CA2065848C - Water-in-oil emulsion explosive composition - Google Patents
Water-in-oil emulsion explosive compositionInfo
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- CA2065848C CA2065848C CA002065848A CA2065848A CA2065848C CA 2065848 C CA2065848 C CA 2065848C CA 002065848 A CA002065848 A CA 002065848A CA 2065848 A CA2065848 A CA 2065848A CA 2065848 C CA2065848 C CA 2065848C
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase
- C06B47/14—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase comprising a solid component and an aqueous phase
- C06B47/145—Water in oil emulsion type explosives in which a carbonaceous fuel forms the continuous phase
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Abstract
Disclosed is a water-in-oil emulsion explosive composition comprising a continuous phase consisting of a carbonaceous component; a disperse phase consisting of an aqueous solution of inorganic oxidizer salt; an emulsifier; an organic gas-retaining agent; and an aluminum powder. The present explosive composition can show especially high underwater explosion energy.
Description
SPECIFICATION
Water-in-oil emulsion explosive composition Technical Field This invention relates to a water-in-oil emulsion explosive (hereinafter abbreviated as W/0 explosive) composition having high underwater explosion energy, which can be used as an explosive for coal mining and in other mining industries.
Background Art When evaluating the power of explosives, studies have conventionally investigated the degree of sympathetic detonation, ballistic mortar value, and the detonation velocity. Recently, underwater explosion energy has also been studied.
Aluminum powder-containing W/0 explosives are disclosed, for example, in the specifications of Japanese Patent Laid-open Application No. 110308/19'19, U.S. Patent Nos. 3'1'10522 and 344?978. These explosives each contain a glass microballoon (GMB) which acts as a gas retaining agent, and an aluminum powder.
One proposed technique of enhancing the underwater explosion energy of the W/0 explosive compositions is to increase the content of inorganic oxidizer salt such as ammonium nitrate, sodium nitrate and potassium nitrate.
However, the W/O explosive compositions disclosed in the above three references may show enhanced power in the detonation velocity, sympathetic detonation and ballistic mortar value, but the amount of the aluminum powder to be added in combination with GMB is limited to about 20 % by weight in view of production limitations. These explosives suffer a problem in that they do not explode if the content of the aluminum powder is increased. Moreover, the content of the inorganic oxidizer salt cannot be increased so much because of production limitations. Therefore the effect of the inorganic oxidizer salt is small.
It is an object of this invention to provide a W/O
explosive composition having excellent emulsion stability and a particularly high underwater explo-sion energy.
It is another object of this invention to provide a W/O explosive composition having high detonation reliability and improved low-temperature detonating properties.
According to one aspect of the invention, there is provided an explosive composition containing an aluminum powder and a water-in-oil emulsion includ-ing a continuous phase, a disperse phase, an emulsi-fier and a gas-retaining agent, characterized in that:
the continuous phase comprises 1 to 10 wt.% of a carbonaceous fuel, based on the total weight of the explosive composition;
the disperse phase comprises 3 to 30 wt.%
of water and 5 to 90 wt.% of an inorganic oxidizer salt, based on the total weight of the explosive composition;
the emulsifier is present in an amount of 0.1 to 10 wt.%, based on the total weight of the explosive composition;
the gas-retaining agent is an organic gas-retaining agent having an average particle size of 10 to 4000 ~.m and is present in an amount of 1 to 50 vol.%, based on the total volume of the explosive composition; and the aluminum powder has an average parti-cle size not greater than 1 mm and is in admixture with the emulsion, the aluminum powder being present in an amount of 10 to 70 wt.%, based on the total weight of the explosive composition, whereby the explosion energy of the emul-sion mixed with the aluminum powder is at least 1.16 times greater than the explosion energy of an emulsion not containing aluminum powder. Such an explosive composition not only has a high underwater explosion energy but also excellent emulsion stability.
According to another aspect of the invention, there is also provided an explosive composition as defined above in which the gas-retaining agent is an organic material and which further includes a sensitizer.
Such an explosive composition has high detonation reliability and excellent low-temperature detonating properties in addition to high underwater explosion energy.
The present invention further provides an explosive composition containing an aluminum powder and a water-in-oil emulsion including a continuous phase, a disperse phase, an emulsifier and a gas-retaining agent, characterized in that:
the continuous phase comprises 2.2 to 2.8 wt.% of a carbonaceous fuel, based on the total weight of the explosive composition;
the disperse phase comprises 9.2 to 11.7 wt.% of water and 70.9 to 82.7 wt.% of an inorganic oxidizer salt, based on the total weight of the explosive composition;
Water-in-oil emulsion explosive composition Technical Field This invention relates to a water-in-oil emulsion explosive (hereinafter abbreviated as W/0 explosive) composition having high underwater explosion energy, which can be used as an explosive for coal mining and in other mining industries.
Background Art When evaluating the power of explosives, studies have conventionally investigated the degree of sympathetic detonation, ballistic mortar value, and the detonation velocity. Recently, underwater explosion energy has also been studied.
Aluminum powder-containing W/0 explosives are disclosed, for example, in the specifications of Japanese Patent Laid-open Application No. 110308/19'19, U.S. Patent Nos. 3'1'10522 and 344?978. These explosives each contain a glass microballoon (GMB) which acts as a gas retaining agent, and an aluminum powder.
One proposed technique of enhancing the underwater explosion energy of the W/0 explosive compositions is to increase the content of inorganic oxidizer salt such as ammonium nitrate, sodium nitrate and potassium nitrate.
However, the W/O explosive compositions disclosed in the above three references may show enhanced power in the detonation velocity, sympathetic detonation and ballistic mortar value, but the amount of the aluminum powder to be added in combination with GMB is limited to about 20 % by weight in view of production limitations. These explosives suffer a problem in that they do not explode if the content of the aluminum powder is increased. Moreover, the content of the inorganic oxidizer salt cannot be increased so much because of production limitations. Therefore the effect of the inorganic oxidizer salt is small.
It is an object of this invention to provide a W/O
explosive composition having excellent emulsion stability and a particularly high underwater explo-sion energy.
It is another object of this invention to provide a W/O explosive composition having high detonation reliability and improved low-temperature detonating properties.
According to one aspect of the invention, there is provided an explosive composition containing an aluminum powder and a water-in-oil emulsion includ-ing a continuous phase, a disperse phase, an emulsi-fier and a gas-retaining agent, characterized in that:
the continuous phase comprises 1 to 10 wt.% of a carbonaceous fuel, based on the total weight of the explosive composition;
the disperse phase comprises 3 to 30 wt.%
of water and 5 to 90 wt.% of an inorganic oxidizer salt, based on the total weight of the explosive composition;
the emulsifier is present in an amount of 0.1 to 10 wt.%, based on the total weight of the explosive composition;
the gas-retaining agent is an organic gas-retaining agent having an average particle size of 10 to 4000 ~.m and is present in an amount of 1 to 50 vol.%, based on the total volume of the explosive composition; and the aluminum powder has an average parti-cle size not greater than 1 mm and is in admixture with the emulsion, the aluminum powder being present in an amount of 10 to 70 wt.%, based on the total weight of the explosive composition, whereby the explosion energy of the emul-sion mixed with the aluminum powder is at least 1.16 times greater than the explosion energy of an emulsion not containing aluminum powder. Such an explosive composition not only has a high underwater explosion energy but also excellent emulsion stability.
According to another aspect of the invention, there is also provided an explosive composition as defined above in which the gas-retaining agent is an organic material and which further includes a sensitizer.
Such an explosive composition has high detonation reliability and excellent low-temperature detonating properties in addition to high underwater explosion energy.
The present invention further provides an explosive composition containing an aluminum powder and a water-in-oil emulsion including a continuous phase, a disperse phase, an emulsifier and a gas-retaining agent, characterized in that:
the continuous phase comprises 2.2 to 2.8 wt.% of a carbonaceous fuel, based on the total weight of the explosive composition;
the disperse phase comprises 9.2 to 11.7 wt.% of water and 70.9 to 82.7 wt.% of an inorganic oxidizer salt, based on the total weight of the explosive composition;
zo s5~ 48 the emulsifier is present in an amount of 2.2 to 2.8 wt. %, based on the total weight of the explosive composition;
the gas-retaining agent is an organic gas-retaining agent having an average particle size of to 4000 ~m and is present in an amount of 0.6 to 2.5 wt.%, based on the total weight of the explosive composition; and the aluminum powder has an average parti-cle size not greater than 1 mm and is in admixture with the emulsion, the aluminum powder being present in an amount of 10 to 70 wt.%, based on the total weight of the explosive composition, whereby the explosion energy of the emul-sion mixed with the aluminum powder is at least 1.16 times greater than the explosion energy of an emulsion not containing aluminum powder.
Preferably, the explosion energy of the emulsion mixed with the aluminum powder is substantially at most 2.13 times greater than the explosion energy of an emulsion not containing aluminum powder.
The carbonaceous fuel which forms a continuous phase includes those conventionally employed in the W/O
explosives; for example, in the first aspect of this invention, hydrocarbons such as paraffinic hydro-carbons, olefinic hydrocarbons, naphthenic hydro-carbons, aromatic hydrocarbons, saturated or unsatu-rated hydrocarbons, petroleum purified mineral oils, lubricants and liquid paraffin; hydrocarbon deriva-tives such as nitrohydrocarbon; waxes including those derived from fuel oils and/or petroleum such as purified or unpurified microcrystalline wax, paraffin wax and petrolatum, mineral waxes such as montan wax, animal waxes such as whale wax and -4a-insect waxes such as beeswax. These carbonaceous fuels can be used alone or in admixture.
Preferred carbonaceous fuels include microcrystal-line wax and petrolatum in view of storage stabi-lity, and particularly preferred is microcrystalline wax. At the same time, preferred carbonaceous fuels to be used in the second aspect of this invention include waxes such as microcrystalline wax, paraffin wax and polyethylene wax; and fuel oils such as light oils of classification No. 2, which are conventionally used in the W/O explosives. The waxes are particularly preferred -S-in view of their texture such as hardness etc.
For the purpose of texture adjustment, a low-molecular Weight hydrocarbon polymer such as a petroleum resin, a low-molecular weight polyethylene and a low-molecular weight polypropylene may be added in combination with the carbonaceous fuel component. The carbonaceous fuel is usually added in an amount of 1 to 10 % by weight based on the total amount of the W/0 explosive.
The inorganic oxidizer salt, which forms the disperse phase in the form of aqueous solution, includes those conventionally used in the W/0 explosive compositions; for example, nitrates of alkali or alkaline earth metals such as ammonium nitrate, sodium nitrate and potassium nitrate; and inorganic chlorates or perchlorates such as sodium chlorate, ammonium perchlorate and sodium perchlorate. Usually ammonium nitrate is used alone or in admixture with other inorganic oxidizer salt. The inorganic oxidizer salt is usually added in an amount of 5 to ' 90 % by weight, preferably 40 to 80 % by weight.
The water content in the W/0 explosive composition according to this invention is preferably in the range of 3 to 30 % by weight, more preferably T to 30 % by weight.
Now, as the emulsifier, which plays a role to stabilize the emulsion, any of those conventionally used in the W/O
explosives can be used; for example, fatty acid esters of sorbitan such as sorbitan monolaurate, sorbitan monooleate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan dioleate and sorbitan trioleate; mono or diglycerides of fatty acids such as stearic acid monoglyceride; fatty acid esters of polyoxyethylene sorb j. tan, oxazoline derivatives, imidazoline derivatives, phosphoric acid esters, alkali or alkaline earth metal salts of fatty acids and primary, secondary or tertiary amine salts. These emulsifiers may be used alone or in admixture. Preferred of these emulsifiers are fatty acid esters of sorbitan. The emulsifier is preferably added in an amount of 0.1 to 10 % by weight, more preferably 1 to 5 % by weight.
As the sensitizer, which enhances detonation reliability and improves low-temperature detonating properties, .those conventionally used in the W/0 explosives such as monomethylamine nitrate, hydrazine nitrate and ethylenediamine nitrate can be used. However, hydrazine nitrate is preferred since it can improve solubility of ammonium nitrate and has high explosion energy. When such sensitizer is used, it is preferably added in an mount of 1 to 40 % by weight, more preferably not more than 30 % by weight, most preferably not more than 20 % by weight in the W/0 explosive composition.
If the percentage of the sensitizer exceeds 40 % by weight, danger in hand:li.ng the explosive composition will sometimes be increased.
Particularly when hydrazine nitrate and the like is used as the sensitizPr, it is advantageous to use a chelating agent such as sodium ethylenediaminetetraacetate so as to prevent decomposition of the hydrazine nitrate. The chelating agent - is preferably ;added in an amount of 0.1 to 10 % by weight based on the amount of the sensitizer.
