CA1090139A - Explosive compositions - Google Patents
Explosive compositionsInfo
- Publication number
- CA1090139A CA1090139A CA270,538A CA270538A CA1090139A CA 1090139 A CA1090139 A CA 1090139A CA 270538 A CA270538 A CA 270538A CA 1090139 A CA1090139 A CA 1090139A
- Authority
- CA
- Canada
- Prior art keywords
- sensitising
- explosive compositions
- auxiliary
- compositions
- per cent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A thickened, water-based, salt-containing explosive composition is provided wherein the sensitising agent com-prises a mixture of a soluble fuel such as dimethyl sulph-oxide, sugar or formamide and an auxiliary sensitising material such as ethylene glycol mononitrate. The mixture produces a synergism which results in marked improvements in sensitivity in aqueous slurry explosives containing the sen-sitizer blend.
A thickened, water-based, salt-containing explosive composition is provided wherein the sensitising agent com-prises a mixture of a soluble fuel such as dimethyl sulph-oxide, sugar or formamide and an auxiliary sensitising material such as ethylene glycol mononitrate. The mixture produces a synergism which results in marked improvements in sensitivity in aqueous slurry explosives containing the sen-sitizer blend.
Description
ll)90i3g The present invention relates to an improved explosive composition. More particularly, it relates to explosive compos-itions of the water bearing type generally known in the art as slurry explosive compositions or slurry explosives or slurried blasting agents which comprise a fuel and a liquid solvent, disperser or carrier for said salt. Although the term 'slurry' is universally applied to such compositions, the degree of consistency may range from pourable to highly viscous extrudable gels. The oxidising salt generally comprises nitrates or perch-lorates of ammonia, sodium, potassium, calcium or barium and mixtures of any two or more of said nitrates. In the most extensively used compositions the oxidising salt is ammonium nitrate alone or in admixture with sodium nitrate.
In slurry explosive compositions the liquid content is sufficient to maintain a reasonably continuous liquid phase, which renders the compositions fluid or plastic for direct loading into boreholes or for packaging in paper or synthetic plastics wrapped cartridges. As is known, the liquid phase can be constituted in various ways. Thusj it may consist mainly of an aqueous solution of oxidising salt but in some known compositions it comprises an emulsion of water in oil or it may be a dispersion of oil in droplet form throughout a thickened aqueous phase. Non-aqueous slurry explosive compositions are also known wherein a liquid chemical compound provides the liquid phase.
Thickening agents have been employed extensively to increase the viscosity of explosive slurry compositions to the desired degree to prevent segregation of the ingredients and to improve their resistance to deterioration in wet conditions.
These agents include various flours or~powders of natural ... -., . ~ -1()90139 i ; polysaccharides (of which guar gum has been the most popular) and biopolymers such as Xanthan gums. Further improvement in homogeneity and storage properties of the slurry compositions has been achieved by chemically crosslinking the thickening agents with crosslinking agents such as potassium and sodium dichromates or potassium pyroantimonates which are compatible with the other components of the explosive slurry compositions.
It is also common practice in the art to aerate -explosive slurry compositions in order to improve their sensitivity to initiation by the well known 'hot spot' technique.
Aeration may be effected by mechanical mixing alone but is generally enhanced by the inclusion of foaming surfactant in the composition. Other methods are the inclusion of gas filled spheres of glass or synthetic plastics material or gas generating compounds in the compositions.
The fuel component is provided in the explosive slurry ;~
composition for oxygen balance and it also enhances the power and sensitises the composition. The range of fuels is large.
Thus, for compositions for use with heavy priming in large diameter, coal, carbon black, sulphur, sugar, aluminium, molasses, starches and various alcohols have been found suitable.
-:.:-. . .
