compound. The amount of void space required in the explosive containing an emulsion depends upon the required bulk energy of the explosive and the desired sensitivity.

Oils of low and high viscosity, and various kinds of waxes, paraffin wax or microcrystalline wax, may be employed in conjunction with the polymerizable or cross- Ir linkable material to add to the control of the rheology of WO 91/01800 PCT/US90/04261 -9- 1 the emulsion or explosive containing an emulsion after polymerization or crosslinking has been effected.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is related to compositions and methods for preparing an emulsion or explosive containing an emulsion which are selectively and controllably crosslinked and/or polymerized in order to control the rheology of the emulsion composition or emulsion phase of the explosive containing an emulsion. By employing the present invention particular physical properties of the emulsion may be chosen for optimizing the intended manufacturing, packaging, transporting, storage, and use of the emulsion or explosive containing an emulsion.

The present invention resides in a crosslinkable and/or polymerizable emulsion or emulsion phase of an explosive containing an emulsion. The emulsion comprises principally a water-in-oil emulsion. The emulsion has a crosslinkable and/or polymerizable component in the external continuous fuel phase. It also has an internal discontinuous oxidizing phase. The explosive containing an emulsion comprises an emulsion phase and a sensitizer, and may also contain additional fuels, additional solid oxidizers, and any other necessary or desirable components to control energy and/or density of the final explosive product.

Traditionally, in prior art compositions, the external carbonaceous fuel phase of an emulsion comprises fuel oils, refined or purified hydrocarbons, waxes, halogenated hydrocarbons, nitrated hydrocarbons or a mixture thereof.

However, when the carbonaceous fuel phase comprises a liquid which is flowable at, or slightly above, ambient temperatures the explosive containing an emulsion is not generally suitable for packaging using conventional explosive packaging or cartridging methods. Such WO 91/01800 PCT/US90/04261 1 explosives may similarly be unsuitable for use in boreholes with fissures and cracks because flowable explosive compositions escape the borehole.

A. Rheoloqy Control Via Polymerization 1. In the emulsion Conventional emulsions attempt to provide a continuous fuel phase which suitably inhibits the crystallization, coalescence, agglomeration and migration of the discontinuous phase by including polymers in the continuous phase or by choosing a particular emulsifier. Conventional emulsions have not, however, sought to control the rheology of the continuous phase by polymerizing the continuous phase in situ in a controlled, predictable, and reliable reaction. The present invention provides a continuous fuel phase that includes high molecular weight hydrocarbon species which can be and are at least partially polymerized and/or crosslinked in order to effect a change in the rheology of the emulsion, and, therefore, of the explosive containing an emulsion, as a whole.

An embodiment of the present invention employs, for example, a polymerizable organic material with hydroxy or epoxy functional groups. Particularly, an embodiment of the present invention comprises polybutadiene as the polymerizable organic fuel. More particularly, the preferred embodiment of the present invention employs hydroxy-terminated polybutadiene (hTPB) as the polymerizable fuel.

HTPB is characterized by the presence of a polymer of from about at least fifty (50) repeating monomer units with at least two functional units capable of bonding with other molecules. Such a material results in long, flexible polymer chains whose mass is pliable and can withstand moderate stress and strain without tearing or crumbling.

The character of the certain polymerized fuel materials WO 91/01800 PCT/US90/04261 -I1- 1 provides the continuous phase of the emulsion with advantageous preselected elastic properties. Suitable substitutes for HTPB include carboxy-terminated polybutadiene, maleic anhydride-terminated polybutadiene, epoxy-terminated polybutadiene, and similar substances. In practice, suitable results are obtained when HTPB is present in amounts ranging up to approximately 5.9%.

Better results are obtained when HTPB exists in the emulsion ranging from about 0.75% to about In one preferred embodiment HTPB is present in concentrations ranging from about 1.0% to about The polymerizable organic fuel of the present invention is polymerized with the assistance of isocyanates compounds. Because of the hazards associated with the vapors of low molecular weight isocyanates, high molecular weight, low vapor pressure isocyanates are preferred. More particularly, Isonate® 143L has proven to give superior results. Satisfactory results using Isonate® 143 L have been obtained when present in an amount ranging up to about More suitable results are obtained when Isonate® 143 L is present ranging from about 0.075% to about 0.3%.

Preferably, Isonate® 143 L is present in an amount ranging from about 0.1% to about 0.2%.

2. In the explosive containing an emulsion An explosive containing an emulsion comprises an emulsion phase, energizing/sensitizing agents, and if desired, additional fuels and oxidizers. In other words, the multiphase emulsion discussed above becomes one phase of the explosive compound. In the same manner that the polymerization of the continuous fuel phase of the emulsion chemically changes the rheology of the emulsion, controlling the rheology of the emulsion phase of the explosive containing an emulsion changes the rheology of the explosive containing the emulsion. In this way, the benefits of controlling the rheology of the emulsion can be WO 91/01800 PCT/US90/04261 -12- 1 transferred over to controlling the rheology of the explosive containing the emulsion. Control of the rheology of the explosive containing the emulsion is of great advantage in the manufacturing, packaging, transporting, storage and placement in use of the explosive composition.

Mixing the emulsion with other phases of the explosive, and packaging the explosive, may now be accomplished at or near room temperature. The emulsion can be formulated so that the explosive matrix is more stable during transportation. The temperature of storage is no longer necessarily detrimental to the integrity of the explosive composition. The intended use or placement of the explosive composition may be optimized by selecting a rheology most conducive to the intended use or placement.

For these reasons, and other reasons which become apparent during the practice of the present invention, the rheology control of the present invention is a significant advance in the art.

B. Rheoloqv Control Via Crosslinking 1. In the emulsion Some known emulsion systems contemplate the use of additives to thicken the composition of the emulsion.

Known additives include agents such as natural waxes, water-soluble gums such as guar gum, and synthetic polymers or waxes. Many of the conventional uses of thickening additives emphasize physical rather than chemical rheology changes.

The present invention provides a change in rheology by means of a chemical reaction within the continuous fuel phase of the water-in-oil emulsion. The chemical reaction adjusts the rheology of the emulsion by chemically crosslinking at least a portion of the fuel phase. The crosslinker operates to crosswise connect parallel and/or adjacent chains of polymerized fuel. The crosslinking may WO 91/01800 PCT/US90/04261 -13- 1 continue until the polymerized fuel phase is bound by a matrix mass of crosslinked polymers. The result of the crosslinking is a relatively fixed continuous phase of the emulsion. The character of certain crosslinked materials provides the continuous phase of the emulsion with advantageous preselected rigidity properties. For example, the preselected or desired rigidity may be a rubbery state, or a stiff, solid state. The fixed nature of the continuous phase operates to lock or hold the discontinuous phase in its location. This aids to inhibit the crystallization, coalescence, agglomeration and migration of oxidizing droplets of the discontinuous phase which plague conventional water-in-oil emulsions.