The gas-retaining agent is an organic material. The organic gas-retaining agent may be selected from various types of single hollow microspheres or bubble assemblies containing a plurality of cells; for example, carbonaceous hollow microspheres obtained from pitch, coal, etc.; synthetic resin hollow microspheres obtained from phenol resins, polyvinylidene chloride, epoxy resins, urea resins, etc. The bubble assembl_'ies containing a plurality of cells include a milled powder and grains prepared by incorporating air into a raw material synthetic high polymer, for example, olefins such as ethylene, propylene and styrene; polymers of vinyl compounds such as vinylidene chloride, vinyl alcohols, vinyl acetate, and acrylic acid, methacrylic acid or esters thereof, or copolymers, modified polymers or mixed polymers thereof;
synthetic polymers such as polyurethane, polyester, polyamide, urea resin, epoxy resin and phenol resin, by means of various technigues solch as mechanical foaming, chemical foaming, micro-encapsulation, incorporation of an easily volatile material, etc., followed by milling.
Preferred of these organic gas-retaining agents are those made from polystyrene, polyethylene or polyv.inylidene chloride.
These organic gas-retaining agents, unlike the inorganic gas-retaining agents such as glass, silica, etc., do not damage the emulsion membrane and can maintain the emulsion stable. These organic gas-retaining agents are superior to the inorganic ones, since they have low specific gravity, they do not assume a form of inactive additive, and they are easily available at low costs.
When an organic gas-retaining agent is used, it never happens that the emulsion is partly damaged by pumping during the process of manufacturing unlike the inorganic gas-retaining agents. Accordingly, an explosive which can exhibit the designed detonation performance and has good storage stability can be provided.
Further, the organic gas-retaining agent may be of single bubbles or assemblies of single bubbles, and the diameter of which is not critical. However, in the first aspect of this invention, one having an average particle size in the range of 10 to 4,000 dam is particularly used. If one having an average particle size of less than 10 izm is used, it comes to r have a greater specific gravity and must be added in an increased amount; whereas if one having an average size of greater than 4 , 000 lzm is used, the underwater explosion energy will be lowered. Incidentally, the particle shape of the gas-retaining agent may be any spherical, cylindrical, polyhedral, etc.
A suitable organic gas-retaining agent is selected depending on the application of the W/0 explosive. The organic gas--retaining agent is preferably added in an amount of 1 to 50 % by volume in the W/O explosive. If the content of the organic gas-retaining agent is less than 1 % by volume, cap-sensitivity of the resulting explosive composition will be lowered or 'the detonation will be interrupted; whereas if the content of the organic gas-retaining agent exceeds 50 %
by volume, the underwater explosion energy tends to be lowered.
The aluminum powder is used as a fuel and also to improve underwater explosion energy. While ordinary aluminum powders can be used, those having a particle size of not more than 1 mm, preferably in the range of 0.01 to 1 mm, more preferably in the range of 0.03 to 0.1 mm, are particularly used in the first aspect of this invention. If an aluminum powder having a particle size of more than 1 mm is used, the underwater explosion energy will be lowered. The particle shape of the aluminum powder. may be any spherical, scaly, etc.
In this invention, the aluminum powder can be used in a greater amount than in the prior art explosive compositions.
If no sensitizer is added, the content of the aluminum powder is in the range of 10 to ?0 % by weight, preferably in the range of 20 to ?0 % by weight; whereas if a sensitizer is added, it is im the range of 10 to ?0 % by weight. If the content of the aluminum powder is less than 10 % by weight, the fuel component will be insufficient to give reduced detonation performance; while if it exceeds ZO % by weight, inactive aluminum powder remains in the resulting composition to reduce the detonation performance.
The preferred compounding ratio of the respective components in the W/0 explosive composition in the first aspect of this invention is as follows: 40 to 90 parts by weight of an inorganic oxidizer salt; Z to 30 parts by weight of water; 0.5 to 10 parts by weight of a carbonaceous fuel; 0.5 to 10 parts by weight of an emulsifier; 1 to 40 parts by weight of a sensitizer; 1 to 50 % by volume of an organic gas-retaining agent having an average particle size of 10 to 4,000 um ; and to ZO % by weight of an aluminum powder having an average particle size of not more than 1 mm . Meanwhile, the preferred compounding ratio of the respective components in the second aspect of this invention is as follows: 40 to 90 parts by weight of an inorganic oxidizer salt; T to 30 parts by weight of water; 0.5 to 10 parts by weight of a carbonaceous fuel; 0.5 to 10 parts by weight of an emulsifier;
1 to 40 parts by weight of a sensitizer; 1 to 50 % by volume of an organic gas-retaining agent; and 10 to TO % by weight of an aluminum powder.
If the content of the inorganic oxidizer salt is less than 40 % by weight, i:he detonation performance of the resulting composition will be lowered; whereas if it exceeds 90 % by weight, solubility thereof will be reduced. If the water content is lees than Z % by weight, solubility of the inorganic oxidizer salt will be lowered; whereas if it exceeds 30 % by weight, the contents of the other components will relatively be smaller to easily lower the detonation performance of the resulting composition. Addition of the carbonaceous f~.iel in an amount of less than 0.5 % by weight cannot give a ~~ery fine emulsion to provide small contact area; whereas .if it exceeds 10 % by weight, the content of the inorganic oxidizer salt will relatively be smaller. If the content of. the emulsifier is less than 0.5 % by weight, stability of the emulsion tends to be lowered; whereas if it exceeds 10 % by weight, detonation performance of the resulting composition can hardly be improved. If the content of the sensitizer is less than 1 % by weight, the resulting composition sheaws insufficient denotation reliability; whereas if it exceeds 40 % by weight, danger in the handling of the resulting composition will be increased. If the content of the organic gas-retaining agent-is less than 1 % by volume, cap-sensitivity of the resulting composition may be reduced and explosion may be interrupted; whereas if it exceeds 50 %
by volume, the underwater explosion energy tends to be lowered. If the aluminum powder is added in an amount of more than or less than the specified range of 10 to ZO % by weight, the detonation performance of the resulting explosive composition tends to be lowered.
The present W/O explosive composition can be prepared, for example, in the following manner.
An inorganic oxidizer salt, optionally together with a sensitizer and a chelating agent, is dissolved in a hot water (ca. 60 to 1.00°C) to prepare an aqueous solution of inorganic oxidizer salt.. Meanwhile, a carbonaceous fuel and an emulsifier are mixed by heating at a temperature where they assume a liquid state, usually at ZO to 90°C, to prepare a combustible material mixture. Next, the aqueous solution of the inorganic oxidizer salt and the combustible material mixture prepared above are mixed by stirring at a temperature of 60 to 90°C at a rate of about 600 to 6,000 rpm to provide a W/0 em~nlsion. S»bsequently, an organic gas-retaining agent and an aluminum powder are admixed to the resulting W/O
emulsion to give a W/0 explosive composition.
The thus obtained W/O explosive composition characteristically shows a particularly enhanced underwater explosion energy owing to the organic gas-retaining agent employed as the gas-retaining agent and also aluminum powder incorporated therein, since the emulsion membrane cannot easily be damaged by the organic: gas-retaining agent unlike by the inorganic gas-retaining agent, and since the organic gas-retaining agent has a smaller specific gravity than the inorganic gas-retaining agent, and thus the proportion of the,emulsion will be greater to allow the aluminum powder to be incorporated in an increased amount.
The underwater explosion energy can be divided into shock energy (Es) and bubble energy {Eb). The ratio of Eb to Es is usually about 3, and the combination of these two energy val,nes Es and Eb is the total underwater explosion energy { see Encyclopedia of Explosives, Vol. 10, 1983, published by American Army Armament Research and Development Command).
Incidentally, the present W/0 explosive composition is of high safety, since it is an emulsion type hydrated explosive.
BEST MODE FOR CARRYING OUT THE INVENTION
Preferred embodiments of this invention will now be described below by way of Examples in comparison with Comparative Examples; wherein parts) mean part{s) by weight.
(Examples 1 to 6) A W/0 explosive composition was prepared using ammonium nitrate as the inorganic oxidizer salt, sorbitan monooleate as the emulsifier, a microcrystalline wax as the carbonaceous fuel, single-bubble assemblies of polystyrene having an average particle size of 300 um as the gas retaining agent, hydrazine nitrate as the sensitizer and an aluminum powder having an average particle size of 30 ~zm. The proportion of the respective components are as shown in the following Tables 1 and 2.
The procedure of preparing the W/O explosive composition is as follows: ,Ammonium nitrate and hydrazine nitrate were dissolved in water by heating at about 85°C. Meanwhile, a mixture of the microcrystalline wax and sorbitan monooleate was melted at about 85°C, and the solution prepared above was added to the melted mixture, followed by stirring by an agitating blade to effect emulsification. The gas-retaining agent and aluminum powder were admixed to the resulting emulsion to provide a W/O explosive composition. Underwater explosion energy was determined for the thus obtained W/0 explosive composition, and the results are also shown in Tables 1 and 2.
Incidentally, measurement of the underwater explosion energy was carried out by laying the explosive at the water depth of 4 m in a pool fc~r determining underwater explosion energy and measuring the shock pulse of the exploded explosive by means of a pressure gauge (Tolmarine gauge) set at the same water depth and at an arbitrary distance so as to calculate Es value and Eb val~.ie, respectively. The total energy was obtained by combining the E> and Eb values in terms of the relative ratio to the values obtained in Comparative Example 1, according to the following equation.
Esn + Ebn Total energy ratio =
Eso + Ebo In the above equation, Eso and Ebo are the values obtained in Comparative Example 1, while Esn and Ebn are the values obtained in Comparative Control Examples.
(Comparative Example i) A W/0 explosive composition was prepared in the same manner as in Examples 1 to 6, except that the aluminum powder was omitted. The thus prepared W/0 explosive composition was tested in the same manner as in Example 1, and the results are as shown in Table 3.
(Comparative Example 2) A W/0 explosive composition was prepared in the same manner as in Example ;3, except that the organic gas-retaining agent was replaced by GMB having an average particle size of 50 pm as the inorganic gas=retaining agent. The thus prepared W/0 explosive composition was tested in the same manner as in Examples 1 to fi, and the results are as shown in Table 3.
Table 1 Table 2 Table 3 The outer percentage of the aluminum powder shown in Tables 1 to 3 is indicated by % by weight per 100 parts by weight of the W/0 explosive composition excluding the aluminum powder.
As can be seen from Tables 1 to 3, the W/0 explosive compositions obtained~in Examples 1 to 6 each showed a high total energy of 116 to 213 as the underwater explosion energy over the one obtained in Comparative Example 1, provided that the value of Comparative Example 1 is 100, and the explosive compositions obtained in Examples 5 and 6 each showed a value more than twice the value of the Comparative Example 1.
On the contrary, the W/0 explosive composition of Comparative Example 1 showed only a low level of underwater explosion energy, since it does not contain an aluminum powder although it contains an.organic gas-retaining agent. Meanwhile, the W/0 explosive composition of Comparative Example 2 found diffic~.ilty in maintaining the shape of the W/0 explosive and did not explode. This was because it uses a combination of an aluminum powder and GMB as the inorganic gas-retaining agent, and the al~.iminum powder was used in an increased amount.
The Es value of the W/O explosive (a standard W/O explosive composition) in Comparative Example 1 is about 0.'I MJ/kg; the Eb value thereof-, about 2.1 MJ/kg; and the total energy, about 2.8 MJ/kg. Meanwhile, the total energy of the W/O explosive composition in each Example is increased to about 3.2 MJ/kg (Example 1) to 6.0 MJ/kg (Example 6).
(Example Z) A W/O explosive was prepared using the explosive composition as shown in Table 4 in the following manner:
To 10.5 parts of. water were added '14.4 parts of ammonium nitrate as the inorganic oxidizer salt, 10 parts of hydrazine nitrate as the sensitizer and 0.5 part of sodium ethylenediaminetetraacetate as the chelating agent, and they were dissolved well with heating at 90°C to prepare an aqueous solution of inorganic oxidizer salt. Meanwhile, 2.3 parts of 2o s5s 48 WARREX* 602 as the carbonaceous fuel and 7. . 3 parts of sorbitan tnonooleate as the emulsifier were mixed with heating at 90°C
to prepare a combustible material mixture. To the resulting mixture was added slowly the aqueous solution of inorganic oxidizer salt to effect emulsification by stirring at 650 rpm with heating at 90°
After completion of emulsification, the resulting emulsion was further stirred at 1,600 rpm for one minute to provide a W/0 emulsion. Subsequently, 0.? part of an organic gas-retaining agent having an average particle size of 300 pm and 11 parts of an aluminum powder were admixed to the W/0 emulsion at 60 to 80°C to give a W/0 explosive composition. Underwater explosion energy was determined for the thus obtained W/0 explosive composition, and the results are as shown in the following Table ?.
(Example 8) A W/0 explosive composition was prepared as shown in Table 4 in the same manner as in Example ?, except that the sensitizer and chelating agent were omitted and that the content of the aluminum powder was changed. Performance of the resulting W/0 explosive composition was evaluated, and the results are as shown in Table ?.
As can be seen from Table ?, the explosive composition prepared here showed a higher total energy ratio than that prepared in Example Z.
(Example 9) A W/0 explosive composition was prepared as shown in Table 4 substantially in the same manner as in Example ?, except that the content of the aluminum powder was increased: Performance * Trade mark of the resulting W/0 explosive composition was evaluated, and the results are as shown in Table T.
As can be seen from Table T, the explosive composition prepared here showed a higher total energy ratio than that prepared in Example Z.