Sensitising components are included in explosive ~-slurry compositions to enhance their sensitivity to initiation. ;~
In order to provide more sensitive compositions requiring less powerful and, therefore, less expensive boosters to initiate them, more effective sensitising components (which may also be fuels) are included. Well known sensitisers proposed or used in this respect have been trinitrotoluene, nitrobenzene, nitric acid, cellulose nitrate, aluminium, magnesium and boron. Such sensitisers have disadvantages in that they are solid or liquid . ~ -- ~ . . ~ -:~ . . . .
water-insoluble materials and are difficult to disperse uniformly and hold in suspension in the slurries. In the case of the liquid water-insoluble sensitisers, syneresis is liable to occur in the explosives slurry compositions as finally prepared.
Frequently, the sensitisers have an objectionable odour or marked physiological properties. Solid sensitisers of light, finely divided elements are difficult to incorporate in a homogeneous manner and explosive slurry compositions containing such components are liable to desensitisation during packaging operations and while kept in storage.
Liquid water-soluble sensitisers, for example ethylene glycol monoitrate, are costly and their high costs hinders a large scale introduction of slurry explosive compositions for blasting purposes. Consequently, although it is feasible technically to replace nitroglycerine based explosive compos-itions with slurry explosive compositions, at present the latter compositions suitable for use in boreholes of small diameters, for instance 25 mm, are not commercially viable as replacements for the conventional nitroglycerine explosives.
The important coneept of this invention is the development of new sensitising components for slurry explosive compositions and it is the principal object of the invention to provide slurry explosive compositions with other sensitising components in order to minimise or eliminate those disadvantages encountered in the prior art.
Investigations conducted overseas about six years ago relating to this subject indicated that most water soluble fuels imparted better sensitivity than insoluble fuels. It was postulated that the sensitising action observed with the use of certain soluble fuels was due to a) solubility of these 13~
fuels in water, so that both the nitrate and the fuel are in the homogeneous phase where initiation starts, b) the presence of a reducing function, and c) lowering of the activation energy for the initiation reaction.
Recent work by the inventor on the problem of finding new ways of sensitising slurry explosive compositions and also reducing the content of known and presently used sensitising compounds therein because of their high costs has led to promising developments. He found, inter alia, that fuels such as dimethyl sulphoxide, for example, could be incorporated in slurry explosive compositions in small amounts together with small amounts of additional or auxiliary sensitising compounds and that marked improvements in sensitivity were obtained thereby in slurry `
explosive compositions. ~
.
Accordingly, this invention provides improved thickened slurry explosive compositions comprising at least one inorganic ;~
oxidising slat, water, thickening agent, density controlling agent and sensitising agent, the improvement comprising the use as the sensitising agent of a homogeneous mixture of a soluble fuel and an auxiliary sensitising compound wherein synergism occurs when the soluble fuel and the auxiliary sensitising compound are mixed together to form the sensiting agent, siad compound being soluble in the soluble fuel and/or in watar.
The sensitising components of this invention are compatible with other ways and means of explosive slurry sens-itisation, such as chemical or mechanical gassing to give density modifications, the use of light elemental sensitisers or other sensitisers. Thus, there may advantageously be included in the composition a foaming surfactant to entrap air during stirring, or chemical gassing agents such as sodium nitrate or or thiourea to generate gas in situ or hollow microballoons.
lVS'(~13~
Advantageously, the soluble fuel comprises dimethyl sulphoxide or other soluble fuels having a reducing function such as thiourea, sugar and glycerol, or soluble fuels capable of dissolving substantial amounts of the inorganic oxidising salt(s) such as formamide, dimethyl formamide and methanol, or mixtures thereof while the auxiliary sensitising compound comprises ethylene glycol mononitrate or other sensitisers such as methylamine nitrate, ethylene diamine dinitrate, methylnitramine, ethylene dinitramine or any sensitising compound soluble in the soluble fuel and/or water or mixtures thereof.
Preferably the slurry explosive compositions contain sensitising agents in which the ratio by weight of soluble fuel to auxiliary sensitising compound is about from 1:10 to 10:1 and, more preferably, for 1:3 to 3:1.