In the present invention, it has been determined that 131 maleic anhydride adducted polybutadiene (131 MA) is an effective crosslinkable polymer. The reactive sites of the 131 MA provide bonding sites at which the crosslinker operates to bind the polymer chains together. Other suitably crosslinkable polymers include compounds having difunctional moieties which may have active bonding sites as are found in anhydride or oxarane groups, nitrogen based groups such as isocyanates, amines, imides, or amides, or carbonyl or hydroxyl groups which in conjunction with a catalyst or accelerator bond with the functional groups of the polymer.

Suitable examples of crosslinkers include ammonia, ethyleneglycol, polyethylene glycol, tri- and monoethanolamine, and other alkaline materials. Satisfactory results using monoethanolamine have been obtained when present in an amount ranging up to about More suitable results are obtained when monoethanolamine is present ranging from about 0.05% to about Preferably, monoethanol amine is present in an amount ranging from about 0.1% to about 0.3%.

WO 91/01800 PCT/US90/04261 -14- 1 Acceptable results using triethanolamine are obtained when triethanolamine is present in a quantity up to about 0.3%..of the emulsion as a whole. More favorable results are obtained when triethanolamine is present in an amount from about 0.1% to about Preferred results occur when triethanolamine is present in quantities from about 0.15% to about 0.2%.

The extent of the crosslinking can be controlled by the selection of the crosslinkable polymer, the crosslinker, the choice of crosslinking coreactant, the amount of crosslinker used, the functional groups added to the polymerized fuel, and the rate of reaction of the crosslinking. The application of the present invention vis-a-vis crosslinkers has resulted in superior results in controllably altering the rheology of the continuous phase of the emulsion, and as a result, inhibiting crystallization, coalescence, agglomeration and migration of the discontinuous phase or phases of dispersed oxidizing components.

The rate of reaction of the crosslinker depends upon the chemistry of the crosslinker, the temperature at which the reaction occurs, and the pH of the environment in which the reaction occurs. The crosslinking process may be enhanced by coreactants including metal organic compositions, and polyhydric alcohols such as polyethylene glycol.

2. In the explosive containing an emulsion For similar reasons as discussed above relative to polymerization, controlling the rheology of the emulsion by crosslinking may be transferred over to controlling the rheology of an explosive by incorporating the emulsion into the explosive composition. If the rheology controlled emulsion is a phase of the explosive composition, then as a result, the rheology of the explosive composition will WO 91/01800 PCT/US90/04261 1 also be controllable. Crosslinking the continuous phase of an emulsion contained in an explosive operates to control the rheology of the explosive compound as well.

C. Rheoloqy Control Via Polymerization And/Or Crosslinkinq One example of an embodiment of the present invention is employing HTPB and 131 MA mutually exclusive of each other. Satisfactory results have been obtained. Another example of an embodiment of the present invention is employing both polymerization and crosslinking. By combining rheology control via polymerization and crosslinking, the character of the resulting composition can provide the continuous phase of the emulsion with a combination of the preselected elastic and rigidity properties optimal for the intended use. An example of a combination use is when one of the fuels of the continuous phase is a butadiene homopolymer adducted with maleic anhydride. Similarly, favorable results are obtained when a butadiene-styrene copolymer, adducted with maleic anhydride, is used as one of the fuels of the continuous phase. Satisfactory re.ults have been obtained when the polymerization of the fuel polymer of the continuous fuel phase is achieved by allowing the 131 MA to be polymerized with the HTPB exclusive of any polymerization enhancer or component, or crosslink reaction.

D. Oxidizing, Density-Control, And Sensitizing Agents 1. In the emulsion Because oxygen balancing is vital for an optimal detonation of explosives, the availability of the oxidizing agent throughout the explosive composition to complete the reaction is of paramount importance. A crucial part of the oxidizing agent for detonation of an explosive containing S an emulsion is provided by the discontinuous oxidizing WO 91/01800 PCT/US90/04261 -16- 1 phase of the emulsion. If the oxidizing droplets or particles of the discontinuous phase of the emulsion crystallize, coalesce, agglomerate or migrate, the intended dispersion effect of the oxidizers is obviously diminished.

Many oxidizing agents and phases are used in convent inal emulsions. The preferable forms of oxidizing agent employed in the present invention include aqueous forms of ammonium nitrate, calcium nitrate, or sodium nitrate, or a mixture thereof.

The present invention also contemplates the use of dry ammonium nitrate-fuel oil prills (ANFO) in conjunction with the oxidizing agents hereinabove discussed.

2. In the explosive containing an emulsion Similarly, homogeneous dispersion of density-control and sensitizing agents is vital for an optimal detonation of explosives. Just as dispersion of oxidizing agents is vital to optimal detonation, the dispersion of densitycontrol and sensitizing agents throughout the explosive composition reaction is also of paramount importance. If dispersed density-control and sensitizing agents of the explosive composition crystallize, coalesce, agglomerate or migrate, the intended dispersion effect is defeated and the air-gap sensitivity and detonation velocity of the explosive composition are diminished.

Density-control and sensitivity components are included in an emulsion to make the emulsion more or less sensitive to shock initiation and to assure that the velocity of detonation through th'e emulsion compound is at a suitable and constant rate. Density-control agents include substances from the group including solid density reducing agents such as expanded polystyrene beads, perlite, microspheres and microballons.

Increased sensitivity can be achieved by using S injected air or gas bubbles, and air or gas bubbles WO 91/01800 PCT/US90/04261 -17- 1 generated in situ from peroxide, nitrite, or carbonate solutions, emulsified gassing agents, and similar gasproducing reactions which do not otherwise compromise the explosive nature of the explosive containing an emulsion.

Sensitivity is also increased by the inclusion of selfexplosives such as, for example, TNT, PETN, RDX, and the like.

E. Emulsifiers Without the presence of an emulsifier the mixed phases of the compositions may tend to separate to form a layered or regional mixture which has little utility as an emulsion.

Suitable emulsifiers for water-in-oil emulsions comprise an amphiphatic compound. The amphiphatic compound is one with at least two or more segments, one of which is only soluble in an oil phase and the other only soluble in an aqueous phase. In other words, a preferred emulsifier comprises an organic emulsifier having a hydrophilic portion and a lipophilic portion, and exhibiting a high solubility in hydrocarbons and a high tolerance to salt solutions. In the case of the present invention, the emulsifier can be selected from the group of known waterin-oil emulsifiers. Examples of suitable emulsifiers include, but is not limited to, sorbitan monooleate, sorbitan tristearate, sorbitan sesquioleate, and glycerides of fat-forming fatty acids, or a mixture thereof.