(Example 10) A W/O explosive composition was prepared as shown in Table 5 substantially in the same manner as in Example 8, except that the content of 'the aluminum powder was increased. Performance of the resulting W/0 explosive composition was evaluated, and the results are as shown in Table S.
As can be seen from Table 8, the explosive composition prepared here showed a higher total energy ratio than that prepared in Example 8.
(Exampl.e 11) A W/0 explosive composition was prepared as shown in Table 5 substantially in the same manner as in Example 9, except that the content of the aluminum powder was increased. Performance of the resulting W/0 explosive composition was evaluated, and the results are as shown in Table 8.
As can be seen from Table 8, the explosive composition prepared here showed a higher total energy ratio than that prepared in Example 9.
(Example 12) A W/O explosive composition was prepared as shown in Table 5 substantially i:n the same manner as in Example 11 , except that the content of the aluminum powder was increased. Performance of the res~.ilting W/O explosive composition was evaluated, and the results are as shown in Table 8.
As can be seen from Table 8, the explosive composition prepared here showed a slightly higher total energy ratio than that prepared :in Example 11.
(Example 13) A W/0 explosive composition was prepared as shown in Table 6 substantially in the same manner as in Example 10, except that the content of the aluminum powder was increased. Performance of the resulting W/O explosive composition was evaluated, and the results are as shown in Table 9.
As can be seen from Table 9, the explosive composition prepared here showed a slightly higher total energy ratio than that prepared 9.n Example 10.
(Example 14) A W/0 explosive composition was prepared as shown in Table 6 substantially in the same manner as in Example 12, except that the content of t:he aluminum powder was increased. Performance of the resulting W/O explosive composition was evaluated, and the results are as shown in Table 9.
As can be seen from Table 9, the explosive composition prepared here showed a slightly higher total energy ratio than that prepared in Example 12.
(Example 15) A W/0 explosive composition was prepared as shown in Table 6 substantially in the same manner as in Example 13, except that the content of the aluminum powder was increased. Performance of the resulting W/O explosive composition was evaluated, and the results are as shown in Table 9.
As can be seen from Table 9, the explosive composition prepared here showed a slightly higher total energy ratio than that prepared in Example 13.
It should be noted here that the abbreviations used in the following Tables 4 to 6 stand for the respective compound as shown below.
MMA nitrate: Monomethylamine nitrate Hyd nitrate: Hydrazine nitrate EDA nitrate: Ethylenediamine nitrate EDTA: Sodium ethylenediaminetetraacetate SMO: Sorbitan monooleate SMG: Monvglyceride stearate Wax (1): WARREX* 602 Wax (2): Microcrystalline Wax 160 Wax (3): POLYWAX* 500 GMB: Glass microballoon (particle size:
20 to 140 ~tm; average particle size: 60 ~tm) SMB: Shirasu microballoon (particle size: 30 to 150 pm; average particle size:
75 pm) RMB (1): Polyvinylidene chloride type resin microballoon (particle size: 10 to 100 ~Zm; average particle size 30 ~Zm) Expanded polystyrene foam (1):
Obtained by prefvaming an expanded polystyrene foam beads (particle size: 180 to 700 ~Zm; average particle size: 300 pm) * Trade mark Table 4 Table 5 Table 6 Table ?
Table 8 Table 9 (Comparative Example 3) A W/0 explosive composition was prepared as shown in Table 10 in the same manner as in Example 1, except that the aluminum powder was omitted. Performance of the resulting W/0 explosive composition was evaluated, and the results are as shown in Table 16. -The thus prepared explosive composition is a standard composition for calculating the respective energy ratio.
(Comparative Example 4) A W/0 explosive composition was prepared as shown in Table 10 in the same manner as in Example ?, except that the content of the aluminum. powder was reduced. Performance of the resulting W/O explosive composition was evaluated, and the results are as shown in Table 16.
As can be seen from Table 16, the explosive composition prepared here showed a lower total energy ratio than that prepared in Example ?.
(Comparative Example 5) A W/0 explosive composition was prepared as shown in Table 10 in the same manner as in Example ?, except that the content of the aluminum powder was increased. Performance of the -2.0-resulting W/0 explosive composition was evaluated, and the results are as shown in Table 16. This explosive composition did not explode.
(Comparative Example 6) A W/0 explosive composition was prepared as shown in Tabl~ 11 smbstantially in the same manner as in Comparative Example. 4, except that an aluminum powder having a greater particle size was used. Performance of the resulting W/0 explosive composition was evaluated, and the results are as shown in Table 1T. This explosive composition did not explode.
(Comparative Example '1) A W/0 explosive composition was prepared as shown in Table 11 s,.ibstant ial ly in the same manner as in Comparat ive Example 5 , except that an aluminum powder having a greater particle size was used. Performance of the resulting W/0 explosive composition was evaluated, and the results are as shown in Table iZ. This explosive composition did not explode.
(Comparative Example 8) A W/0 explosive composition was prepared as shown in Table il substantially in the same manner as in Example 8, except that the content of th.e aluminum powder was reduced. Performance of the resulting W/O explosive composition was evaluated, and the results are as shown in Table iZ.
As can be seen from Table iT, the explosive composition prepared here showed a lower total energy ratio than that prepared in Example 8.
(Comparative Example 9) A W/0 explosive composition was prepared as shown in Table 12 substantially in the same manner as in Example 8, except that the content of the aluminum powder was increased.
Performance of the resulting W/0 explosive composition was evaluated, and the results are as shown in Table 18. This explosive composition did not explode.
(Comparative Example 10) A W/0 explosive composition was prepared as shown in Table 12 substantially in the same manner as~ in Comparative Example 8, except that an aluminum powder having a greater particle size was used. Performance of the resulting W/O explosive composition was evaluated, and the results are as shown in Table 18. This explosive composition did not explode.
(Comparative Exarnple il) A W/O explosive composition was prepared as shown in Table 12 substantially in the same manner as in Comparative Example 9, except that an aluminum powder having a greater particle size was used. Per:Eormance of the resulting W/0 explosive composition was evaluated, and the results are as shown in Table 18. This explosive composition did not explode.
(Comparative Example 12) As can be seen from Table 19, the explosive composition prepared here showed a lower total energy ratio than that prepared in Example 9.
(Comparative Example 13) A W/0 explosive composition was prepared as shown in Table 13 substantially in the same manner as in Example 9, except,that a resin microballoon (RMB) having a smaller average particle size was used as the gas-retaining agent . Performance of the resulting W/O explosive composition was evaluated, and the results are as shown in Table 19.
As can be seen from Table 19, the explosive composition prepared here showed a lower total energy ratio than that prepared in Example 9.
(Comparative Example 14) A W/O explosive composition was prepared as shown in Table 13 substantially in the same manner as in Example 9, except that an expanded polystyrene foam having a greater average particle size was used as the gas-retaining agent.
Performance of the resulting Wj0 explosive composition was evaluated, and the results are as shown in Table 19. This explosive composition did not explode.
(Comparative Example 15) A W/0 explosive composition was prepared as shown in Table 14 smbstantially in the same manner as in Example 10, except that the organic gas-retaining agent used as the gas-retaining agent was replaced by a Shirasu microballoon (SMB) which is an inorganic gas-retaining agent. Performance of the resulting W/0 explosive composition was evaluated, and the results are as shown in Table 20.
As can be seen from Table 20, the explosive composition prepared here showed a lower total energy ratio than that prepared in Example 10.
(Comparative Example 16) A W/O explosive composition was prepared as shown in Table 14 substantially in the same manner as in Example 10, except that a resin microballoon (RMB) having a smaller average particle size was used as the gas-retaining agent.
Performance of the resulting W/0 explosive composition was evaluated, and the results are as shown in Table 20.
As can be seen from Table 20, the explosive composition prepared here showed a lower total energy ratio than that prepared in Example 10.
(Comparative Example 1'I) A W/O explosive composition was prepared as shown in Table 14 substantially in the same manner as in Example 10, except that an expanded polystyrene foam having a greater average particle size was used as the gas retaining agent.
Performance of t:he resulting W/0 explosive composition was evaluated, and Clue results are as shown in Table 20. This explosive composition did not explode.
(Comparative Example 18) A W/0 explosive composition was prepared as shown in Table 15 substantially in the same manner as in Comparative Example 3, except that the content of the organic gas-retaining agent was increased. Performance of the resulting W/O explosive composition was evaluated, and the results are as shown in Table 21. This explosive composition did not explode.
(Comparative Example 19) A W/0 explosive composition was prepared as shown in Table 15 substantially in 'the same manner as in Comparative Example 3, except that the organic gas-retaining agent was omitted.
Performance of the resulting W/O explosive composition was evaluated, and the results are as shown in Table 21. This explosive compo~>ition did not explode.
(Comparative Example 20) A W/0 explosive composition was prepared as shown in Table 15 SLlbStantially in the same manner as in Comparative Example 3, except that the content of the organic gas-retaining agent was increased. Performance of the resulting W/O explosive composition was evaluated, and the results are as shown in Table 21. This explosive composition did not explode.
(Comparative Example 21) A W/0 explosive .composition was prepared as shown in Table 15 substantially in the same manner as in Comparative Example 3, except that the organic gas-retaining agent and sensitizer were omitted. Performance of .the resulting W/0 explosive composition was evaluated, and the results are as shown in Table 21. This explosive composition did not explode.
It should be noted here that the abbreviations used in the following Tables 10 to 15 respectively stand for the compounds as shown below:
Expanded St 300 y An expanded polystyrene foam (average particle size: 300 yzm) Expanded St 4100 ~i An expanded polystyrene foam (average particle size : 4100 pm) RMB (2): Polyvinylidene chloride type resin microballoon (particle size . 5 to 30 }zm; average particle size: 8 ~zm) Table 10 Table 11 Table 12 Table 13 Table 14 Table 15 Table 16 Table 1Z
Table 18 Table 19 Table 20 Table 21 As shown in Tables Z to 9, the W/O explosive compositions obtained in Examples Z to 15 each showed a total energy value of underwater explosion energy of 116 to 213 which is considerably higher than the value in Comparative Example 3, provided that the total energy of Comparative Example 3 is 100. The total energy values of Examples 11, 12 and 13 are more than twice the value of Comparative Example 3.
On the contrary, the W/O explosive compositions of the respective Comparative Examples either did not explode at all, or showed a low underwater explosion energy.
The total energy in Comparative Example 3 was about 2.8 M.J/kg; whereas those of Examples were in the range of 3.2 MJ/kg (Exampl.e 7;' to 6.0 MJ/kg (Example 14). It can be seen that the total energy values of Examples are considerably higher than that in Comparative Example 3.
It should be appreciated that this invention is not limited to the above Examples, and many other modifications and variations of this invention as hereinbefore set forth can be made without departing from the spirit and scope of the invention.
Industrial App licability As has been described heretofore, since the present W/O
explosive compo~~ition has a high underwater explosion energy, it can suitably be employed as an explosive for coal mining and other mining industries.
_~'able 1 2 0 Example 1 2 3 Aqueous Ammonium 74 74 74 oxidizer nitrate salt Water 10.5 10.5 10.5 Sensitizer Hydrazine 10.5 10.5 10 nitrate .
Emulsifier Sorbitan 2,2 2.2 2.2 monooleate Carbonaceous Micro-Com- fuel crystalline 2.2 2.2 2.2 position wax Organic gas-retaining agent (Unit 0.6 0.6 0.6 of the parenthesized values (18.5) (17.7) (16.6) is volume o) by- Inorganic gas-retaining agent weight) (Unit of the parenthesized values - - -is volume o) Aluminum 10 20 30 powder (The parenthesized values are (11) (25) (43) outer ercenta e) Performance Apparent 1,17 1 1 specific 29 34 gravity ( /cc) . .
Underwater Ratio of 101 122 130 shock energy Explosion energy Ratio of 121 165 200 bubble energy Ratio of 116 154 183 total energy 2o s5s ~8 able 2 Example 4 5 6 Aqueous Ammonium oxidizer nitrate salt Water 10.5 10.5 10.5 Hydrazine Sensitizer 10.5 10 10 nitrate . .
Emulsifier Sorbitan 2.2 2 2 monooleate . .
Carbonaceous Micro-Com- fuel crystalline 2.2 2.2 2.2 position wax Organic gas-retaining agent 0.6 0.6 0.6 (Unit of the parenthesized (13.9) (11.1) (10.0) values is volume o) ( by- Inorganic gas-retaining agent weight) (Unit of the parenthesized values - - -is volume ) Aluminum powder (The parenthesized values are (100) (186) (233) outer ercenta e) Performance Apparent 1,56 1 1 specific 79 88 gravity ( ~CC) . .
Underwater Ratio of 100 98 95 shock energy Explosion energy Ratio of 245 250 252 bubble energy Ratio of 209 212 213 total energy a 2p 658 48 able 3 Comparative 1 2 Example Aqueou Ammonium s oxidizer nitrate salt Water 10.5 10.5 Sensitizer Hydrazine 10 10 nitrate . .
Emulsifier Sorbitan 2.2 2 monooleate .