Slurry explosive compositions of the invention may comprise, by weight based on the total composition, about from 10 to 75 percent of ammonium nitrate, about from 0 to 30 percent ~
of sodium nitrate, about from 3 to 20 percent of water, about -from 0.3 to 2 percent of guar gum crosslinked with, based on the weight of the guar gum, about from 0.02 to 2.0 percent of crosslinking agent, (such as, for example, potassium ~-pyroantimonate, zinc chromate or dichromate of sodium or pota-ssium), about from 0.1 to 10 percent of surfactant/stabiliser paste to generate and retain stabilised bubbles throughout the composition, said composition being sensitised by about from 5 to 30 percent of a sensitising agent, which is a homogeneous mix ure of about from 1 to 10 percent soluble fuel and about from 1 to 20 percent of auxiliary sensitising compound.
Additional ingredients may be added such as are known or used in the prior art and other convenient fuel ' - , 3~
materials including aluminium powder, urea and flours of cellulosic materials.
In the following examples, wh~ich illustrate this invention, the percentages and ratio~ are by weight unless otherwise indicated. The Table shows three slurry explosive compositions, each of which had incorporated therein an amount of 7 percent of sensitising agent. It will be observed that ~- -the first composition contained dimethyl sulphoxide, the second composition contained ethylene glycol mononitrate and the third composition contained a mixture of 3 percent of ~-DMSO and 4 percent of EGMN. It will be observed further that the first and second compositions failed to initiate even with the aid of a booster whereas the third composition was - ;~
initiated by a detonator only. A type 6D detonator has a base charge of 350 milligrams of pentaerithritol tetranitrate (PETN) and the "Anstart" (Registered Trade Mark of AE & CI Limited) brand of booster has a base charge of 1.35 gm. of PETN. This significant test result clearly indicates the synergistic effect of the two components in the sensitising agent.
:
1(~90~39 TABLE
._ , _ Dimethyl sulphoxide (DMSO)7.00 Nil 3.00 Ethylene glycol mononitrateNil 14.00 8.00 liquor* (EGMN) (=7% EGMN) (,4% EGMN) Water 8.00 7.00 8.00 Ammonium nitrate (AN) 62.33 51.63 55.73 Sodium nitrate 15.00 15.00 15.00 Aluminium (atomised) 6.00 6.00 6.00 Wood meal Nil 4.70 2.60 HP-l Guar gum 0.50 0.50 0.50 Potassium pyroantimonate 0.02 0.02 0.02 Surfactant/stabiliser ..
paste** 0.65 0.65 0.65 Acetic acid/sodium acetate ~ -buffer 0.50 0.50 0.60 Density g/cm3 1.17 1.17 1.17 Minimum initiator : .
(unconfined) >6D ~ Anstar 76D ~ Anstart 6D
Temperature 28C 28C 28C
Diameter 25 mm 25 mm 25 mm * EGMN 50%
AN 28%
Water 18%
Glycol 4% :-** paste acutally used was a mixture of 3.3 parts ethoxylated ammonium lauryl sulphate to 1 part of a blend of C20 - C22 aliphatic amines.
.. ,~. ... . .
,." , ' ,' :
In slurry explosive compositions the liquid content is sufficient to maintain a reasonably continuous liquid phase, which renders the compositions fluid or plastic for direct loading into boreholes or for packaging in paper or synthetic plastics wrapped cartridges. As is known, the liquid phase can be constituted in various ways. Thusj it may consist mainly of an aqueous solution of oxidising salt but in some known compositions it comprises an emulsion of water in oil or it may be a dispersion of oil in droplet form throughout a thickened aqueous phase. Non-aqueous slurry explosive compositions are also known wherein a liquid chemical compound provides the liquid phase.
Thickening agents have been employed extensively to increase the viscosity of explosive slurry compositions to the desired degree to prevent segregation of the ingredients and to improve their resistance to deterioration in wet conditions.
These agents include various flours or~powders of natural ... -., . ~ -1()90139 i ; polysaccharides (of which guar gum has been the most popular) and biopolymers such as Xanthan gums. Further improvement in homogeneity and storage properties of the slurry compositions has been achieved by chemically crosslinking the thickening agents with crosslinking agents such as potassium and sodium dichromates or potassium pyroantimonates which are compatible with the other components of the explosive slurry compositions.