The effective combination of the above discussed components of the emulsion of the present invention results is an emulsion or explosive containing an emulsion whose rheology can be controlled to meet the needs and demands of the user. This is particularly evident during the course of the manufacturing, packaging, transporting, storage, and the ultimate placement of the explosive, where the rheology of the emulsion composition plays such an important role.

WO 91/01800 PCr/US90/04261 -18- 1 For example, during the manufacture of an emulsion compound, it is vital to homogeneously disperse the discontinuous oxidizing phase in the continuous fuel phase.

This is most easily accomplished when the continuous phase or phases have low viscosity such that the oxidizing phase can be thoroughly agitated and blended into the continuous fuel phase. If the rheology of the continuous phase is too rigid, the task of agitating and blending is made less efficient and effective. However, once the manufacturing stage has progressed to a point at which the discontinuous phase is homogeneously dispersed, it is typically desirable to have the discontinuous phase remain dispersed in the continuous phase without the detrimental effects of crystallization, coalescence, agglomeration or migration of the discontinuous phase. The present invention permits the manufacturer/producer to lock the dispersed, discontinuous phase of the emulsion or other phases of the explosive containing an emulsion in place by employing the polymerizing and/or crosslinking reactions of the present invention. These reactions can be accomplished at the high manufacturing temperature of the emulsion or at ambient temperature after the emulsion phase of the explosive composition has been allowed to cool. "Locking the dispersed, discontinuous phase" is meant to describe the effect of causing a change in the rheology of the continuous phase such that the crystallization, coalescence, agglomeration, or migration of th.

discontinuous phase is inhibited by a chemical reaction which structurally alters the host continuous phase.

Similarly, during packaging, it is very difficult to cause a sticky, highly viscous emulsion to flow into and fill a cartridge or package. It is most desirable that at the time of packaging that the emulsion be readily pumpable and formable to the intended package without the S inconsistencies of void and air pockets and without the WO 91/01800 PCIr/US9/04261 -19- 1 need to maintain the emulsion at unwanted higher temperatures. As a result of use of the present invention, high temperature cartridging can be avoided because the chemical reaction may occur at or below the manufacturing temperature. Likewise, the ready transporting, storage, and handling of an emulsion is often dependent upon the theology and temperature of the emulsion.

Furthermore, the ultimate and proper placement of the explosive at the intended site is vital to the performance of the explosive. If the intended situs of the detonation is in a vertically upward borehole in an underground mine, in a vertically downward borehole in an open pit mine, in a horizonal borehole on a coal or tunnel face, or in any shape of borehole at any angle in between, the ability of the laborer to effectively load, prime, and stem the borehole is directly related to the handling characteristics of the explosive as dictated by the rheology of the explosive composition. The theology of the emulsion or explosive containing an emulsion is, therefore, critical.

The compositions and methods of the present invention provide for an emulsion whose physical characteristics such as surface adhesion, water resistance, viscosity and surface moisture may also be regulated as desired by the user. Because these physical characteristics are closely related to rheology, such physical characteristics may also be selected in accordance with the optimum use and performance of the emulsion. For example, in some circumstances it. is desired to have an emulsion which has a greasy consistency. In another situation, a nongreasy, yet sticky emulsion may be optimal. In another situation, a thin syrupy emulsion may be desired. In yet another situation, a rigid emulsion may be advantageous. Similarly, any phase state in-between may be desirous ultimately or at some stage of the life of the emulsion.

WO 91/01800 PCT/US90/04261 1 The mechanism for polymerizing or crosslinking the continuous phase of the emulsion of the present invention to control the rheology of the emulsion varies. In some cases, polymerization of the continuous phase is sufficient to attain the desired rheology. In other cases crosslinking is required to stabilize the emulsion phase(s). Polymerizing and/or crosslinking the continuous phase of the emulsion permits one to control the rneology of the emulsion.

Polymerizing or crosslinking the continuous phase of the emulsion provides an emulsion whose rheology may be chosen corresponding to the desired and intended manufacturing, packaging, transporting, handling, storage, use and the like. The range of the rheology is determined by controlling the period of time over which the polymerization takes place or by choosing the appropriate crosslinker which will provide the desired crosslink of the continuous phase of the emulsion.

Crystallization, coalescence, agglomeration and migration of dispersed particles is a function of the affinity of the dispersed element to the interfacing substance, of gravity, of density, and of the rheology of the continuous phase. Maintaining the dispersed nature of an oxidizing agent is important to the most desirable performance of the emulsion vis-a-vis oxygen balancing of the blasting reaction. By polymerizing and/or crosslinking the continuous fuel phase the discontinuous phases of the emulsion or explosive containing an emulsion are stabilized.

The ability to control the change of rheology of the present invention focuses on a chemical reaction which is less dependent on temperature than the rheology control of known emulsion and emulsion-containing compounds. In addition, once the desired rheology is attained by employing the present invention, the steady state of the WO 91/01800 PCT/US90/04261 -21- 1 rheology is also less effected by changes in ambient temperature than the steady state of currently available emulsion compounds. This is a result of the chemical bonding between the polymeric components of the emulsion.

Conventional emulsions relied primarily upon the physical mixture of the substituent elements and any help that the emulsifier might provide in maintaining the steady state of the phase distinctions. The chemical reaction of the present invention operates to interconnect and bind together at least some of the monomers and polymers of the continuous phase in such a way that the discontinuous phases are locked or held in place as if they resided in interstitial space in a molecular structure. In this way, the discontinuous phases remain dispersed throughout the continuous phase, thereby maintaining the intimate contact between the fuel phase and oxidizing phase of the emulsion and promoting the detonability of the explosive containing an emulsion.

In addition to the selection of the rheology of the emulsion, the present invention is directed to the ability of the user of the present invention to select a range of rheology of the subject emulsion over a period of time, if desired, by controlling the rate of reaction of the polymerization or crosslinking. It is a well known fact that the rate of many chemical reactions can be controlled by factors such as concentration, temperature, pH, and the like. In the case of polymerizable or crosslinkable polymers, the ratio of functional groups on the polymer tr the function groups on the crosslinker or polymerizer plays a significant role in the rate of reaction of the polymerization or crosslinking. The present invention permits the controlled variation in the rate of reaction of polymerization and crosslinking. In this case the extent of polymerization or crosslinking determines the rheology of S the emulsion at any given time. If it is desired that the WO 91/01800 PCT/US90/04261 -22- 1 emulsion be fluid for a certain period of time and later set to a more rigid state, the extent and rate of polymerization and/or crosslinking is controlled by choosing the appropriate polymer and polymerization process and the corresponding crosslinking reaction.

EXAMPLES

The following examples are given to illustrate the general scope of the present invention, but these examples are not intended to limit the scope of the invention.

Similarly, while the following examples represent a range of composition substituents of suitable emulsions and emulsion phases of explosives containing an emulsion, other ranges of composition substituents outside the ranges illustrated by the following examples also provide suitable emulsions and emulsion phases of explosives containing an emulsion.

The emulsions in the following examples were allowed to cool to room temperature before other ingredients were added. This practice was convenient in the laboratory, but does not imply that similar compositions could not be obtained by incorporating all ingredients into the final composition with the emulsion still at its elevated temperature of mixing.

1 In each example, the number of days of curing is quoted. This is the time at which the ultimate rheology was examined, and not the time taken for the crosslinking or polymerization reaction to become effective.

Example 1 An explosive containing a polymerized emulsion compound was prepared by mixing the following ingredients: Ingredients Percentage Ammonium Nitrate 63.2 Sodium Nitrate 13.9 WO 91/01800 PCT/US90/04261 -23- 1 Water 12.0 Emulsifier Diesel Oil 5.3 HTPB Isonate® 143 L 0.1 Perlite The emulsion was made in the conventional manner by dissolving the ammonium nitrate and sodium nitrate in the water at elevated temperature to form an aqueous phase.

This aqueous phase was added with vigorous stirring to the polymerizable HTPB, to which had been added the emulsifier and fuel oil, until an emulsion was formed. The emulsion was allowed to cool to room temperature. Thereafter, the Perlite and the Isonate® 143 L were added with stirring.

The explosive containing the emulsion cured for one (1) day.

The thus formed explosive containing an emulsion resulted in a discontinuous oxidizing phase uniformly dispersed in a polymerized continuous fuel phase. The consistency of the explosive was non-tacky rubber.

An compound Example 2 explosive containing a polymerized emulsion was prepared by mixing the following ingredients: Ingredients Percentage Ammonium Nitrate 24.4 Calcium Nitrate 18.3 Water 10.0 Ammonium Nitrate Prills 38.8 Emulsifier 0.9 Diesel Oil HTPB 1.2 Isonate® 143 L 0.2 Polystyrene Beads 0.7 WO 91/01800 PCT/US90/04261 -24- 1 The emulsion was made in the conventional manner by dissolving the ammonium nitrate and calcium nitrate in the water at elevated temperature to form an aqueous phase.

This aqueous phase was added with vigorous stirring to the polymerizable HTPB, to which had been added the emulsifier and fuel oil until an emulsion was formed. The emulsion was allowed to cool to room temperature. Thereafter, the Isonate® 143 L, the ammonium nitrate prills and the polystyrene beads were added with stirring. The explosive containing the emulsion cured for over seven days.

The thus formed emulsion resulted in a discontinuous oxidizing phase uniformly dispersed in a polymerized continuous fuel phase. The consistency of the thus formed explosive was firm and rubbery. The explosive remained detonable by 150g of Pentolite in 3 inch diameter tubes for at least 4 weeks.

An compound Example 3 explosive containing a polymerized emulsion was prepared by mixing the following ingredients: Ingredients Percentage Ammonium Nitrate 24.5 Calcium Nitra 'e 18.4 Water 10.0 Ammonium Nitrate Prills 39.0 Emulsifier 0.9 Diesel Oil HTPB 1.2 Isonate® 143 L 0.2 Nitrite Solution 0.3 The emulsion was made in the conventional manner by dissolving the ammonium nitrate and calcium nitrate in the water at elevated temperature to form an aqueous phase.

This aqueous phase was added by vigorous stirring to the polymerizable HTPB, to which had been added the emulsifier WO 91/01800 PCT/US90/04261 1 and fuel oil until an emulsion was formed. The emulsion was allowed to cool to room temperature. The ammonium nitrate prills were added with stirring. Thereafter, the Isonate® 143 L was added with stirring. The explosive containing the emulsion cured for over fourteen (14) days.

The thus formed emulsion resulted in a discontinuous oxidizing phase uniformly dispersed in a polymerized continuous fuel phase. The consistency of the explosive was firm and rubbery.

Example 4 An explosive containing a crosslinked emulsion compound was prepared by mixing the following ingredients: Ingredients Percentage Ammonium Nitrate 21.95 Calcium Nitrate 16.38 Water 8.76 Ammonium Nitrate Prills 44.90 Emulsifier 0.53 Diesel Oil 5.77 131 MA 1.09 Triethanolamine 0.12 Polystyrene Beads 0.50 The emulsion was made in the conventional manner by dissolving the ammonium nitrate and calcium nitrate in the water at elevated temperature to form an aqueous phase.

This aqueous phase was added by vigorous stirring to the crosslinkable 131 MA, to which had been added the emulsifier and fuel oil until an emulsion was formed. The emulsion was allowed to cool to room temperature.

Thereafter, the ammonium nitrate, polystyrene beads and triethanol amine were added with stirring. The explosive containing the emulsion cured for six days.

The thus formed emulsion phase of the explosive S resulted in a discontinuous oxidizing phase uniformly WO 91/01800 PCT/US90/04261 -26- 1 dispersed in a crosslinked continuous fuel phase, with the consistency of non-tacky rubber. The consistency of the explosive was firm and rubbery.

Example An explosive containing a crosslinked emulsion compound was prepared by mixing the following ingredients: Ingredients Percentage Ammonium Nitrate 51.1 Calcium Nitrate 27.4 Water 10.5 Emulsifier Diesel Oil 3.9 131 MA 2.4 Triethanolamine 0.2 Perlite 3.2 The emulsion was made in the conventional manner by dissolving the ammonium nitrate and calcium nitrate in the water at elevated temperature to form an aqueous phase.

This aqueous phase was added by vigorous stirring to the crosslinkable 131 MA, to which had been added the emulsifier and fuel oil until an emulsion was formed. The emulsion was allowed to cool to room temperature.

Thereafter, the perlite and triethanol amine were added with stirring. The explosive containing the emulsion cured for two days.

The thus formed emulsion resulted in a discontinuous oxidizing phase uniformly dispersed in a crosslinked continuous fuel phase, with the consistency of non-tacky rubber. The thus formed explosive had a consistency similar to that of its emulsion phase.

Example 6 An explosive containing a crosslinked emulsion compound was prepared by mixing the following ingredients: WO 91/01800 PCT/US90/04261 -27- 1Ingredients Percentage Ammonium Nitrate 52.2 Calcium Nitrate 28.0 Water 10.7 Emulsifier Diesel Oil 131 MA 2.4 Triethanolamine 0.2 Polystyrene Beads The emulsion was made in the conventional manner by dissolving the ammonium nitrate and calcium nitrate in the water at elevated temperature to form an aqueous phase.

This aqueous phase was added by vigorous stirring to the crosslinkable 131 MA, to which had been added the emulsifier and fuel oil until an emulsion was formed. The emulsion was allowed to cool to room temperature.

Thereafter, the triethanolamine and polystyrene beads were added with stirring. The explosive containing the emulsion cured for two days.

The thus formed emulsion resulted in a discontinuous oxidizing phase uniformly dispersed in a crosslinked continuous fuel phase, with the consistency of non-tacky rubber. The explosive containing the emulsion had a consistency of non-tacky rubber.

Example 7 An explosive containing a crosslinked emulsion compound was prepared by mixing the following ingredients: Ingredients Percentage Ammonium Nitrate 24.6 Calcium Nitrate 6.2 Water 8.4 Ammonium Nitrate Prills 53.0 Emulsifier 0.4 Diesel Oil 5.4 WO 91/01800 PCT/US90/04261 -28- 1 131 MA 0.9 Triethanolamine 0.1 -The emulsion was made in the conventional manner by dissolving the ammonium nitrate and calcium nitrate in the water at elevated temperature to form an aqueous phase.

This aqueous phase was added by vigorous stirring to the crosslinkable 131 MA, to which had been added the emulsifier and fuel oil, until an emulsion was formed. The emulsion was allowed to cool to room temperature.

Thereafter, the ammonium nitrate prills and the triethanolamine were added. The explosive containing the emulsion cured for one day.

The thus formed emulsion resulted in a discontinuous oxidizing phase uniformly dispersed in a crosslinked continuous fuel phase, with the consistency of a firm substance. The explosive had a similar but firmer consistency.

Example 8 An explosive containing a polymerized emulsion compound was prepared by mixing the following ingredients: Ingredients Percentage Ammonium Nitrate 48.7 Calcium Nitrate 30.7 Water 10.8 Emulsifier Diesel Oil HTPB Isonate® 143 L 0.1 Microballons The emulsion was made in the conventional manner by dissolving the ammonium nitrate and calcium nitrate in the water at elevated temperature to form an aqueous phase.

This aqueous phase was added by vigorous stirring to the polymerizable HTPB, to which had been added the emulsifier WO 91/01800 PCT/US90/04261 -29- 1 and fuel oil until an emulsion was formed. The emulsion was allowed to cool to room temperature. Thereafter, the Isonate® microballoons and 143 L were added. The explosive containing the emulsion cured for one day.

The thus formed emulsion resulted in a discontinuous oxidizing phase uniformly dispersed in a polymerized continuous fuel phase, with the consistency of sticky rubber. The explosive had a similar consistency.

Example 9 An explosive containing a polymerized emulsion compound was prepared by mixing the following ingredients: Ingredients Percentage Ammonium Nitrate 40.4 Calcium Nitrate 25.5 Water 7.6 Ammonium Nitrate Prills 15.0 Emulsifier 1.6 Diesel Oil 4.9 HTPB 1.6 Isonate® 143 L 0.2 Nitrite solution 0.2 Aluminum The emulsion was made in the conventional manner by dissolving the ammonium nitrate and calcium nitrate in the water at elevated temperature to form an aqueous phase.

This aqueous phase was added by vigorous stirring to the polymerizable HTPB, to which had been added the emulsifier and fuel oil until an emulsion was formed. The emulsion was allowed to cool to room temperature. Thereafter, the remaining ingredients Isonate® 143 L were added with stirring. The explosive containing the emulsion cured for one day.

The thus formed emulsion resulted in a discontinuous oxidizing phase uniformly dispersed in a polymerized WO 91/01800 PCT/US90/04261 1 continuous fuel phase, with the consistency of non-tacky rubber. The explosive was firm and rubbery.

Example An explosive containing a polymerized emulsion compound was prepared by mixing the following ingredients: Ingredients Percentage Ammonium Nitrate 12.2 Calcium Nitrate 7.7 Water 2.3 Ammonium Nitrate Prills 81.0 Emulsifier 0.2 Diesel Oil 6.1 HTPB Isonate® 143 L 0.1 The emulsion was made in the conventional manner by dissolving the ammonium nitrate and calcium nitrate in the water at elevated temperature to form an aqueous phase.

This aqueous phase was added by vigorous stirring to the polymerizable HTPB, to which had been added the emulsifier and fuel oil until an emulsion was formed. The emulsion was allowed to cool to room temperature. Thereafter, the ammonium nitrate prills and Isonate® 143 L were added with stirring. The explosive containing the emulsion cured for twenty-one (21) days.

The thus formed emulsion resulted in a discontinuous oxidizing phase uniformly dispersed in a polymerized continuous fuel phase. The explosive had the consistency of a coherent mass of prills.

WO 91/01800 PCT/US90/04261 -31- 1 Example 11 A polymerized and crosslinked emulsion compound suitable for use in an explosive was prepared by mixing the following ingredients: Ingredients Percentage Ammonium Nitrate 41.1 Calcium Nitrate 30.7 Water 16.4 Emulsifier Diesel Oil 7.3 HTPB 131 MA The emulsion was made in the conventional manner by dissolving the ammonium nitrate, and calcium nitrate in the water at elevated temperature to form an aqueous phase.

This aqueous phase was added by vigorous stirring to the polymerizable HTPB, to which had been added the emulsifier, and fuel oil until an emulsion was formed. The emulsion was allowed to cool to room temperature. The 131 MA was gently stirred into the emulsion. This emulsion cured for twenty-two (22) days.

The thus formed emulsion resulted in a discontinuous oxidizing phase uniformly dispersed in a polymerized and crosslinked continuous fuel phase, with the consistency of non-tacky rubber.

Example 12 A crosslinked emulsion compound suitable for use in an explosive was prepared by mixing the following ingredients: Ingredients Percentage Ammonium Nitrate 71.1 Water 16.6 Emulsifier Diesel Oil 10.0 Ir 131 MA WO 91/01800 PCT/US90/04261 -32- 1 Monoethanolamine The emulsion was made in the conventional manner by dissolving the ammonium nittate in the water at elevated temperature to form an aqueous phase. This aqueous phase was added by vigorous stirring to the crosslinkable 131 MA, to which had been added the emulsifier, and fuel oil until an emulsion was formed. The emulsion was allowed to cool to room temperature. Thereafter, the monoethanolamine is added. This emulsion cured for eight weeks.

The thus formed emulsion resulted in a discontinuous oxidizing phase uniformly dispersed in a crosslinked continuous fuel phase, with the consistency of a rubbery nontacky gel.