Carbonaceous Micro-Com- fuel crystalline 2.2 2.2 position wax Organic gas-retaining agent 0.6 -(Unit of the parenthesized (21) values is volume o) by- Inorganic gas-retaining agent weight) (Unit of the parenthesized (18) values is volume o Aluminum powder (The -parenthesized values are (43) outer ercenta e) Performance Apparent 1 1 specific 10 34 gravity ( ~CC) , .
Underwater Rat io of 100 -shock energy Explosion energy Ratio of 100 -bubble energy Ratio of 100 -total energy 2o s58 ~8 'able 4 Example 7 8 9 NHqN03 74.4 77.5 66.7 Aqueous inorganic NaN03 - 5.2 4.2 oxidizer salt Water 10.5 11.7 9.2 MMA nitrate - - 15.0 Sensitizer Hyd nitrate 10.0 - -Composi- EDA nitrate - - -t ion (parts Chelating EDTA 0.5 = -by weight) agent Tartaric acid - - 0.3 Emulsifier SMO 2.3 2.8 -SMG - - 2.3 wAx (1) 2.3 - -Carbonaceous WAX (2) - 2.8 0.4 fuel WAX (3) - - 1.9 Gas-retaining RMB (1) _ 1.3 agent (17.2) (Unit of the Expanded parenthesized polystyrene 0.7 0.7 -values is foam (1) (18.5) (17.7) volume Load of aluminu m powder 11 25 43 (Unit of the renthesized (10) (20) (30) pa values is ~ by wei ht) 20 65s 4s 'able 5 Example 10 11 12 NH4N03 82.7 74.4 68.6 Aqueous inorganic NaN03 - - 5 oxidizer .
salt Water 11.7 10.5 11.2 MMA nitrate - - -Sensitizer Hyd nitrate - - 10.0 Composi- EDA nitrate - 10.0 -tion (parts Chelating EDTA - 0.5 0.4 by weight) agent Tartaric acid - - -Emulsifier , SfLO 2.8 2.3 2.3 SMG - - -WAX (1) 1.4 2.3 -Carbonaceous WAX (2) 1.9 - 0.4 fuel WAX (3) - - 1.9 Gas-retaining RMB (1) 1.3 0.8 -agent (17.1) (11.1) (Unit of the Expanded parenthesized polystyrene - 0.4 0.7 values is foam (1) (7.2) (11.1) volume a ) Load of aluminumpowder (Unit of the renthesized (30) (50) (65) pa values is ~ b wei ht) 'able 6 Example 13 14 15 NH4N03 77.5 74.4 82.7 Aqueous inorganic NaN03 5.2 - -oxidizer salt Water 11.7 10.5 11.7 MMA nitrate - - -Sensitizer Hyd nitrate - 10.0 -Composi- EDA nitrate - - -tion (parts Chelating EDTA - 0.5 -by weight) agent Tartaric acid - - -Emulsifier SMO 2.8 2.3 2.8 SMG - - -wAX (1) 2.8 2.3 2.8 Carbonaceous WAX (2) - - -fuel wAX (3) - - -Gas-retaining 1.3 1.3 agent RMB (1) (13.2) (11.5) (Unit of the Expanded parenthesized polystyrene - 0.7 -values is foam (1) (10.0) volume ) Load of aluminumpowder (Unit of the enthesized (65) (70) (70) par values is o b ei ht) w 'able 7 Example 7 8 9 Apparent specific Performance ravit ( /cc) 1.17 1.27 1.34 Underwater Ratio of shock energy 101 117 134 Explosion energy Ratio of bubble energy 121 198 202 Ratio of total energy 116 138 184 Table 8 Example 10 11 12 Apparent specific Performance ravit (q/cc) 1.31 1.55 1.79 Underwater Ratio of shock energy 122 102 97 Explosion energy Ratio of bubble energy 180 248 250 Ratio of total energy 165 210 211 Table 9 Example 13 14 15 Apparent specific Performance 1.75 1.88 1.82 ravit ( /cc) Underwater Ratio of shock energy 95 95 92 Explosion energy Ratio of bubble energy 230 252 235 Ratio of total energy 188 213 189 _ 7 _ 'able 10 Comparative 3 9 5 Example NHqN03 74.4 74.4 74.4 Aqueous inorganic NaN03 - - -oxidizer salt Water 10.5 10.5 10.5 MMA - - -nitrate Sensitizer Hyd 10.0 10.0 10.0 nitrate Composi- EDA - - -nitrate tion (parts Chelating EDTA 0.5 0.5 0.5 by weight) agent Tartaric - - -acid Emulsifier SMO 2.3 2.3 2.3 SMG - - -WAX 2.3 2.3 2.3 (1) Carbonaceous WAX - -(2) fuel wAx - - -( ) Gas-retaining Expanded Expanded Expanded agent (Unit of the St St St parenthesized values is volume 300. 300~L 300.
o ) 0.7 0.7 0.7 (21.0) (19.7) (8.9) Load of aluminum Particle powder size (Unit of the 0.1 mm - 5.3 300 parenthesized (5.0) (75) values is o 1.2 mm - - -by wei ht) _ g _ 20 658 48 .~
'able 11 Comparative 6 7 8 Example NHqN03 66.7 66.7 82.7 Aqueous inorganic NaN03 4.2 4.2 -oxidizer salt Water 9.2 9.2 11.7 MMA 15.0 15.0 -nitrate Sensitizer Hyd - - -nitrate Composi- EDA - - -nitrate tion (parts Chelating EDTA - - -b weightj agent Tartaric p.3 0 -acid .
Emulsifier SMO - - 2.8 SMG 2.3 2.3 -WAX - - 1 . 4 ( ) Carbonaceous WAX 0.4 0.4 1.4 (2) fuel WAX 1.9 1.9 -(3) Gas-retaining Expanded Expanded Expanded agent (Unit of the St St St parenthesized values is volume 300. 300 300.
o) 0.7 0.7 0.7 (19.8) (8.9) (19.4) Load of aluminum Particle powder size (Unit of the 0.1 mm - - 5.3 parenthesized (5.0) values is o 1.2 mm 5.3 300 -by wei ht) (5.0) (75) able 12 Comparative 9 10 11 Example NHqN03 82.7 77.5 77.5 Aqueous inorganic NaN03 - 5.2 5.2 oxidizer salt Water 11.7 11.7 11.7 MMA - - -nitrate Sensitizer Hyd - - -nitrate Composi- EDA - - -nitrate tion (parts b Chelating EDTA - - -weight agent Tartaric - - -acid Emulsifier SMO 2.8 - -SMG - 2.8 2.8 WAX 1.4 - -(1) Carbonaceous WAX 1.4 0.5 0.5 (2) fuel WAX - 2.3 2.3 (3) Gas-retaining Expanded Expanded Expanded agent (Unit of the St St St parenthesized values is 3001 3001 300.1.
volume o ) 0.7 0.7 0.7 (8.7) (19.5) (8.7) Load of aluminum Particle powder size (Unit of the 0.1 mm 300 - -parenthesized (75) values is 1.2 mm - 5.3 300 by wei ht) (5.0) (75) 'able 13 Comparative 12 13 14 Example NHqN03 68.6 68.6 68 Aqueous .
inorganic NaNO
3 5.2 5.2 5 oxidizer .
salt Water 11.2 11.2 11.2 MMA - - -nitrate Sensitizer Hyd - - -nitrate Composi- EDA 10:0 10.0 10 nitrate 0 t ion .
(parts Chelating EDTA 0.4 0.4 0.4 by weight) agent Tartaric - --acid Emulsifier SMO 2.3 2.3 2.3 SMG - - -WAX - - -(1) Carbonaceous WAX 2.3 2.3 2 (2) 3 fuel .
WAX - - -(3) Gas-retaining Expanded agent (Unit of the GMB RMB (2) St parenthesized values is 7.0 2.5 4100.
volume o) (16.0) (18.0) 0.3 (15.3) Load of aluminum Particle powder size (Unit of the 0.1 mm 43 93 43 parenthesized (30) (30) (30) values is 1.2 mm - - -~ by wei ht) 2o s58 ~8 'able 14 Comparative 15 16 17 Example NH4N03 82.7 82.7 82.7 Aqueous inorganic NaN03 - - -oxidizer salt Water 11.7 11.7 11.7 MMA - - -nitrate Sensitizer Hyd - - -nitrate Composi- EDA - - -nitrate tion (parts Chelating EDTA - - -by weight) agent Tartaric - - -acid Emulsifier SMO - - -SMG 2.8 2.8 2.8 WAX 2.8 2.8 2.8 (1) Carbonaceous WAX - - -(2) fuel WAx - - -(3) Gas-retaining Expanded agent (Unit of the SMB RMB (2) St parenthesized values is 7 . 4 2 . 5 41001.
volume o ) (16.1) (18.0) 0.3 (15.1) Load of aluminum Particle powder size (Unit of the 0.1 mm 43 43 43 parenthesized (30) (30) (30) values is 1.2 mm - - -by wei ht) 2Q 658 4~8 able 15 Comparative 18 19 20 21 Example NHqN03 74.4 74.4 77.5 77.5 Aqueous inorganic NaNO - -3 5.2 5.2 oxidizer salt Water 10.5 10.5 11.7 11.7 MMA - - - -nitrate Sensitizer Hyd 10.0 10.0 - -nitrate Composi- EDA - - - -nitrate tion (parts Chelating by EDTA - - - -weight) agent Tartaric p.5 0.5 - -acid SMO 2.3 2.3 2.8 2.8 Emulsifier SMG - - - -WAX - - 1.4 1.4 (1) Carbonaceous WAX 0.4 0.4 1.4 1.4 (2) fuel WAX 1.9 1.9 - -(3) Gas-retaining Expanded Expanded agent (Unit of the St - St -parenthesized values is 3001 300, volume o ) 1.8 1.8 (53.0) (52.0) Load of aluminum Particle powder size (Unit of the 0.1 mm - - - -parenthesized values is 1.2 mm - - - -o by wei ht) 'able 16 Comparative 3 4 5 Example Performance APParent specific 1 1 2 ravit ( /cc) . . .
Underwater Ratio of shock energy 100 100 -Explosion energy Ratio of bubble energy 100 108 -Ratio of total energy 100 105 -Table 17 Ccmparative 6 7 8 Example Performance APParent specific 1.12 2 1 aravit (ct/cc) . .
Underwater Rat io of shock energy - - g2 Explosion energy Ratio of bubble energy - - 95 Ratio of total energy - - 94 Table 18 Comparative 9 10 11 Example Performance Apparent specific 2.00 l 2 ll 00 aravitv ( /cc) . .
Underwater Rat io of shock energy - - -Explosion energy Ratio of bubble energy - - -Ratio of total energy - - -able 19 Comparative 12 13 14 Example Apparent specific Performance ravit ( /cc) 1.40 1.34 1.25 Underwater Ratio of shock energy 116 120 -Explosion energy Ratio of bubble energy 158 175 -Ratio of total energy 145 161 -Table 20 Comparative 15 16 17 Example Apparent specific Performance ravit ( /cc) 1.39 1.33 1.25 Underwater Ratio of shock energy 108 110 -E~:plosion energy Ratio of bubble energy 132 158 -Ratio of total energy 119 143 -Table 21 Comparative 18 19 20 21 Example Performance Apparent specific 0.55 1.41 0.52 1.40 ravity ( /cc) Underwater Ratio of shock energy - - - -Explosion energy Ratio of bubble energy - - - -Ratio of total energy - - - -
the gas-retaining agent is an organic gas-retaining agent having an average particle size of to 4000 ~m and is present in an amount of 0.6 to 2.5 wt.%, based on the total weight of the explosive composition; and the aluminum powder has an average parti-cle size not greater than 1 mm and is in admixture with the emulsion, the aluminum powder being present in an amount of 10 to 70 wt.%, based on the total weight of the explosive composition, whereby the explosion energy of the emul-sion mixed with the aluminum powder is at least 1.16 times greater than the explosion energy of an emulsion not containing aluminum powder.
Preferably, the explosion energy of the emulsion mixed with the aluminum powder is substantially at most 2.13 times greater than the explosion energy of an emulsion not containing aluminum powder.
The carbonaceous fuel which forms a continuous phase includes those conventionally employed in the W/O
explosives; for example, in the first aspect of this invention, hydrocarbons such as paraffinic hydro-carbons, olefinic hydrocarbons, naphthenic hydro-carbons, aromatic hydrocarbons, saturated or unsatu-rated hydrocarbons, petroleum purified mineral oils, lubricants and liquid paraffin; hydrocarbon deriva-tives such as nitrohydrocarbon; waxes including those derived from fuel oils and/or petroleum such as purified or unpurified microcrystalline wax, paraffin wax and petrolatum, mineral waxes such as montan wax, animal waxes such as whale wax and -4a-insect waxes such as beeswax. These carbonaceous fuels can be used alone or in admixture.
Preferred carbonaceous fuels include microcrystal-line wax and petrolatum in view of storage stabi-lity, and particularly preferred is microcrystalline wax. At the same time, preferred carbonaceous fuels to be used in the second aspect of this invention include waxes such as microcrystalline wax, paraffin wax and polyethylene wax; and fuel oils such as light oils of classification No. 2, which are conventionally used in the W/O explosives. The waxes are particularly preferred -S-in view of their texture such as hardness etc.