It is also common practice in the art to aerate -explosive slurry compositions in order to improve their sensitivity to initiation by the well known 'hot spot' technique.
Aeration may be effected by mechanical mixing alone but is generally enhanced by the inclusion of foaming surfactant in the composition. Other methods are the inclusion of gas filled spheres of glass or synthetic plastics material or gas generating compounds in the compositions.
The fuel component is provided in the explosive slurry ;~
composition for oxygen balance and it also enhances the power and sensitises the composition. The range of fuels is large.
Thus, for compositions for use with heavy priming in large diameter, coal, carbon black, sulphur, sugar, aluminium, molasses, starches and various alcohols have been found suitable.
-:.:-. . .
Sensitising components are included in explosive ~-slurry compositions to enhance their sensitivity to initiation. ;~
In order to provide more sensitive compositions requiring less powerful and, therefore, less expensive boosters to initiate them, more effective sensitising components (which may also be fuels) are included. Well known sensitisers proposed or used in this respect have been trinitrotoluene, nitrobenzene, nitric acid, cellulose nitrate, aluminium, magnesium and boron. Such sensitisers have disadvantages in that they are solid or liquid . ~ -- ~ . . ~ -:~ . . . .
water-insoluble materials and are difficult to disperse uniformly and hold in suspension in the slurries. In the case of the liquid water-insoluble sensitisers, syneresis is liable to occur in the explosives slurry compositions as finally prepared.
Frequently, the sensitisers have an objectionable odour or marked physiological properties. Solid sensitisers of light, finely divided elements are difficult to incorporate in a homogeneous manner and explosive slurry compositions containing such components are liable to desensitisation during packaging operations and while kept in storage.
Liquid water-soluble sensitisers, for example ethylene glycol monoitrate, are costly and their high costs hinders a large scale introduction of slurry explosive compositions for blasting purposes. Consequently, although it is feasible technically to replace nitroglycerine based explosive compos-itions with slurry explosive compositions, at present the latter compositions suitable for use in boreholes of small diameters, for instance 25 mm, are not commercially viable as replacements for the conventional nitroglycerine explosives.
The important coneept of this invention is the development of new sensitising components for slurry explosive compositions and it is the principal object of the invention to provide slurry explosive compositions with other sensitising components in order to minimise or eliminate those disadvantages encountered in the prior art.
Investigations conducted overseas about six years ago relating to this subject indicated that most water soluble fuels imparted better sensitivity than insoluble fuels. It was postulated that the sensitising action observed with the use of certain soluble fuels was due to a) solubility of these 13~
fuels in water, so that both the nitrate and the fuel are in the homogeneous phase where initiation starts, b) the presence of a reducing function, and c) lowering of the activation energy for the initiation reaction.
Recent work by the inventor on the problem of finding new ways of sensitising slurry explosive compositions and also reducing the content of known and presently used sensitising compounds therein because of their high costs has led to promising developments. He found, inter alia, that fuels such as dimethyl sulphoxide, for example, could be incorporated in slurry explosive compositions in small amounts together with small amounts of additional or auxiliary sensitising compounds and that marked improvements in sensitivity were obtained thereby in slurry `
explosive compositions. ~
.
Accordingly, this invention provides improved thickened slurry explosive compositions comprising at least one inorganic ;~
oxidising slat, water, thickening agent, density controlling agent and sensitising agent, the improvement comprising the use as the sensitising agent of a homogeneous mixture of a soluble fuel and an auxiliary sensitising compound wherein synergism occurs when the soluble fuel and the auxiliary sensitising compound are mixed together to form the sensiting agent, siad compound being soluble in the soluble fuel and/or in watar.