Example 13 A polymerized emulsion compound suitable for use in an explosive was prepared by mixing the following ingredients: Ingredients Percentage Ammonium Nitrate 48.2 Calcium Nitrate 30.4 Water 10.3 Emulsifier Mineral Oil 3.9 HTPB 2.9 Isonate® 143 L 0.3 The emulsion was made in the conventional manner by dissolving the ammonium nitrate and calcium nitrate in the water at elevated temperature to form an aqueous phase.

This aqueous phase was added by vigorous stirring to the polymerizable HTPB, to which had been added the emulsifier, and mineral oil until an emulsion was formed. The emulsion was allowed to cool to room temperature. Thereafter, the Isonate® 143 L was added. This emulsion cured for twentyone (21) days.

WO 91/01800 PCT/US90/04261 -33- 1 The thus formed emulsion resulted in a discontinuous oxidizing phase uniformly dispersed in a polymerized continuous fuel phase, with the consistency of non-tacky rubber.

Example 14 A polymerized emulsion compound suitable for use in an explosive was prepared by mixing the following ingredients: Ingredients Percentage Ammonium Nitrate 50.3 Calcium Nitrate 31.9 Water 9.7 Emulsifier Diesel Oil Paraffin Wax HTPB Isonate® 143 L 0.1 The emulsion was made in the conventional manner by dissolving the ammonium nitrate and calcium nitrate in the water at elevated temperature to form an aqueous phase.

This aqueous phase was added by vigorous stirring to the polymerizable HTPB, to which had been added the emulsifier, diesel oil, and paraffin wax until an emulsion was formed.

The emulsion was allowed to cool. Thereafter, the Isonate® 143 L was added. The explosive containing the emulsion cured for one day.

The thus formed emulsion resulted in a discontinuous oxidizing phase uniformly dispersed in a polymerized continuous fuel phase with the consistency of a moldable nontacky putty; rehealable rubber.

WO 91/01800 PC/US90/04261 -34- 1 Example A polymerized emulsion compound was prepared by mixing the following ingredients: Ingredientj Percentage Ammonium Nitrate 49.1 Calcium Nitrate 31.0 Water HTPB 5.9 Isonate® 143 L 0.6 The emulsion was made in the conventional manner by dissolving the ammonium nitrate and calcium nitrate in the water at elevated temperature to form an aqueous phase.

This aqueous phase was added by vigorous stirring to the polymerizable HTPB, to which had been added the emulsifier until an emulsion was formed. The emulsion was allowed to cool. Thereafter, the Isonate® 143 L was added. The explosive containing the emulsion cured for four hours.

The thus formed emulsion resulted in a discontinuous oxidizing phase uniformly dispersed in a polymerized continuous fuel phase with the consistency of a thick, stiff wax.

While the foregoing examples de facto illustrate ranges of the substituent ingredients of the emulsion or emulsion phase of an explosive containing an emulsion, ranges of substituent ingredients outside the ranges illustrated above also provide suitable emulsions or emulsion phases of explosives containing an emulsion.

Summary It can be seen, therefore, that the present invention compositions and methods for polymerizing and/or crosslinking the continuous phase of the emulsion or the emulsion phase of an explosive containing an emulsion.

This is accomp.ished by not only choosing polymerizable and/or crosslinkable polymers as components of the fuel WO 91/01800 PCT/US90/04261 1 phase of the emulsion, but actually polymerizing and/or crosslinking the monomers and polymers of the continuous phase- to lock or hold the discontinuous phase in its dispersed position, thereby, inhibiting crystallization, coalescence, agglomeration or migration of the discontinuous oxidizing or sensitizing phase.

It will be appreciated that the advancement of the present invention provides several improvements over conventional emulsions and explosives containing an emulsion. For example, by choosing the appropriate polymerizable or crosslinkable polymer, and by polymerizing and/or crosslinking the polymer, a desired rheology of the subject emulsion may be obtained to suit the particular need of the user. Similarly, the matrix of the desired emulsion can be polymerized and/or crosslinked chemically at room temperature and the resulting emulsion is not as sensitive to changes in ambient temperature as the currently available emulsions are. Furthermore, the rate of reaction of the polymerization or crosslinking can be controlled so as to permit the selection of different rheologies of the same emulsion over a given period of time to the advantage of the manufacturing, packaging, transporting, storage, and use processes and procedures.

The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The described embodiments are to be considered in all respects only as illustrative and not restrictive. The scope of the invention is, therefore, indicated by the appended claims rather than by the foregoing description. All changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.

What is claimed is:

Claims (47)

1. A water-in-oil emulsion for use in an explosive comprising: a continuous phase comprising a blend of organic fuel materials, at least one of the organic fuel materials being at least partially polymerized and crosslinked to achieve a nonrigid rheology, the polymerized organic fuel material being hydroxy or epoxy terminated, and at least one of the organic fuel materials being substantially unpolymerized, the polymerized organic fuel material being generally soluble in the unpolymerized organic fuel material; and a discontinuous phase of an aqueous solution comprising at least one oxygen-containing salt.

2. A water-in-oil emulsion for use in an explosive as defined in claim 1 wherein the organic fuel material comprises a butadiene homopolymer adducted with maleic anhydride.

3. A water-in-oil emulsion for use in an explosive as defined in claim 1 wherein the organic fuel material comprises a polymer with hydroxyl functional groups.

4. A water-in-oil emulsion for use in an explosive as defined in claim 1 wherein the organic fuel material comprises polybutadiene with hydroxyl functional groups.

A water-in-oil emulsion for use in an explosive as defined in claim 1 wherein the crosslinking occurs in the presence of coreactants selected from the group including of be primary, secondary or tertiary amines, metal organic compounds; metallic salts, amides, thiols, and species containing hydroxy functional groups.

6. A water-in-oil emulsion for use in an explosive as defined in claim 1 wherein the oxygen-containing salt comprises ammonium nitrate.

7. A water-in-oil emulsion for use in an explosive as defined in claim 1 wherein the oxygen-containing salt comprises ammonium nitrate and alkali metal nitrates.

8. A water-in-oil emulsion for use in an explosive i0 as defined in claim 1 wherein water is present in an amount up to about 25% of the emulsion.

9. A water-in-oil emulsion for use in an explosive as defined in claim 1 wherein the organic fuel material is crosslinked in a nonexothermic reaction.

A water-in-oil emulsion for use in an explosive as defined in claim 1 wherein the organic fuel material is present in an amount up to about 20% of the emulsion.

11. A water-in-oil emulsion for use in an explosive as defined in claim 1 further comprising aluminum.

12. A water-in-oil emulsion for use in an explosive as defined in claim 1 wherein the discontinuous phase further comprise a solid oxidizer.

13. A water-in-oil emulsion for use in an explosive as defined in claimA44 wherein the solid oxidizer comprises ammonium nitrate.

14. An explosive containing a water-in-oil emulsion comprising: an emulsion comprising 37 38 a continuous phase comprising a blend of organic fuel materials, at least one of the organic fuel materials being at least partially polymerized and crosslinked to achieve a nonrigid rheology, the polymerized organic fuel material being hydroxy or epoxy terminated, and at least one of tne organic fuel materials being substantially unpolymerized, the polymerized organic fuel material being generally soluble in 3 the unpolymerized organic fuel material; and (ii) a discontinuous phase of an aqueous solution comprising at least one oxygen- containing salt, and at least one sensitizer.

An explosive containing a water-in-oil emulsion as defined in claim 4 wherein the organic fuel material comprises polybutadiene with hydroxyl functional groups. 2C

16. An explosive containing a water-in-oil emulsion as defined in claimA4~ wherein the organic fuel material is present in a concentration ranging from about 0.5% to about 16% of the emulsion. 2

17. An explosive containing a water-in-oil emulsion as defined in claimA.4 wherein the oxygen-containing salt comprises ammonium nitrate.

18. An explosive containing a water-in-oil emulsion a as defined in claimA wherein the oxygen-containing salt comprises ammonium nitrate and at least one alkali metal nitrate.

19. An explosive containing a water-in-oil emulsion as defined in claim 14 wherein the oxygen-containing salt comprises ammonium nitrate and at least one alkaline earth metal nitrate.

An explosive containing a water-in-oil emulsion as defined in claim 14 wherein the organic fuel material is polymerized in a nonexothermic reaction.

21. An explosive containing a water-in-oil emulsion as defined in claim 14 wherein the organic fuel materials are present in an amount up to 20% of the emulsion.

22. An explosive containing water-in-oil emulsion as defined in claim 14 further comprising aluminum.

23. An explosive containing a water-in-oil emulsion as defined in claim 14 wherein the discontinuous phase further comprises a solid oxidizer.

24. An explosive containing a water-in-oil emulsion as defined in claim 23 wherein the solid oxidizer is ammonium nitrate.

An explosive containing a water-in-oil emulsion as defined in claim 14 wherein the sensitizer is selected from the group including microspheres, expanded polystyrene, perlite, void containing material, emulsified gassing agents, gas-generating chemicals, reactions which generate gas bubbles in situ, and self-explosives.

26. An explosive containing a water-in-oil emulsion as defined in claim 14 wherein the polymerized organic fuel material is crosslinked.

27. An explosive containing a water-in-oil emulsion as defined in claimA43. wherein the organic fuel material comprises butadiene homopolymer adducted with maleic anhydride.

28. An explosive containing a water-in-oil emulsion as defined in claim 4- wherein the organic fuel material comprises butadiene-styrene homopolymer adducted with maleic anhydride.

29. An explosive containing a water-in-oil emulsion 2 as defined in claim wherein the crosslinking occurs in the presence of reagents selected from the group consisting of primary, secondary or tertiary amines, metal organic compounds; metallic salts, amides, thiols, and species containing hydroxy functional groups.

A method of achieving a desired, ultimate rheology of an emulsion or emulsion phase of an explosive containing an emulsion, the method comprising the steps of: obtaining an emulsion comprising a continuous phase comprising a blend of organic fuel materials, at least one of the organic fuel materials being at least partially polymerized and crosslinked to achieve a nonrigid rheology, the polyermerized organic fuel material being hydroxy or epoxy terminated, and at least one of the organic fuel materials being substantially unpolymerized, the polymerized organic fuel material being generally soluble in the unpolymerized organic fuel material; (ii) a discontinuous phase comprising at least one oxygen-containing salt, and adding a polymerizing agent in sufficient amount to polymerize at least a portion of the organic fuel material until the preselected rheology is obtained.

31. A method of preselecting the ultimate rheology of an emulsion or emulsion phase of an explosive containing an 30 emulsion as defined in claim A.4 wherein the organic fuel material comprises polybutadiene with hydroxyl functional groups.

32. A method of preselecting the ultimate rheology of 1 0 an emulsion or emulsion phase of an explosive containing an emulsion as defined in claimA-3- wherein the organic fuel material is polymerized in a nonexothermic reaction.

33. A method of preselecting the ultimate rheology of an emulsion or emulsion phase of an explosive containing an emulsion as defined in claim 44- wherein the organic fuel material is crosslinked.

34. A method of preselecting the ultimate rheology of an emulsion or emulsion phase of an explosive containing an emulsion, the method comprising the steps of: obtaining an emulsion comprising a continuous phase comprising at least one crosslinkable, insoluble organic fuel material, (ii) a discontinuous phase comprising at least one oxygen-containing salt, and adding a crosslinking agent in sufficient amount to crosslink at least a portion of the organic fuel material until the preselected rheology is obtained.

A method of preselecting the ultimate rheology of an emulsion or emulsion phase of an explosive containing an I uj 34- emulsion as defined in claimA44 wherein the organic fuel material comprises a butadiene homopolymer adducted with maleic anhydride.

36. A method of preselecting the ultimate rheology of 3 an emulsion or emulsion phase of an explosive containing an emulsion as defined in claimA wherein the organic fuel material comprises a butadiene-styrene homopclymer adducted with maleic anhydride. 0

37. A method of preselecting the ultimate rheology of an emulsion or emulsion phase of an explosive containing an .47 emulsion as defined in claimA4. wherein the crosslinking occurs in the presence of coreactants selected from the group including primary, secondary, or tertiary amines, metal organic compounds, metallic salts, amides, thiols, and species containing hydroxy functional groups.

38. A water-in-oil emulsion for use in an explosive as defined in claim 1 wherein the oxygen-containing salt comprises ammonium nitrate and at least one alkaline earth metal nitrate.

39. A water-in-oil emulsion for use in an explosive comprising: a continuous phase comprising a blend of organic fuel materials, at least one of the organic fuel materials being at least partially polymerized and crosslinked to achieve a preselected malleable, non self-supporting rheology, the polymerized organic fuel material being hydroxy-terminated polybutadiene, and at least one of the organic fuel materials being substantially unpolymerized, the unpolymerized organic fuel material being an oil; and a discontinuous phase of an aqueous solution comprising at least one oxygen-containing salt.

A water-in-oil emulsion for use in an explosive as in claim 39, wherein the unpolymerized organic fuel material is mineral oil.

41. A water-in-oil emulsion for use in an explosive as in claim 39, wherein the hydroxy-terminated polybutadiene is crosslinked by isocyanates or maleic anhydride.

42. An explosive containing a water-in-oil emulsion comprising: an emulsion comprising a continuous phase comprising a blend of organic fuel materials, at least one of the organic fuel materials being at least partially polymerized and crosslinked to achieve a preselected malleable, non self-supporting rheology, the polymerized organic fuel material being hydroxy-terminated polybutadiene, and at least one of the organic fuel materials being substantially unpolymerized, the unpolymerized organic fuel material being an oil; and (ii) a discontinuous phase of an aqueous solution comprising at least one oxygen- containing salt, and at least one sensitizer.

43. An explosive containing a water-in-oil emulsion as in claim 42, wherein the unpolymerized organic fuel material is mineral oil.

44. An explosive containing a water-in-oil emulsion as in claim 42, wherein the hydroxy-terminated polybutadiene is crosslinked by isocyanates or maleic anhydride.

A method of achieving a desired, ultimate rheology of an emulsion or emulsion phase of an explosive containing an emulsion, the method comprising the steps of: obtaining an emulsion comprising .0 a continuous phase comprising a blend of organic fuel materials, at least one of the organic fuel materials being at least partially polymerized and crosslinked to achieve a preselected malleable, non self-supporting rheology, the polyermerized organic fuel material being hydroxy or epoxy terminated, and at least one of the organic fuel materials being substantially unpolymerized, the polymerized organic fuel material being generally soluble in 0 the unpolymerized organic fuel material; (ii) a discontinuous phase comprising at least one oxygen-containing salt, and adding a polymerizing agent in sufficient amount to polymerize at least a portion of the organic fuel material until the preselected rheology is obtained.

46. A method of achieving a desired, ultimate rheology of an emulsion or emulsion phase of an explosive containing an emulsion as in claim 45, wherein the unpolymerized organic fuel material is mineral oil.

47. A method of achieving a desired, ultimate rheology of an emulsion or emulsion phase of an explosive containing an emulsion as in claim 45, wherein hydroxy- 1 A terminated polybutadiene is crosslinked by isocyanates or maleic anhydride. Dated.this 20 day of March 1992. MINING SERVICES INTERNATIONAL CORPORATION S By Its Patent Attorneys: GRIFFITH HACK CO. Fellows Institute of Patent Attorneys of Australia. ID INTERNATIONAL SEARCH REPORT International Anolication No PCT/US9O/04261 1. CLASSIFICATION OF SUBJECT MATTER lit several CtaSSifiC~tion symbols apply, indicate all)t Accrding to Intmrational Patent Classification (IPC) or to o hNatio I sic g132, /0 IPC E301J 13/00; C0611 3304, 6 t 724; ClOL1/270 U.S. cl 44/7.3,7.6,51; 149/2,43,108.8,109.2,118; 524/801; (con't) IL. FIELDS SEARCHED -Minimum, Documentation Searched Classification System Cassification S 1 mools U.S. 44/7.3,7.6,51; 149/2,43,108.8,109.2,118; 524/801; 525/332.5; 526/219.5,932 Documentation Searched other tha~n Minimumn Documentation to the Extent tha! such Documnents are Inctuded in the Fields 1t1. DOCUMENTS CONSIDERED TO HE RELEVANT 14 Category Citvtion of Document, I' with indication, where aoorooriate, of the retevitnt passages Retevant to Ctaimn No.I Y US,A 4,077,931 (LEIUM-rISR Er AL) 1-75 07 March 1978 See Examples 1,3 7-9; Colum 4, Line 53; Column 6, Line 19 Column 7, Line 3; Column 8, Lines 45-57; Column 9, Line 42 Column 10, Line 2. Y US,A 4,343,663 (BREZA Er AL) 10 August 1982 1-75 See Col.umn 4, Lines 33-37; Colum 5, Lines 9, Lines 30-34; Column 10, Lines 21-42. Y US,A 4,385,164 (SINCLAIR Er AL) 24 May 1983 See Examples 4,5-7 8; Column 4, Line Column 5, Lines 12; Column 5, Line 16 Column 6, Line 57. A US,A 3,447,978 (BLM) 03 June 1969 1-75 (CON' Special categories of cited documents: t' later document Olubtished after the international filing dat0 document defining the general stale of the art which is not or, priority dale and not in conflict with the application but considered to be of particular relevance cited to understand the principle or theory underlying the invention farllqr document but published on or alter the international document of particular relevance: the ctaimed invention filling date cannot be considered novel or cannot be considered to document which may throw doubts on priority claim(s) or involve an inventive step which Is cited to establish the jublication date of another document ot pArticular relevance: the clatmed invention citation or other special reason (,ta specified) cannot be considered to involve an inventive steo, when the I'O' document referring to an orat disclosure, iuse, exhibition or document is combined with one or more other such dOCU. other means ments, Such Combination being obvious to a person sllited document published prior to the internainat fI'ling date but in the art. later than the priority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Comoletion of the International Search 2 Date of Maiting of this International Serrch Report 29 OCTBER 1990 9JAN 1 International Searching Authority I tueof Authorized Ofrice ISA/US RIGARD D. LOVERING I Form PCTIISA/21 0 Isscoeld shoit) IMay 1988) International Apolication No. PCT/US90/04261 FURTHER INFORMATION CONTINUED FROM THE SECOND SHEET A CLASSIFICATION OF SUITECT MATTER U.S. Cl 525/332.5; 526/219.5,932 US,A 4,736,683 (BACHMAN ET AL) 12 April 1988 1-75 V OBSERVATIONS WHERE CERTAIN CLAIMS WERE FOUND UNSEARCHABLE 1 This international search report has not been established in resrpct of certain claims under Article 17(2) for the following reasons: Claim numbers because they relate to sublect matter I not required to be searched by this Authority, namely: Claim numbers because they relate to parts of the international application that do not comply wilh the rirescribed require. ments to such an extent that no meaningful international search can be carried out I, specifically: 3, O Claim numbers because they ae dependent claims not drafted in accordance with the seconnd ad tmird sentences of PCT Rule 6.4(a), VI.0 OBSERVATIONS WHERE UNITY OF INVENTION IS LACKING 2 This International Searching Authority found multiple inventions in this international application as follows: As all required additional search fees were timely paid by the applicant, this international search report covers all searchable claims of the International application. 2.1 As only some of the required additional search fees were tlmel' paid by the applicant, this international searcn report covers only those claims of the international application for which fees were paid, specifically claims: 3.7 No required additional search fees were timely paid by the applicant. Consequently, this international search report Is restricted to the invention first mentioned In the claims; At s covered by claim numbers: 4 As all searchable claims could be searched without effort lustifying an additional fee, the International Searching Authority did not invite payment of any additional lee. Remark or Protest 0 The tddilional search fees were accompanied by applicant's protest, No plotest accompan, the payment of additional search fees. Form PCT/ISA210 (upolmnuntal st (Rev. 4.90)