For the purpose of texture adjustment, a low-molecular Weight hydrocarbon polymer such as a petroleum resin, a low-molecular weight polyethylene and a low-molecular weight polypropylene may be added in combination with the carbonaceous fuel component. The carbonaceous fuel is usually added in an amount of 1 to 10 % by weight based on the total amount of the W/0 explosive.
The inorganic oxidizer salt, which forms the disperse phase in the form of aqueous solution, includes those conventionally used in the W/0 explosive compositions; for example, nitrates of alkali or alkaline earth metals such as ammonium nitrate, sodium nitrate and potassium nitrate; and inorganic chlorates or perchlorates such as sodium chlorate, ammonium perchlorate and sodium perchlorate. Usually ammonium nitrate is used alone or in admixture with other inorganic oxidizer salt. The inorganic oxidizer salt is usually added in an amount of 5 to ' 90 % by weight, preferably 40 to 80 % by weight.
The water content in the W/0 explosive composition according to this invention is preferably in the range of 3 to 30 % by weight, more preferably T to 30 % by weight.
Now, as the emulsifier, which plays a role to stabilize the emulsion, any of those conventionally used in the W/O
explosives can be used; for example, fatty acid esters of sorbitan such as sorbitan monolaurate, sorbitan monooleate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan dioleate and sorbitan trioleate; mono or diglycerides of fatty acids such as stearic acid monoglyceride; fatty acid esters of polyoxyethylene sorb j. tan, oxazoline derivatives, imidazoline derivatives, phosphoric acid esters, alkali or alkaline earth metal salts of fatty acids and primary, secondary or tertiary amine salts. These emulsifiers may be used alone or in admixture. Preferred of these emulsifiers are fatty acid esters of sorbitan. The emulsifier is preferably added in an amount of 0.1 to 10 % by weight, more preferably 1 to 5 % by weight.
As the sensitizer, which enhances detonation reliability and improves low-temperature detonating properties, .those conventionally used in the W/0 explosives such as monomethylamine nitrate, hydrazine nitrate and ethylenediamine nitrate can be used. However, hydrazine nitrate is preferred since it can improve solubility of ammonium nitrate and has high explosion energy. When such sensitizer is used, it is preferably added in an mount of 1 to 40 % by weight, more preferably not more than 30 % by weight, most preferably not more than 20 % by weight in the W/0 explosive composition.
If the percentage of the sensitizer exceeds 40 % by weight, danger in hand:li.ng the explosive composition will sometimes be increased.
Particularly when hydrazine nitrate and the like is used as the sensitizPr, it is advantageous to use a chelating agent such as sodium ethylenediaminetetraacetate so as to prevent decomposition of the hydrazine nitrate. The chelating agent - is preferably ;added in an amount of 0.1 to 10 % by weight based on the amount of the sensitizer.
The gas-retaining agent is an organic material. The organic gas-retaining agent may be selected from various types of single hollow microspheres or bubble assemblies containing a plurality of cells; for example, carbonaceous hollow microspheres obtained from pitch, coal, etc.; synthetic resin hollow microspheres obtained from phenol resins, polyvinylidene chloride, epoxy resins, urea resins, etc. The bubble assembl_'ies containing a plurality of cells include a milled powder and grains prepared by incorporating air into a raw material synthetic high polymer, for example, olefins such as ethylene, propylene and styrene; polymers of vinyl compounds such as vinylidene chloride, vinyl alcohols, vinyl acetate, and acrylic acid, methacrylic acid or esters thereof, or copolymers, modified polymers or mixed polymers thereof;
synthetic polymers such as polyurethane, polyester, polyamide, urea resin, epoxy resin and phenol resin, by means of various technigues solch as mechanical foaming, chemical foaming, micro-encapsulation, incorporation of an easily volatile material, etc., followed by milling.
Preferred of these organic gas-retaining agents are those made from polystyrene, polyethylene or polyv.inylidene chloride.
These organic gas-retaining agents, unlike the inorganic gas-retaining agents such as glass, silica, etc., do not damage the emulsion membrane and can maintain the emulsion stable. These organic gas-retaining agents are superior to the inorganic ones, since they have low specific gravity, they do not assume a form of inactive additive, and they are easily available at low costs.
When an organic gas-retaining agent is used, it never happens that the emulsion is partly damaged by pumping during the process of manufacturing unlike the inorganic gas-retaining agents. Accordingly, an explosive which can exhibit the designed detonation performance and has good storage stability can be provided.
Further, the organic gas-retaining agent may be of single bubbles or assemblies of single bubbles, and the diameter of which is not critical. However, in the first aspect of this invention, one having an average particle size in the range of 10 to 4,000 dam is particularly used. If one having an average particle size of less than 10 izm is used, it comes to r have a greater specific gravity and must be added in an increased amount; whereas if one having an average size of greater than 4 , 000 lzm is used, the underwater explosion energy will be lowered. Incidentally, the particle shape of the gas-retaining agent may be any spherical, cylindrical, polyhedral, etc.
A suitable organic gas-retaining agent is selected depending on the application of the W/0 explosive. The organic gas--retaining agent is preferably added in an amount of 1 to 50 % by volume in the W/O explosive. If the content of the organic gas-retaining agent is less than 1 % by volume, cap-sensitivity of the resulting explosive composition will be lowered or 'the detonation will be interrupted; whereas if the content of the organic gas-retaining agent exceeds 50 %
by volume, the underwater explosion energy tends to be lowered.
The aluminum powder is used as a fuel and also to improve underwater explosion energy. While ordinary aluminum powders can be used, those having a particle size of not more than 1 mm, preferably in the range of 0.01 to 1 mm, more preferably in the range of 0.03 to 0.1 mm, are particularly used in the first aspect of this invention. If an aluminum powder having a particle size of more than 1 mm is used, the underwater explosion energy will be lowered. The particle shape of the aluminum powder. may be any spherical, scaly, etc.
In this invention, the aluminum powder can be used in a greater amount than in the prior art explosive compositions.
If no sensitizer is added, the content of the aluminum powder is in the range of 10 to ?0 % by weight, preferably in the range of 20 to ?0 % by weight; whereas if a sensitizer is added, it is im the range of 10 to ?0 % by weight. If the content of the aluminum powder is less than 10 % by weight, the fuel component will be insufficient to give reduced detonation performance; while if it exceeds ZO % by weight, inactive aluminum powder remains in the resulting composition to reduce the detonation performance.
The preferred compounding ratio of the respective components in the W/0 explosive composition in the first aspect of this invention is as follows: 40 to 90 parts by weight of an inorganic oxidizer salt; Z to 30 parts by weight of water; 0.5 to 10 parts by weight of a carbonaceous fuel; 0.5 to 10 parts by weight of an emulsifier; 1 to 40 parts by weight of a sensitizer; 1 to 50 % by volume of an organic gas-retaining agent having an average particle size of 10 to 4,000 um ; and to ZO % by weight of an aluminum powder having an average particle size of not more than 1 mm . Meanwhile, the preferred compounding ratio of the respective components in the second aspect of this invention is as follows: 40 to 90 parts by weight of an inorganic oxidizer salt; T to 30 parts by weight of water; 0.5 to 10 parts by weight of a carbonaceous fuel; 0.5 to 10 parts by weight of an emulsifier;
1 to 40 parts by weight of a sensitizer; 1 to 50 % by volume of an organic gas-retaining agent; and 10 to TO % by weight of an aluminum powder.
If the content of the inorganic oxidizer salt is less than 40 % by weight, i:he detonation performance of the resulting composition will be lowered; whereas if it exceeds 90 % by weight, solubility thereof will be reduced. If the water content is lees than Z % by weight, solubility of the inorganic oxidizer salt will be lowered; whereas if it exceeds 30 % by weight, the contents of the other components will relatively be smaller to easily lower the detonation performance of the resulting composition. Addition of the carbonaceous f~.iel in an amount of less than 0.5 % by weight cannot give a ~~ery fine emulsion to provide small contact area; whereas .if it exceeds 10 % by weight, the content of the inorganic oxidizer salt will relatively be smaller. If the content of. the emulsifier is less than 0.5 % by weight, stability of the emulsion tends to be lowered; whereas if it exceeds 10 % by weight, detonation performance of the resulting composition can hardly be improved. If the content of the sensitizer is less than 1 % by weight, the resulting composition sheaws insufficient denotation reliability; whereas if it exceeds 40 % by weight, danger in the handling of the resulting composition will be increased. If the content of the organic gas-retaining agent-is less than 1 % by volume, cap-sensitivity of the resulting composition may be reduced and explosion may be interrupted; whereas if it exceeds 50 %
by volume, the underwater explosion energy tends to be lowered. If the aluminum powder is added in an amount of more than or less than the specified range of 10 to ZO % by weight, the detonation performance of the resulting explosive composition tends to be lowered.
The present W/O explosive composition can be prepared, for example, in the following manner.
An inorganic oxidizer salt, optionally together with a sensitizer and a chelating agent, is dissolved in a hot water (ca. 60 to 1.00°C) to prepare an aqueous solution of inorganic oxidizer salt.. Meanwhile, a carbonaceous fuel and an emulsifier are mixed by heating at a temperature where they assume a liquid state, usually at ZO to 90°C, to prepare a combustible material mixture. Next, the aqueous solution of the inorganic oxidizer salt and the combustible material mixture prepared above are mixed by stirring at a temperature of 60 to 90°C at a rate of about 600 to 6,000 rpm to provide a W/0 em~nlsion. S»bsequently, an organic gas-retaining agent and an aluminum powder are admixed to the resulting W/O
emulsion to give a W/0 explosive composition.
The thus obtained W/O explosive composition characteristically shows a particularly enhanced underwater explosion energy owing to the organic gas-retaining agent employed as the gas-retaining agent and also aluminum powder incorporated therein, since the emulsion membrane cannot easily be damaged by the organic: gas-retaining agent unlike by the inorganic gas-retaining agent, and since the organic gas-retaining agent has a smaller specific gravity than the inorganic gas-retaining agent, and thus the proportion of the,emulsion will be greater to allow the aluminum powder to be incorporated in an increased amount.
The underwater explosion energy can be divided into shock energy (Es) and bubble energy {Eb). The ratio of Eb to Es is usually about 3, and the combination of these two energy val,nes Es and Eb is the total underwater explosion energy { see Encyclopedia of Explosives, Vol. 10, 1983, published by American Army Armament Research and Development Command).
Incidentally, the present W/0 explosive composition is of high safety, since it is an emulsion type hydrated explosive.
BEST MODE FOR CARRYING OUT THE INVENTION
Preferred embodiments of this invention will now be described below by way of Examples in comparison with Comparative Examples; wherein parts) mean part{s) by weight.
(Examples 1 to 6) A W/0 explosive composition was prepared using ammonium nitrate as the inorganic oxidizer salt, sorbitan monooleate as the emulsifier, a microcrystalline wax as the carbonaceous fuel, single-bubble assemblies of polystyrene having an average particle size of 300 um as the gas retaining agent, hydrazine nitrate as the sensitizer and an aluminum powder having an average particle size of 30 ~zm. The proportion of the respective components are as shown in the following Tables 1 and 2.
The procedure of preparing the W/O explosive composition is as follows: ,Ammonium nitrate and hydrazine nitrate were dissolved in water by heating at about 85°C. Meanwhile, a mixture of the microcrystalline wax and sorbitan monooleate was melted at about 85°C, and the solution prepared above was added to the melted mixture, followed by stirring by an agitating blade to effect emulsification. The gas-retaining agent and aluminum powder were admixed to the resulting emulsion to provide a W/O explosive composition. Underwater explosion energy was determined for the thus obtained W/0 explosive composition, and the results are also shown in Tables 1 and 2.
Incidentally, measurement of the underwater explosion energy was carried out by laying the explosive at the water depth of 4 m in a pool fc~r determining underwater explosion energy and measuring the shock pulse of the exploded explosive by means of a pressure gauge (Tolmarine gauge) set at the same water depth and at an arbitrary distance so as to calculate Es value and Eb val~.ie, respectively. The total energy was obtained by combining the E> and Eb values in terms of the relative ratio to the values obtained in Comparative Example 1, according to the following equation.
Esn + Ebn Total energy ratio =
Eso + Ebo In the above equation, Eso and Ebo are the values obtained in Comparative Example 1, while Esn and Ebn are the values obtained in Comparative Control Examples.
(Comparative Example i) A W/0 explosive composition was prepared in the same manner as in Examples 1 to 6, except that the aluminum powder was omitted. The thus prepared W/0 explosive composition was tested in the same manner as in Example 1, and the results are as shown in Table 3.
(Comparative Example 2) A W/0 explosive composition was prepared in the same manner as in Example ;3, except that the organic gas-retaining agent was replaced by GMB having an average particle size of 50 pm as the inorganic gas=retaining agent. The thus prepared W/0 explosive composition was tested in the same manner as in Examples 1 to fi, and the results are as shown in Table 3.
Table 1 Table 2 Table 3 The outer percentage of the aluminum powder shown in Tables 1 to 3 is indicated by % by weight per 100 parts by weight of the W/0 explosive composition excluding the aluminum powder.
As can be seen from Tables 1 to 3, the W/0 explosive compositions obtained~in Examples 1 to 6 each showed a high total energy of 116 to 213 as the underwater explosion energy over the one obtained in Comparative Example 1, provided that the value of Comparative Example 1 is 100, and the explosive compositions obtained in Examples 5 and 6 each showed a value more than twice the value of the Comparative Example 1.
On the contrary, the W/0 explosive composition of Comparative Example 1 showed only a low level of underwater explosion energy, since it does not contain an aluminum powder although it contains an.organic gas-retaining agent. Meanwhile, the W/0 explosive composition of Comparative Example 2 found diffic~.ilty in maintaining the shape of the W/0 explosive and did not explode. This was because it uses a combination of an aluminum powder and GMB as the inorganic gas-retaining agent, and the al~.iminum powder was used in an increased amount.
The Es value of the W/O explosive (a standard W/O explosive composition) in Comparative Example 1 is about 0.'I MJ/kg; the Eb value thereof-, about 2.1 MJ/kg; and the total energy, about 2.8 MJ/kg. Meanwhile, the total energy of the W/O explosive composition in each Example is increased to about 3.2 MJ/kg (Example 1) to 6.0 MJ/kg (Example 6).
(Example Z) A W/O explosive was prepared using the explosive composition as shown in Table 4 in the following manner:
To 10.5 parts of. water were added '14.4 parts of ammonium nitrate as the inorganic oxidizer salt, 10 parts of hydrazine nitrate as the sensitizer and 0.5 part of sodium ethylenediaminetetraacetate as the chelating agent, and they were dissolved well with heating at 90°C to prepare an aqueous solution of inorganic oxidizer salt. Meanwhile, 2.3 parts of 2o s5s 48 WARREX* 602 as the carbonaceous fuel and 7. . 3 parts of sorbitan tnonooleate as the emulsifier were mixed with heating at 90°C
to prepare a combustible material mixture. To the resulting mixture was added slowly the aqueous solution of inorganic oxidizer salt to effect emulsification by stirring at 650 rpm with heating at 90°
After completion of emulsification, the resulting emulsion was further stirred at 1,600 rpm for one minute to provide a W/0 emulsion. Subsequently, 0.? part of an organic gas-retaining agent having an average particle size of 300 pm and 11 parts of an aluminum powder were admixed to the W/0 emulsion at 60 to 80°C to give a W/0 explosive composition. Underwater explosion energy was determined for the thus obtained W/0 explosive composition, and the results are as shown in the following Table ?.
(Example 8) A W/0 explosive composition was prepared as shown in Table 4 in the same manner as in Example ?, except that the sensitizer and chelating agent were omitted and that the content of the aluminum powder was changed. Performance of the resulting W/0 explosive composition was evaluated, and the results are as shown in Table ?.
As can be seen from Table ?, the explosive composition prepared here showed a higher total energy ratio than that prepared in Example Z.
(Example 9) A W/0 explosive composition was prepared as shown in Table 4 substantially in the same manner as in Example ?, except that the content of the aluminum powder was increased: Performance * Trade mark of the resulting W/0 explosive composition was evaluated, and the results are as shown in Table T.
As can be seen from Table T, the explosive composition prepared here showed a higher total energy ratio than that prepared in Example Z.
(Example 10) A W/O explosive composition was prepared as shown in Table 5 substantially in the same manner as in Example 8, except that the content of 'the aluminum powder was increased. Performance of the resulting W/0 explosive composition was evaluated, and the results are as shown in Table S.
As can be seen from Table 8, the explosive composition prepared here showed a higher total energy ratio than that prepared in Example 8.
(Exampl.e 11) A W/0 explosive composition was prepared as shown in Table 5 substantially in the same manner as in Example 9, except that the content of the aluminum powder was increased. Performance of the resulting W/0 explosive composition was evaluated, and the results are as shown in Table 8.
As can be seen from Table 8, the explosive composition prepared here showed a higher total energy ratio than that prepared in Example 9.
(Example 12) A W/O explosive composition was prepared as shown in Table 5 substantially i:n the same manner as in Example 11 , except that the content of the aluminum powder was increased. Performance of the res~.ilting W/O explosive composition was evaluated, and the results are as shown in Table 8.
As can be seen from Table 8, the explosive composition prepared here showed a slightly higher total energy ratio than that prepared :in Example 11.
(Example 13) A W/0 explosive composition was prepared as shown in Table 6 substantially in the same manner as in Example 10, except that the content of the aluminum powder was increased. Performance of the resulting W/O explosive composition was evaluated, and the results are as shown in Table 9.
As can be seen from Table 9, the explosive composition prepared here showed a slightly higher total energy ratio than that prepared 9.n Example 10.
(Example 14) A W/0 explosive composition was prepared as shown in Table 6 substantially in the same manner as in Example 12, except that the content of t:he aluminum powder was increased. Performance of the resulting W/O explosive composition was evaluated, and the results are as shown in Table 9.
As can be seen from Table 9, the explosive composition prepared here showed a slightly higher total energy ratio than that prepared in Example 12.
(Example 15) A W/0 explosive composition was prepared as shown in Table 6 substantially in the same manner as in Example 13, except that the content of the aluminum powder was increased. Performance of the resulting W/O explosive composition was evaluated, and the results are as shown in Table 9.
As can be seen from Table 9, the explosive composition prepared here showed a slightly higher total energy ratio than that prepared in Example 13.
It should be noted here that the abbreviations used in the following Tables 4 to 6 stand for the respective compound as shown below.
MMA nitrate: Monomethylamine nitrate Hyd nitrate: Hydrazine nitrate EDA nitrate: Ethylenediamine nitrate EDTA: Sodium ethylenediaminetetraacetate SMO: Sorbitan monooleate SMG: Monvglyceride stearate Wax (1): WARREX* 602 Wax (2): Microcrystalline Wax 160 Wax (3): POLYWAX* 500 GMB: Glass microballoon (particle size:
20 to 140 ~tm; average particle size: 60 ~tm) SMB: Shirasu microballoon (particle size: 30 to 150 pm; average particle size:
75 pm) RMB (1): Polyvinylidene chloride type resin microballoon (particle size: 10 to 100 ~Zm; average particle size 30 ~Zm) Expanded polystyrene foam (1):
Obtained by prefvaming an expanded polystyrene foam beads (particle size: 180 to 700 ~Zm; average particle size: 300 pm) * Trade mark Table 4 Table 5 Table 6 Table ?
Table 8 Table 9 (Comparative Example 3) A W/0 explosive composition was prepared as shown in Table 10 in the same manner as in Example 1, except that the aluminum powder was omitted. Performance of the resulting W/0 explosive composition was evaluated, and the results are as shown in Table 16. -The thus prepared explosive composition is a standard composition for calculating the respective energy ratio.
(Comparative Example 4) A W/0 explosive composition was prepared as shown in Table 10 in the same manner as in Example ?, except that the content of the aluminum. powder was reduced. Performance of the resulting W/O explosive composition was evaluated, and the results are as shown in Table 16.
As can be seen from Table 16, the explosive composition prepared here showed a lower total energy ratio than that prepared in Example ?.
(Comparative Example 5) A W/0 explosive composition was prepared as shown in Table 10 in the same manner as in Example ?, except that the content of the aluminum powder was increased. Performance of the -2.0-resulting W/0 explosive composition was evaluated, and the results are as shown in Table 16. This explosive composition did not explode.
(Comparative Example 6) A W/0 explosive composition was prepared as shown in Tabl~ 11 smbstantially in the same manner as in Comparative Example. 4, except that an aluminum powder having a greater particle size was used. Performance of the resulting W/0 explosive composition was evaluated, and the results are as shown in Table 1T. This explosive composition did not explode.
(Comparative Example '1) A W/0 explosive composition was prepared as shown in Table 11 s,.ibstant ial ly in the same manner as in Comparat ive Example 5 , except that an aluminum powder having a greater particle size was used. Performance of the resulting W/0 explosive composition was evaluated, and the results are as shown in Table iZ. This explosive composition did not explode.
(Comparative Example 8) A W/0 explosive composition was prepared as shown in Table il substantially in the same manner as in Example 8, except that the content of th.e aluminum powder was reduced. Performance of the resulting W/O explosive composition was evaluated, and the results are as shown in Table iZ.
As can be seen from Table iT, the explosive composition prepared here showed a lower total energy ratio than that prepared in Example 8.
(Comparative Example 9) A W/0 explosive composition was prepared as shown in Table 12 substantially in the same manner as in Example 8, except that the content of the aluminum powder was increased.
Performance of the resulting W/0 explosive composition was evaluated, and the results are as shown in Table 18. This explosive composition did not explode.
(Comparative Example 10) A W/0 explosive composition was prepared as shown in Table 12 substantially in the same manner as~ in Comparative Example 8, except that an aluminum powder having a greater particle size was used. Performance of the resulting W/O explosive composition was evaluated, and the results are as shown in Table 18. This explosive composition did not explode.
(Comparative Exarnple il) A W/O explosive composition was prepared as shown in Table 12 substantially in the same manner as in Comparative Example 9, except that an aluminum powder having a greater particle size was used. Per:Eormance of the resulting W/0 explosive composition was evaluated, and the results are as shown in Table 18. This explosive composition did not explode.
(Comparative Example 12) As can be seen from Table 19, the explosive composition prepared here showed a lower total energy ratio than that prepared in Example 9.
(Comparative Example 13) A W/0 explosive composition was prepared as shown in Table 13 substantially in the same manner as in Example 9, except,that a resin microballoon (RMB) having a smaller average particle size was used as the gas-retaining agent . Performance of the resulting W/O explosive composition was evaluated, and the results are as shown in Table 19.
As can be seen from Table 19, the explosive composition prepared here showed a lower total energy ratio than that prepared in Example 9.
(Comparative Example 14) A W/O explosive composition was prepared as shown in Table 13 substantially in the same manner as in Example 9, except that an expanded polystyrene foam having a greater average particle size was used as the gas-retaining agent.
Performance of the resulting Wj0 explosive composition was evaluated, and the results are as shown in Table 19. This explosive composition did not explode.
(Comparative Example 15) A W/0 explosive composition was prepared as shown in Table 14 smbstantially in the same manner as in Example 10, except that the organic gas-retaining agent used as the gas-retaining agent was replaced by a Shirasu microballoon (SMB) which is an inorganic gas-retaining agent. Performance of the resulting W/0 explosive composition was evaluated, and the results are as shown in Table 20.
As can be seen from Table 20, the explosive composition prepared here showed a lower total energy ratio than that prepared in Example 10.
(Comparative Example 16) A W/O explosive composition was prepared as shown in Table 14 substantially in the same manner as in Example 10, except that a resin microballoon (RMB) having a smaller average particle size was used as the gas-retaining agent.
Performance of the resulting W/0 explosive composition was evaluated, and the results are as shown in Table 20.
As can be seen from Table 20, the explosive composition prepared here showed a lower total energy ratio than that prepared in Example 10.
(Comparative Example 1'I) A W/O explosive composition was prepared as shown in Table 14 substantially in the same manner as in Example 10, except that an expanded polystyrene foam having a greater average particle size was used as the gas retaining agent.
Performance of t:he resulting W/0 explosive composition was evaluated, and Clue results are as shown in Table 20. This explosive composition did not explode.
(Comparative Example 18) A W/0 explosive composition was prepared as shown in Table 15 substantially in the same manner as in Comparative Example 3, except that the content of the organic gas-retaining agent was increased. Performance of the resulting W/O explosive composition was evaluated, and the results are as shown in Table 21. This explosive composition did not explode.
(Comparative Example 19) A W/0 explosive composition was prepared as shown in Table 15 substantially in 'the same manner as in Comparative Example 3, except that the organic gas-retaining agent was omitted.
Performance of the resulting W/O explosive composition was evaluated, and the results are as shown in Table 21. This explosive compo~>ition did not explode.
(Comparative Example 20) A W/0 explosive composition was prepared as shown in Table 15 SLlbStantially in the same manner as in Comparative Example 3, except that the content of the organic gas-retaining agent was increased. Performance of the resulting W/O explosive composition was evaluated, and the results are as shown in Table 21. This explosive composition did not explode.
(Comparative Example 21) A W/0 explosive .composition was prepared as shown in Table 15 substantially in the same manner as in Comparative Example 3, except that the organic gas-retaining agent and sensitizer were omitted. Performance of .the resulting W/0 explosive composition was evaluated, and the results are as shown in Table 21. This explosive composition did not explode.
It should be noted here that the abbreviations used in the following Tables 10 to 15 respectively stand for the compounds as shown below:
Expanded St 300 y An expanded polystyrene foam (average particle size: 300 yzm) Expanded St 4100 ~i An expanded polystyrene foam (average particle size : 4100 pm) RMB (2): Polyvinylidene chloride type resin microballoon (particle size . 5 to 30 }zm; average particle size: 8 ~zm) Table 10 Table 11 Table 12 Table 13 Table 14 Table 15 Table 16 Table 1Z
Table 18 Table 19 Table 20 Table 21 As shown in Tables Z to 9, the W/O explosive compositions obtained in Examples Z to 15 each showed a total energy value of underwater explosion energy of 116 to 213 which is considerably higher than the value in Comparative Example 3, provided that the total energy of Comparative Example 3 is 100. The total energy values of Examples 11, 12 and 13 are more than twice the value of Comparative Example 3.
On the contrary, the W/O explosive compositions of the respective Comparative Examples either did not explode at all, or showed a low underwater explosion energy.
The total energy in Comparative Example 3 was about 2.8 M.J/kg; whereas those of Examples were in the range of 3.2 MJ/kg (Exampl.e 7;' to 6.0 MJ/kg (Example 14). It can be seen that the total energy values of Examples are considerably higher than that in Comparative Example 3.
It should be appreciated that this invention is not limited to the above Examples, and many other modifications and variations of this invention as hereinbefore set forth can be made without departing from the spirit and scope of the invention.
Industrial App licability As has been described heretofore, since the present W/O
explosive compo~~ition has a high underwater explosion energy, it can suitably be employed as an explosive for coal mining and other mining industries.
_~'able 1 2 0 Example 1 2 3 Aqueous Ammonium 74 74 74 oxidizer nitrate salt Water 10.5 10.5 10.5 Sensitizer Hydrazine 10.5 10.5 10 nitrate .
Emulsifier Sorbitan 2,2 2.2 2.2 monooleate Carbonaceous Micro-Com- fuel crystalline 2.2 2.2 2.2 position wax Organic gas-retaining agent (Unit 0.6 0.6 0.6 of the parenthesized values (18.5) (17.7) (16.6) is volume o) by- Inorganic gas-retaining agent weight) (Unit of the parenthesized values - - -is volume o) Aluminum 10 20 30 powder (The parenthesized values are (11) (25) (43) outer ercenta e) Performance Apparent 1,17 1 1 specific 29 34 gravity ( /cc) . .
Underwater Ratio of 101 122 130 shock energy Explosion energy Ratio of 121 165 200 bubble energy Ratio of 116 154 183 total energy 2o s5s ~8 able 2 Example 4 5 6 Aqueous Ammonium oxidizer nitrate salt Water 10.5 10.5 10.5 Hydrazine Sensitizer 10.5 10 10 nitrate . .
Emulsifier Sorbitan 2.2 2 2 monooleate . .
Carbonaceous Micro-Com- fuel crystalline 2.2 2.2 2.2 position wax Organic gas-retaining agent 0.6 0.6 0.6 (Unit of the parenthesized (13.9) (11.1) (10.0) values is volume o) ( by- Inorganic gas-retaining agent weight) (Unit of the parenthesized values - - -is volume ) Aluminum powder (The parenthesized values are (100) (186) (233) outer ercenta e) Performance Apparent 1,56 1 1 specific 79 88 gravity ( ~CC) . .
Underwater Ratio of 100 98 95 shock energy Explosion energy Ratio of 245 250 252 bubble energy Ratio of 209 212 213 total energy a 2p 658 48 able 3 Comparative 1 2 Example Aqueou Ammonium s oxidizer nitrate salt Water 10.5 10.5 Sensitizer Hydrazine 10 10 nitrate . .
Emulsifier Sorbitan 2.2 2 monooleate .
Carbonaceous Micro-Com- fuel crystalline 2.2 2.2 position wax Organic gas-retaining agent 0.6 -(Unit of the parenthesized (21) values is volume o) by- Inorganic gas-retaining agent weight) (Unit of the parenthesized (18) values is volume o Aluminum powder (The -parenthesized values are (43) outer ercenta e) Performance Apparent 1 1 specific 10 34 gravity ( ~CC) , .
Underwater Rat io of 100 -shock energy Explosion energy Ratio of 100 -bubble energy Ratio of 100 -total energy 2o s58 ~8 'able 4 Example 7 8 9 NHqN03 74.4 77.5 66.7 Aqueous inorganic NaN03 - 5.2 4.2 oxidizer salt Water 10.5 11.7 9.2 MMA nitrate - - 15.0 Sensitizer Hyd nitrate 10.0 - -Composi- EDA nitrate - - -t ion (parts Chelating EDTA 0.5 = -by weight) agent Tartaric acid - - 0.3 Emulsifier SMO 2.3 2.8 -SMG - - 2.3 wAx (1) 2.3 - -Carbonaceous WAX (2) - 2.8 0.4 fuel WAX (3) - - 1.9 Gas-retaining RMB (1) _ 1.3 agent (17.2) (Unit of the Expanded parenthesized polystyrene 0.7 0.7 -values is foam (1) (18.5) (17.7) volume Load of aluminu m powder 11 25 43 (Unit of the renthesized (10) (20) (30) pa values is ~ by wei ht) 20 65s 4s 'able 5 Example 10 11 12 NH4N03 82.7 74.4 68.6 Aqueous inorganic NaN03 - - 5 oxidizer .
salt Water 11.7 10.5 11.2 MMA nitrate - - -Sensitizer Hyd nitrate - - 10.0 Composi- EDA nitrate - 10.0 -tion (parts Chelating EDTA - 0.5 0.4 by weight) agent Tartaric acid - - -Emulsifier , SfLO 2.8 2.3 2.3 SMG - - -WAX (1) 1.4 2.3 -Carbonaceous WAX (2) 1.9 - 0.4 fuel WAX (3) - - 1.9 Gas-retaining RMB (1) 1.3 0.8 -agent (17.1) (11.1) (Unit of the Expanded parenthesized polystyrene - 0.4 0.7 values is foam (1) (7.2) (11.1) volume a ) Load of aluminumpowder (Unit of the renthesized (30) (50) (65) pa values is ~ b wei ht) 'able 6 Example 13 14 15 NH4N03 77.5 74.4 82.7 Aqueous inorganic NaN03 5.2 - -oxidizer salt Water 11.7 10.5 11.7 MMA nitrate - - -Sensitizer Hyd nitrate - 10.0 -Composi- EDA nitrate - - -tion (parts Chelating EDTA - 0.5 -by weight) agent Tartaric acid - - -Emulsifier SMO 2.8 2.3 2.8 SMG - - -wAX (1) 2.8 2.3 2.8 Carbonaceous WAX (2) - - -fuel wAX (3) - - -Gas-retaining 1.3 1.3 agent RMB (1) (13.2) (11.5) (Unit of the Expanded parenthesized polystyrene - 0.7 -values is foam (1) (10.0) volume ) Load of aluminumpowder (Unit of the enthesized (65) (70) (70) par values is o b ei ht) w 'able 7 Example 7 8 9 Apparent specific Performance ravit ( /cc) 1.17 1.27 1.34 Underwater Ratio of shock energy 101 117 134 Explosion energy Ratio of bubble energy 121 198 202 Ratio of total energy 116 138 184 Table 8 Example 10 11 12 Apparent specific Performance ravit (q/cc) 1.31 1.55 1.79 Underwater Ratio of shock energy 122 102 97 Explosion energy Ratio of bubble energy 180 248 250 Ratio of total energy 165 210 211 Table 9 Example 13 14 15 Apparent specific Performance 1.75 1.88 1.82 ravit ( /cc) Underwater Ratio of shock energy 95 95 92 Explosion energy Ratio of bubble energy 230 252 235 Ratio of total energy 188 213 189 _ 7 _ 'able 10 Comparative 3 9 5 Example NHqN03 74.4 74.4 74.4 Aqueous inorganic NaN03 - - -oxidizer salt Water 10.5 10.5 10.5 MMA - - -nitrate Sensitizer Hyd 10.0 10.0 10.0 nitrate Composi- EDA - - -nitrate tion (parts Chelating EDTA 0.5 0.5 0.5 by weight) agent Tartaric - - -acid Emulsifier SMO 2.3 2.3 2.3 SMG - - -WAX 2.3 2.3 2.3 (1) Carbonaceous WAX - -(2) fuel wAx - - -( ) Gas-retaining Expanded Expanded Expanded agent (Unit of the St St St parenthesized values is volume 300. 300~L 300.
o ) 0.7 0.7 0.7 (21.0) (19.7) (8.9) Load of aluminum Particle powder size (Unit of the 0.1 mm - 5.3 300 parenthesized (5.0) (75) values is o 1.2 mm - - -by wei ht) _ g _ 20 658 48 .~
'able 11 Comparative 6 7 8 Example NHqN03 66.7 66.7 82.7 Aqueous inorganic NaN03 4.2 4.2 -oxidizer salt Water 9.2 9.2 11.7 MMA 15.0 15.0 -nitrate Sensitizer Hyd - - -nitrate Composi- EDA - - -nitrate tion (parts Chelating EDTA - - -b weightj agent Tartaric p.3 0 -acid .
Emulsifier SMO - - 2.8 SMG 2.3 2.3 -WAX - - 1 . 4 ( ) Carbonaceous WAX 0.4 0.4 1.4 (2) fuel WAX 1.9 1.9 -(3) Gas-retaining Expanded Expanded Expanded agent (Unit of the St St St parenthesized values is volume 300. 300 300.
o) 0.7 0.7 0.7 (19.8) (8.9) (19.4) Load of aluminum Particle powder size (Unit of the 0.1 mm - - 5.3 parenthesized (5.0) values is o 1.2 mm 5.3 300 -by wei ht) (5.0) (75) able 12 Comparative 9 10 11 Example NHqN03 82.7 77.5 77.5 Aqueous inorganic NaN03 - 5.2 5.2 oxidizer salt Water 11.7 11.7 11.7 MMA - - -nitrate Sensitizer Hyd - - -nitrate Composi- EDA - - -nitrate tion (parts b Chelating EDTA - - -weight agent Tartaric - - -acid Emulsifier SMO 2.8 - -SMG - 2.8 2.8 WAX 1.4 - -(1) Carbonaceous WAX 1.4 0.5 0.5 (2) fuel WAX - 2.3 2.3 (3) Gas-retaining Expanded Expanded Expanded agent (Unit of the St St St parenthesized values is 3001 3001 300.1.
volume o ) 0.7 0.7 0.7 (8.7) (19.5) (8.7) Load of aluminum Particle powder size (Unit of the 0.1 mm 300 - -parenthesized (75) values is 1.2 mm - 5.3 300 by wei ht) (5.0) (75) 'able 13 Comparative 12 13 14 Example NHqN03 68.6 68.6 68 Aqueous .
inorganic NaNO
3 5.2 5.2 5 oxidizer .
salt Water 11.2 11.2 11.2 MMA - - -nitrate Sensitizer Hyd - - -nitrate Composi- EDA 10:0 10.0 10 nitrate 0 t ion .
(parts Chelating EDTA 0.4 0.4 0.4 by weight) agent Tartaric - --acid Emulsifier SMO 2.3 2.3 2.3 SMG - - -WAX - - -(1) Carbonaceous WAX 2.3 2.3 2 (2) 3 fuel .
WAX - - -(3) Gas-retaining Expanded agent (Unit of the GMB RMB (2) St parenthesized values is 7.0 2.5 4100.
volume o) (16.0) (18.0) 0.3 (15.3) Load of aluminum Particle powder size (Unit of the 0.1 mm 43 93 43 parenthesized (30) (30) (30) values is 1.2 mm - - -~ by wei ht) 2o s58 ~8 'able 14 Comparative 15 16 17 Example NH4N03 82.7 82.7 82.7 Aqueous inorganic NaN03 - - -oxidizer salt Water 11.7 11.7 11.7 MMA - - -nitrate Sensitizer Hyd - - -nitrate Composi- EDA - - -nitrate tion (parts Chelating EDTA - - -by weight) agent Tartaric - - -acid Emulsifier SMO - - -SMG 2.8 2.8 2.8 WAX 2.8 2.8 2.8 (1) Carbonaceous WAX - - -(2) fuel WAx - - -(3) Gas-retaining Expanded agent (Unit of the SMB RMB (2) St parenthesized values is 7 . 4 2 . 5 41001.
volume o ) (16.1) (18.0) 0.3 (15.1) Load of aluminum Particle powder size (Unit of the 0.1 mm 43 43 43 parenthesized (30) (30) (30) values is 1.2 mm - - -by wei ht) 2Q 658 4~8 able 15 Comparative 18 19 20 21 Example NHqN03 74.4 74.4 77.5 77.5 Aqueous inorganic NaNO - -3 5.2 5.2 oxidizer salt Water 10.5 10.5 11.7 11.7 MMA - - - -nitrate Sensitizer Hyd 10.0 10.0 - -nitrate Composi- EDA - - - -nitrate tion (parts Chelating by EDTA - - - -weight) agent Tartaric p.5 0.5 - -acid SMO 2.3 2.3 2.8 2.8 Emulsifier SMG - - - -WAX - - 1.4 1.4 (1) Carbonaceous WAX 0.4 0.4 1.4 1.4 (2) fuel WAX 1.9 1.9 - -(3) Gas-retaining Expanded Expanded agent (Unit of the St - St -parenthesized values is 3001 300, volume o ) 1.8 1.8 (53.0) (52.0) Load of aluminum Particle powder size (Unit of the 0.1 mm - - - -parenthesized values is 1.2 mm - - - -o by wei ht) 'able 16 Comparative 3 4 5 Example Performance APParent specific 1 1 2 ravit ( /cc) . . .
Underwater Ratio of shock energy 100 100 -Explosion energy Ratio of bubble energy 100 108 -Ratio of total energy 100 105 -Table 17 Ccmparative 6 7 8 Example Performance APParent specific 1.12 2 1 aravit (ct/cc) . .
Underwater Rat io of shock energy - - g2 Explosion energy Ratio of bubble energy - - 95 Ratio of total energy - - 94 Table 18 Comparative 9 10 11 Example Performance Apparent specific 2.00 l 2 ll 00 aravitv ( /cc) . .
Underwater Rat io of shock energy - - -Explosion energy Ratio of bubble energy - - -Ratio of total energy - - -able 19 Comparative 12 13 14 Example Apparent specific Performance ravit ( /cc) 1.40 1.34 1.25 Underwater Ratio of shock energy 116 120 -Explosion energy Ratio of bubble energy 158 175 -Ratio of total energy 145 161 -Table 20 Comparative 15 16 17 Example Apparent specific Performance ravit ( /cc) 1.39 1.33 1.25 Underwater Ratio of shock energy 108 110 -E~:plosion energy Ratio of bubble energy 132 158 -Ratio of total energy 119 143 -Table 21 Comparative 18 19 20 21 Example Performance Apparent specific 0.55 1.41 0.52 1.40 ravity ( /cc) Underwater Ratio of shock energy - - - -Explosion energy Ratio of bubble energy - - - -Ratio of total energy - - - -
Claims (31)
1. An explosive composition containing an aluminum powder and a water-in-oil emulsion including a continuous phase, a disperse phase, an emulsifier and a gas-retaining agent, characterized in that:
said continuous phase comprises 1 to 10 wt.% of a carbonaceous fuel, based on the total weight of the explosive composition;
said disperse phase comprises 3 to 30 wt.%
of water and 5 to 90 wt.% of an inorganic oxidizer salt, based on the total weight of the explosive composition;
said emulsifier is present in an amount of 0.1 to 10 wt.%, based on the total weight of the explosive composition;
said gas-retaining agent is an organic gas-retaining agent having an average particle size of 10 to 4000 µm and is present in an amount of 1 to 50 vol.%, based on the total volume of the explosive composition; and said aluminum powder has an average particle size not greater than 1 mm and is in admixture with said emulsion, said aluminum powder being present in an amount of 10 to 70 wt.%, based on the total weight of the explosive composition, whereby the explosion energy of said emulsion mixed with said aluminum powder is at least 1.16 times greater than the explosion energy of an emulsion not containing aluminum powder.
said continuous phase comprises 1 to 10 wt.% of a carbonaceous fuel, based on the total weight of the explosive composition;
said disperse phase comprises 3 to 30 wt.%
of water and 5 to 90 wt.% of an inorganic oxidizer salt, based on the total weight of the explosive composition;
said emulsifier is present in an amount of 0.1 to 10 wt.%, based on the total weight of the explosive composition;
said gas-retaining agent is an organic gas-retaining agent having an average particle size of 10 to 4000 µm and is present in an amount of 1 to 50 vol.%, based on the total volume of the explosive composition; and said aluminum powder has an average particle size not greater than 1 mm and is in admixture with said emulsion, said aluminum powder being present in an amount of 10 to 70 wt.%, based on the total weight of the explosive composition, whereby the explosion energy of said emulsion mixed with said aluminum powder is at least 1.16 times greater than the explosion energy of an emulsion not containing aluminum powder.
2. An explosive composition according to claim 1, wherein the explosion energy of said emulsion mixed with said aluminum powder is at most 2.13 times greater than the explosion energy of an emulsion not containing aluminum powder.
3. An explosive composition according to claim 1, wherein said aluminum powder has an average particle size ranging from 0.01 to 1 mm.
4. An explosive composition according to claim 1 or 3, wherein the particles of aluminum are spherical or scaly.
5. An explosive composition according to claim 1, wherein said gas-retaining agent is selected from the group consisting of polystyrene, polyethylene and polyvinylidene chloride.
6. An explosive composition according to claim 1, wherein said disperse phase comprises 7 to 30 wt.% of water.
7. An explosive composition according to claim 1, wherein said disperse phase comprises 40 to 80 wt.% of said inorganic oxidizer salt.
8. An explosive composition according to claim 1 or 7, wherein said inorganic oxidizer salt contains ammonium nitrate as a major component.
9. An explosive composition according to claim 1, wherein said emulsifier is present in an amount of 1 to 5 wt.%.
10. An explosive composition according to claim 1, further including a sensitizer.
11. An explosive composition according to claim 10, wherein said sensitizer is present in an amount of 1 to 40 wt.%, based on the total weight of the explosive composition.
12. An explosive composition according to claim 11, wherein said sensitizer is present in an amount of 1 to 20 wt.%.
13. An explosive composition according to claim 10, 11 or 12, wherein said sensitizer is selected from the group consisting of monomethylamine nitrate, hydrazine nitrate and ethylenediamine nitrate.
14. An explosive composition according to claim 13, wherein said sensitizer is hydrazine nitrate.
15. An explosive composition according to claim 14, further including a chelating agent.
16. An explosive composition according to claim 15, wherein the hydrazine nitrate is present in an amount of 1 to 20 wt.%, based on the total weight of the explosive composition, and wherein the chelating agent is present in an amount of 0.1 to 10 wt.%, based on the weight of hydrazine nitrate.
17. An explosive composition according to claim 1, wherein said disperse phase comprises 7 to 30 wt.% of water and 40 to 80 wt.% of said inorganic oxidizer salt, and wherein said emulsifier is present in an amount of 1 to 5 wt.%.
18. An explosive composition according to claim 17, wherein said inorganic oxidizer salt contains ammonium nitrate as a major component.
19. An explosive composition containing an aluminum powder and a water-in-oil emulsion including a continuous phase, a disperse phase, an emulsifier and a gas-retaining agent, characterized in that:
said continuous phase comprises 2.2 to 2.8 wt.% of a carbonaceous fuel, based on the total weight of the explosive composition;
said disperse phase comprises 9.2 to 11.7 wt.% of water and 70.9 to 82.7 wt.% of an inorganic oxidizer salt, based on the total weight of the explosive composition;
said emulsifier is present in an amount of 2.2 to 2.8 wt.%, based on the total weight of the explosive composition;
said gas-retaining agent is an organic gas-retaining agent having an average particle size of 10 to 4000 µm and is present in an amount of 0.6 to 2.5 wt.%, based on the weight of the explosive composition; and said aluminum powder has an average particle size not greater than 1 mm and is in admixture with said emulsion, said aluminum powder being present in an amount of 10 to 70 wt.%, based on the total weight of the explosive composition, whereby the explosion energy of said emulsion mixed with said aluminum powder is at least 1.16 times greater than the explosion energy of an emulsion not containing aluminum powder.
said continuous phase comprises 2.2 to 2.8 wt.% of a carbonaceous fuel, based on the total weight of the explosive composition;
said disperse phase comprises 9.2 to 11.7 wt.% of water and 70.9 to 82.7 wt.% of an inorganic oxidizer salt, based on the total weight of the explosive composition;
said emulsifier is present in an amount of 2.2 to 2.8 wt.%, based on the total weight of the explosive composition;
said gas-retaining agent is an organic gas-retaining agent having an average particle size of 10 to 4000 µm and is present in an amount of 0.6 to 2.5 wt.%, based on the weight of the explosive composition; and said aluminum powder has an average particle size not greater than 1 mm and is in admixture with said emulsion, said aluminum powder being present in an amount of 10 to 70 wt.%, based on the total weight of the explosive composition, whereby the explosion energy of said emulsion mixed with said aluminum powder is at least 1.16 times greater than the explosion energy of an emulsion not containing aluminum powder.
20. An explosive composition according to claim 19, wherein the explosion energy of said emulsion mixed with said aluminum powder is at most 2.13 times greater than the explosion energy of an emulsion not containing aluminum powder.
21. An explosive composition according to claim 20, wherein said aluminum powder has an average particle size ranging from 0.01 to 1 mm.
22. An explosive composition according to claim 19 or 21, wherein the particles of aluminum are spherical or scaly.
23. An explosive composition according to claim 19, wherein said gas-retaining agent is selected from the group consisting of polystyrene, polyethylene and polyvinylidene chloride.
24. An explosive composition according to claim 19, wherein said inorganic oxidizer salt contains ammonium nitrate as a major component.
25. An explosive composition according to claim 19, further including a sensitizer.
26. An explosive composition according to claim 25, wherein said sensitizer is present in an amount of 1 to 40 wt.%, based on the total weight of the explosive composition.
27. An explosive composition according to claim 26, wherein said sensitizer is present in an amount of 1 to 20 wt.%.
28. An explosive composition according to claim 25, 26 or 27, wherein said sensitizer is selected from the group consisting of monomethylamine nitrate, hydrazine nitrate and ethylenediamine nitrate.
29. An explosive composition according to claim 28, wherein said sensitizer is hydrazine nitrate.
30. An explosive composition according to claim 29, further including a chelating agent.
31. An explosive composition according to claim 30, wherein the hydrazine nitrate is present in an amount of 1 to 20 wt.%, based on the total weight of the explosive composition, and wherein the chelating agent is present in an amount of 0.1 to 10 wt.%, based on the weight of hydrazine nitrate.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1-216656 | 1989-08-23 | ||
| JP21665689 | 1989-08-23 | ||
| JP2-205522 | 1990-08-01 | ||
| JP02205522A JP3019375B2 (en) | 1989-08-23 | 1990-08-01 | Water-in-oil emulsion explosive composition |
| PCT/JP1990/001068 WO1991002706A1 (en) | 1989-08-23 | 1990-08-22 | W/o emulsion explosive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2065848A1 CA2065848A1 (en) | 1991-02-24 |
| CA2065848C true CA2065848C (en) | 1999-12-14 |
Family
ID=26515098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002065848A Expired - Fee Related CA2065848C (en) | 1989-08-23 | 1990-08-22 | Water-in-oil emulsion explosive composition |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0598115B1 (en) |
| CA (1) | CA2065848C (en) |
| DE (1) | DE69032230T2 (en) |
| WO (1) | WO1991002706A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2780726B1 (en) * | 1998-07-03 | 2000-08-25 | Nobel Explosifs France | ENERGY CARTRIDGE EXPLOSIVE EMULSIONS |
| US6113715A (en) * | 1998-07-09 | 2000-09-05 | Dyno Nobel Inc. | Method for forming an emulsion explosive composition |
| DE10031917B4 (en) * | 2000-06-07 | 2005-08-04 | H. Hiendl Gmbh & Co. Kg | Use of a water-in-oil emulsion as a concrete release agent |
| AU2013232234B9 (en) | 2012-03-12 | 2017-08-24 | The Texas A&M University System | Compositions having aluminum particles dispersed in a continuous phase |
| CN103130590A (en) * | 2012-12-17 | 2013-06-05 | 薛世忠 | Production method of explosive capable of discharging in a low-carbon mode |
| FR3021313B1 (en) * | 2014-05-20 | 2016-06-17 | Nitrates & Innovation | EXPLOSIVE CARTRIDGE PRODUCT OBTAINED FROM MIXTURE OF EMULSION AND POLYSTYRENE BALLS |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3151009A (en) * | 1961-08-25 | 1964-09-29 | Jr Harry A Toulmin | Catalyzed metal fuel |
| GB1593741A (en) * | 1977-06-24 | 1981-07-22 | Alcan Res & Dev | Aluminium powder blasting slurry sensitizer |
| ZW23483A1 (en) * | 1982-11-04 | 1985-07-12 | Aeci Ltd | An emulsion explosive having a solid fuel component of ferrosilicon |
| JPS6090887A (en) * | 1983-10-21 | 1985-05-22 | 日本油脂株式会社 | Water-in-oil emulsion explosive composition |
| JPH0637344B2 (en) * | 1986-03-10 | 1994-05-18 | 日本油脂株式会社 | Water-in-oil emulsion explosive composition |
| JPH0684273B2 (en) * | 1987-08-25 | 1994-10-26 | 日本油脂株式会社 | Water-in-oil emulsion explosive composition |
-
1990
- 1990-08-22 CA CA002065848A patent/CA2065848C/en not_active Expired - Fee Related
- 1990-08-22 EP EP90912461A patent/EP0598115B1/en not_active Expired - Lifetime
- 1990-08-22 WO PCT/JP1990/001068 patent/WO1991002706A1/en active IP Right Grant
- 1990-08-22 DE DE69032230T patent/DE69032230T2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0598115A1 (en) | 1994-05-25 |
| EP0598115A4 (en) | 1993-01-18 |
| EP0598115B1 (en) | 1998-04-08 |
| CA2065848A1 (en) | 1991-02-24 |
| DE69032230D1 (en) | 1998-05-14 |
| DE69032230T2 (en) | 1998-08-06 |
| WO1991002706A1 (en) | 1991-03-07 |
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| Date | Code | Title | Description |
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| EEER | Examination request | ||
| MKLA | Lapsed |