The sensitising components of this invention are compatible with other ways and means of explosive slurry sens-itisation, such as chemical or mechanical gassing to give density modifications, the use of light elemental sensitisers or other sensitisers. Thus, there may advantageously be included in the composition a foaming surfactant to entrap air during stirring, or chemical gassing agents such as sodium nitrate or or thiourea to generate gas in situ or hollow microballoons.
lVS'(~13~
Advantageously, the soluble fuel comprises dimethyl sulphoxide or other soluble fuels having a reducing function such as thiourea, sugar and glycerol, or soluble fuels capable of dissolving substantial amounts of the inorganic oxidising salt(s) such as formamide, dimethyl formamide and methanol, or mixtures thereof while the auxiliary sensitising compound comprises ethylene glycol mononitrate or other sensitisers such as methylamine nitrate, ethylene diamine dinitrate, methylnitramine, ethylene dinitramine or any sensitising compound soluble in the soluble fuel and/or water or mixtures thereof.
Preferably the slurry explosive compositions contain sensitising agents in which the ratio by weight of soluble fuel to auxiliary sensitising compound is about from 1:10 to 10:1 and, more preferably, for 1:3 to 3:1.
Slurry explosive compositions of the invention may comprise, by weight based on the total composition, about from 10 to 75 percent of ammonium nitrate, about from 0 to 30 percent ~
of sodium nitrate, about from 3 to 20 percent of water, about -from 0.3 to 2 percent of guar gum crosslinked with, based on the weight of the guar gum, about from 0.02 to 2.0 percent of crosslinking agent, (such as, for example, potassium ~-pyroantimonate, zinc chromate or dichromate of sodium or pota-ssium), about from 0.1 to 10 percent of surfactant/stabiliser paste to generate and retain stabilised bubbles throughout the composition, said composition being sensitised by about from 5 to 30 percent of a sensitising agent, which is a homogeneous mix ure of about from 1 to 10 percent soluble fuel and about from 1 to 20 percent of auxiliary sensitising compound.
Additional ingredients may be added such as are known or used in the prior art and other convenient fuel ' - , 3~
materials including aluminium powder, urea and flours of cellulosic materials.
In the following examples, wh~ich illustrate this invention, the percentages and ratio~ are by weight unless otherwise indicated. The Table shows three slurry explosive compositions, each of which had incorporated therein an amount of 7 percent of sensitising agent. It will be observed that ~- -the first composition contained dimethyl sulphoxide, the second composition contained ethylene glycol mononitrate and the third composition contained a mixture of 3 percent of ~-DMSO and 4 percent of EGMN. It will be observed further that the first and second compositions failed to initiate even with the aid of a booster whereas the third composition was - ;~
initiated by a detonator only. A type 6D detonator has a base charge of 350 milligrams of pentaerithritol tetranitrate (PETN) and the "Anstart" (Registered Trade Mark of AE & CI Limited) brand of booster has a base charge of 1.35 gm. of PETN. This significant test result clearly indicates the synergistic effect of the two components in the sensitising agent.
:
1(~90~39 TABLE
._ , _ Dimethyl sulphoxide (DMSO)7.00 Nil 3.00 Ethylene glycol mononitrateNil 14.00 8.00 liquor* (EGMN) (=7% EGMN) (,4% EGMN) Water 8.00 7.00 8.00 Ammonium nitrate (AN) 62.33 51.63 55.73 Sodium nitrate 15.00 15.00 15.00 Aluminium (atomised) 6.00 6.00 6.00 Wood meal Nil 4.70 2.60 HP-l Guar gum 0.50 0.50 0.50 Potassium pyroantimonate 0.02 0.02 0.02 Surfactant/stabiliser ..
paste** 0.65 0.65 0.65 Acetic acid/sodium acetate ~ -buffer 0.50 0.50 0.60 Density g/cm3 1.17 1.17 1.17 Minimum initiator : .
(unconfined) >6D ~ Anstar 76D ~ Anstart 6D
Temperature 28C 28C 28C
Diameter 25 mm 25 mm 25 mm * EGMN 50%
AN 28%
Water 18%
Glycol 4% :-** paste acutally used was a mixture of 3.3 parts ethoxylated ammonium lauryl sulphate to 1 part of a blend of C20 - C22 aliphatic amines.
.. ,~. ... . .
,." , ' ,' :
Claims (12)
1. In thickened slurry explosive compositions comprising at least one inorganic oxidising salt, water, thickening agent, density controlling agent and sensitising agent, the improvement comprising the use as the sensitising agent of a homogeneous mixture of a soluble fuel and an auxiliary sensitising compound wherein synergism occurs when the soluble fuel and the auxiliary sensitising compound are mixed together to form the sensitising agent, said compound being soluble in the soluble fuel and/or in water.
2. Explosive compositions as claimed in claim 1 wherein the soluble fuel is dimethyl sulphoxide.
3. Explosive compositions as claimed in claim 1 wherein the soluble fuel is selected from thiourea, sugar and glycerol.
4. Explosive compositions as claimed in claim 1 wherein the soluble fuel is selected from formamide, dimethyl formamide and methanol.
5. Explosive compositions as claimed in claim 1 wherein the soluble fuel is a mixture of any two or more of dimethyl sulphoxide, thiourea, sugar, glycerol, formamide, dimethyl formamide and methanol.
6. Explosive compositions as claimed in Claim 1 wherein the auxiliary sensitising compound is ethylene glycol mononitrate.
7. Explosive compositions as claimed in Claim 1 wherein the auxiliary sensitising compound is selected from methylamine nitrate, ethylene diamine dinitrate, methyl nitramine and ethylene dinitramine.
8. Explosive compositions as claimed in Claim 1 wherein the auxiliary sensitising compound is a mixture of any two or more of ethyleneglycol mononitrate, methylamine nitrate, ethylene diamine dinitrate, methyl nitramine and ethylene dinitramine.
9. Explosive compositions as claimed in Claim 1 wherein the compositions contain sensitising agents in which the ratio by weight of soluble fuel to auxiliary sensitising compound is about from 1:10 to 10:1.
10. Explosive compositions as claimed in Claim 9 wherein the ratio by weight of soluble fuel to auxiliary sensitising compound is from 1:3 to 3:1.
11. Explosive compositions as claimed in Claim 1 wherein the density controlling agent comprises a combination of a foaming surfactant and a stabilising surfactant to retain entrapped gas bubbles within the compositions.
12. Explosive compositions as claimed in claim 1 and comprising, by weight based on the total composition, about from 10 to 75 per cent of ammonium nitrate, about from 0 to 30 per cent of sodium nitrate, about from 3 to 20 per cent of water, about from 0,3 to 2 per cent of guar gum crosslinked with, based on the weight of the guar gum, about from 0,02 to 2,0 per cent of crosslinking agent, about from 0,1 to 10 per cent of surfactant/stabiliser paste to generate and retain stabilised bubbles throughout the composition, said composition being sensitised by about from 5 to 30 per cent of a sensitising agent, which is a homogeneous mixture of about from 1 to 10 per cent soluble fuel and about from 1 to 20 per cent of auxiliary sensitising compound.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ZA76/0430 | 1976-01-27 | ||
| ZA760430A ZA76430B (en) | 1976-01-27 | 1976-01-27 | Improvements in and relating to explosive compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1090139A true CA1090139A (en) | 1980-11-25 |
Family
ID=25569907
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA270,538A Expired CA1090139A (en) | 1976-01-27 | 1977-01-27 | Explosive compositions |
Country Status (5)
| Country | Link |
|---|---|
| AU (1) | AU2088176A (en) |
| BR (1) | BR7700093A (en) |
| CA (1) | CA1090139A (en) |
| GB (1) | GB1523020A (en) |
| ZA (1) | ZA76430B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA919516B (en) * | 1990-12-10 | 1993-06-03 | Dantex Explosives | Explosive composition. |
-
1976
- 1976-01-27 ZA ZA760430A patent/ZA76430B/en unknown
- 1976-12-23 AU AU20881/76A patent/AU2088176A/en not_active Expired
- 1976-12-29 GB GB54237/76A patent/GB1523020A/en not_active Expired
-
1977
- 1977-01-07 BR BR7700093A patent/BR7700093A/en unknown
- 1977-01-27 CA CA270,538A patent/CA1090139A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB1523020A (en) | 1978-08-31 |
| BR7700093A (en) | 1977-09-20 |
| AU2088176A (en) | 1978-06-29 |
| ZA76430B (en) | 1977-09-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |