EP0097030B1 - Explosive Wasser-in-Öl-Emulsion-Zusammensetzung und Verfahren zu ihrer Herstellung - Google Patents

Explosive Wasser-in-Öl-Emulsion-Zusammensetzung und Verfahren zu ihrer Herstellung Download PDF

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Publication number
EP0097030B1
EP0097030B1 EP19830303340 EP83303340A EP0097030B1 EP 0097030 B1 EP0097030 B1 EP 0097030B1 EP 19830303340 EP19830303340 EP 19830303340 EP 83303340 A EP83303340 A EP 83303340A EP 0097030 B1 EP0097030 B1 EP 0097030B1
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EP
European Patent Office
Prior art keywords
water
emulsion explosive
explosive composition
emulsion
composition according
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Expired
Application number
EP19830303340
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English (en)
French (fr)
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EP0097030A2 (de
EP0097030A3 (en
Inventor
Kenneth Andrew William Mitchell
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Orica Ltd
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ICI Australia Ltd
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Priority to AT83303340T priority Critical patent/ATE23985T1/de
Publication of EP0097030A2 publication Critical patent/EP0097030A2/de
Publication of EP0097030A3 publication Critical patent/EP0097030A3/en
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Publication of EP0097030B1 publication Critical patent/EP0097030B1/de
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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
    • C06B47/145—Water in oil emulsion type explosives in which a carbonaceous fuel forms the continuous phase

Definitions

  • This invention relates to a water-in-oil emulsion explosive composition having a discontinuous aqueous phase and a continuous oil or water-immiscible liquid organic phase and in particular to a water-in-oil emulsion explosive composition containing sump oil as the continuous phase and to processes for the preparation thereof.
  • Emulsion explosive compositions have been widely accepted in the explosive industry because of their excellent explosive properties and ease of handling.
  • the emulsion explosive compositions now in common use in the industry were first disclosed by Bluhm in United States Patent No. 3 447 978 and comprise three essential components: (a) a discontinuous aqueous phase comprising discrete droplets of an aqueous solution of inorganic oxygen-releasing salts; (b) a continuous water-immiscible organic phase throughout which the droplets are dispersed; and (c) an emulsifier which forms an emulsion of the droplets of oxidizer salt solution throughout the continuous organic phase.
  • oils may be used as the continuous, water-immiscible organic phase, or fuel, in emulsion explosive compositions.
  • oil may be used as the continuous, water-immiscible organic phase, or fuel, in emulsion explosive compositions.
  • the invention provides a water-in-oil emulsion explosive composition
  • a discontinuous aqueous phase comprising at least one oxygen-releasing salt, a continuous water-immiscible organic phase comprising sump oil, and an emulsifying agent.
  • Suitable oxygen-releasing salts for use in the aqueous phase component of the composition of the present invention include the alkali and alkaline earth metal nitrates, chlorates and perchlorates, ammonium nitrate, ammonium chlorate, ammonium perchlorate and mixtures thereof.
  • the preferred oxygen-releasing salts include ammonium nitrate, sodium nitrate and calcium nitrate.
  • the oxygen-releasing salt component of the compositions of the present invention comprises from 60 to 95% and preferably from 70 to 90% by weight of the total composition.
  • the preferred composition range for such a blend is from 5 to 40 parts of sodium nitrate for every 100 parts of ammonium nitrate. Therefore, in the preferred compositions of the present invention the oxygen-releasing salt component comprises from 70 to 90% by weight (of the total composition) ammonium nitrate or a mixture of from 5 to 30% by weight (of the total composition) sodium nitrate and from 40 to 85% by weight (of the total composition) ammonium nitrate.
  • the oxygen-releasing salt is in aqueous solution.
  • the amount of water employed in the compositions of the present invention is in the range of from 2 to 30% by weight of the total composition.
  • the amount employed is from 5 to 25%, and more preferably from 10 to 20%, by weight of the total composition.
  • the water-immiscible organic phase component of the composition of the present invention comprises sump oil as the continuous "oil" phase of the water-in-oil emulsion and comprises the fuel.
  • the term "sump oil” is used herein to mean used motor lubricating oil.
  • the sump oil may be mixed with other water-immiscible organic fuels such as fuel oil, diesel oil, distillate, kerosene, naphtha, waxes, paraffin oils, benzene, toluene, xylenes, asphaltic materials, polymeric oils such as the low molecular weight polymers of olefins, animal oils, fish oils, and other mineral, hydrocarbon or fatty oils, and mixtures thereof.
  • sump oil as the continuous oil phase in water-in-oil emulsion explosive compositions.
  • sump oil is regarded as waste which is difficult to dispose of in an environmentally acceptable manner and is therefore readily available and inexpensive.
  • the use of sump oil leads to an explosive composition having a significantly improved sensitivity and storage stability. Therefore, preferably the water-immiscible organic phase component of the composition of the present invention comprises at least 20% by weight of sump oil.
  • the organic fuel or continuous phase of the emulsion explosive composition of the present invention comprises from 2 to 15% by weight and preferably 5 to 10% by weight of the total composition.
  • the emulsifying agent component of the composition of the present invention may be chosen from the wide range of emulsifying agents known in the art for the preparatimn of water-in-oil emulsion explosive compositions.
  • emulsifying agents include alcohol alkoxylates, phenol alkoxylates, poly(oxyalkylene) glycols, poly(oxyalkylene) fatty acid esters, amine alkoxylates, fatty acid esters of sorbitol and glycerol, fatty acid salts, sorbitan esters, poly(oxyalkylene) sorbitan esters, fatty amine alkoxylates, poly(oxyalkylene)glycol esters, fatty acid amides, fatty acid amide alkoxylates, fatty amines, quaternary amines, alkyloxazolines, alkenyloxazolines, imidazolines, alkylsulfonates, alkylarylsulfonates, alkylsulfos
  • the preferred emulsifying agents are the 2-alkyl- and 2-alkenyl-4,4'-bis(hydroxymethy()oxazolines, the fatty acid esters of sorbitol, lecithin, copolymers of poly(oxyalkylene) glycols and poly(12-hydroxystearic acid), and mixtures thereof, and particularly sorbitan mono-oleate, sorbitan sesquioleate, 2-oleyl-4,4'- bis(hydroxymethyl)oxazoline, a mixture of sorbitan sesquioleate, lecithin and a copolymer of poly(oxyalkylene) glycol and poly(12-hydroxystearic acid), and mixtures thereof.
  • the emulsifying agent component of the composition of the present invention comprises up to 5% by weight of the total composition. Higher proportions of the emulsifying agent may be used and may serve as a supplemental fuel for the composition but in general it is not necessary to add more than 5% by weight of emulsifying agent to achieve the desired effect.
  • One of the advantages of the compositions of the present invention is that stable emulsions can be formed using relatively low levels of emulsifying agent and for reasons of economy it is preferable to keep the amount of emulsifying agent used to the minimum required to have the desired effect.
  • the preferred level of emulsifying agent used is in the range from 0.1 to 2.0% by weight of the total composition.
  • the emulsion explosive compositions of the present invention comprise a density reducing agent to reduce their density and enhance their sensitivity.
  • the agent may be incorporated into the compositions of the present invention as fine gas bubbles dispersed throughout the composition, hollow particles which are often referred to as microballoons, porous particles, or mixtures thereof.
  • a discontinuous phase of fine gas bubbles may be incorporated into the compositions of the present invention by mechanical agitation, injection or bubbling the gas through the composition, or by in situ generation of the gas by chemical means.
  • Suitable for the in situ generation of gas bubbles include peroxides such as, for example, hydrogen peroxide, nitrites such as, for example sodium nitrite, nitrosoamines such as, for example, N,N' - dinitrosopentamethylene tetramine, alkali metal borohydrides such as, for example, sodium borohydride, and carbonates such as sodium carbonate.
  • Preferred chemicals for the in situ generation of gas bubbles are nitrous acid and its salts which decompose under conditions of acid pH to produce gas bubbles.
  • Thiourea may be used to accelerate the decomposition of a nitrite gassing agent.
  • suitable hollow particles include small hollow microspheres of glass and resinous materials such as phenol-formaldehyde and urea-formaldehyde.
  • suitable porous materials include expanded minerals such as perlite.
  • secondary fuels may be incorporated into the compositions of the present invention is addition to the water-immiscible organic fuel phase.
  • secondary fuels include finely divided solids, and water-miscible organic liquids which can be used to partially replace water as a solvent for the oxygen-releasing salts or to extend the aqueous solvent for the oxygen-releasing salts.
  • solid secondary fuels include finely divided materials such as: sulfur; aluminium; and carbonaceous materials such as gilsonite, comminuted coke or charcoal, carbon black, resin acids such as abietic acid, sugars such as glucose or dextrose and other vegetable products such as starch, nut meal, grain meal and wood pulp.
  • water-miscible organic liquids include alcohols such as methanol, glycols such as ethylene glycol, amides such as formamide and amines such as methylamine.
  • the optionally secondary fuel component of the compositins of the present invention comprise from 0 to 30% by weight of the total composition.
  • compositions of the present invention are not narrowly critical. In order to obtain best performance from the compositions preferably their oxygen balance is in the range of from +0.5% to -1.5%. However, compositions having satisfactory performance can be prepared which have a highly negative oxygen balance.
  • the emulsion explosive compositions of the present invention which comprise sump oil as the sole component of the continuous organic phase or fuel have a surpisingly high viscosity when compared to prior art compositions prepared from fuels which are fluid at ambient temperatures.
  • This property of the compositions of the present invention can be advantageous in the preparation of viscous water-in-oil emulsion explosive compositions for use in up-holes where viscous or gelled compositions are required to avoid loss of the explosive composition from the hole.
  • Viscous water-in-oil emulsion explosive compositions can be made according to the prior art by incorporating into the continuous organic phase fuels such as waxes which are solids at ambient temperatures. However, in order to prepare such compositions the continuous organic phase must be heated to a temperature above the melting point of the wax. In contrast as sump oil is fluid at ambient temperatures viscous water-in-oil emulsion explosive compositions of the invention may be prepared without the need to heat the continuous organic phase prior to emulsification, which is a decided advantage in the on-site preparation of bulk emulsion explosive compositions.
  • the aqueous phase of the compositions of the present invention may comprise optional thickening agent(s) which optionally may be crosslinked.
  • the thickening agents when used in the compositions of the present invention, are suitably polymeric materials, especially gum materials typified by the galactomannan gums such as locust bean gum or guar gum or derivatives thereof such as hydroxypropyl guar gum.
  • gums are the so-called bipolymeric gums such as the heteropolysaccharides prepared by the microbial transformation of carbohydrate material, for example the treatment of glucose with a plant pathogen of the genus Xanthomonas typified by Xanthomonas campestris.
  • Other useful thickening agents include synthetic polymeric materials and in particular synthetic polymeric materials which are derived, at least in part, from the monomer acrylamide.
  • the optional thickening agent component of the compositions of the present invention comprises from 0 to 2% by weight of the total composition.
  • the thickening agent when used in the compositions of the present invention, the thickening agent optionally may be crosslinked. It is convenient for this purpose to use conventional crosslinking agents such as zinc chromate or a dichromate either as a separate entity or as a component of a conventional redox system such as, for example, a mixture of potassium dichromate and potassium antimony tartrate.
  • conventional crosslinking agents such as zinc chromate or a dichromate either as a separate entity or as a component of a conventional redox system such as, for example, a mixture of potassium dichromate and potassium antimony tartrate.
  • the optional crosslinking agent component of the compositions of the present invention comprises from 0 to 0.5% and preferably from 0 to 0.1% by weight of the total composition.
  • the pH of the emulsion explosive compositions of the present invention is not narrowly critical. However, in general the pH is between 0 and 8 and preferably the pH is between 1 and 5.
  • compositions of the present invention may be prepared by a number of methods.
  • compositions are prepared by:
  • the invention provides a method for the preparation of the novel emulsion explosive compositions herein described.
  • This Example illustrates the preparation of a water-in-oil emulsion explosive composition of the present invention.
  • a mixture of ammonium nitrate (2512.8 parts), sodium nitrate (740 parts) and water (443.2 parts) was heated with stirring to a temperature of 90°C to give an aqueous solution.
  • the hot aqueous solution was added, with rapid stirring, to a solution of 2 - oleyl - 4,4' - bis - (hydroxymethyl)oxazoline (40 parts) in sump oil (204) parts. Stirring was continued until a uniform emulsion was obtained.
  • Glass micro-balloons (100 g) were added to the emulsion and thoroughly mixed therein.
  • the composition was packaged into 25 mm diameter waxed paper cartridges and allowed to cool.
  • the emulsion explosive composition prepared as described above had a density of 1.13 g/ml and an average aqueous phase droplet size in the range from 1 to 4 micrometers.
  • This Example illustrates the improved detonation sensitivity of an explosive composition of the present invention.
  • Example 1 The explosive compositions prepared as described in Example 1 were tested for detonation sensitivity by firing in a test cell at a temperature of 8°C.
  • explosive compositions using paraffin oil as the oil phase were prepared following the same procedure described in Example 1 and stored and test fired under the same conditions as the explosive composition of the present invention.
  • composition of the present invention and the comparative composition had the same velocity of detonation as measured using Dautrich Plates.
  • An aqueous oxidizer salt solution was prepared by dissolving the oxidizing salt(s) in water at a temperature of 90°C.
  • the hot aqueous oxidizer salt solution was added to the hot continuous phase, comprising the oil or fuel and the emulsifying agent, while stirring at approximately 200 rpm in a Hobart Mixer Model 120A (Trade Mark).
  • the emulsion was refined by mixing for a further 5 minutes at approximately 350 rpm and then glass microballoons or a gassing agent were added and thoroughly blended into the emulsion. Samples of the composition were then run off into 85 mm diameter waxed cardboard tubes for testing purposes and allowed to cool to ambient temperature.
  • compositions detailed in Table 2 below were prepared following the above procedure.
  • This Example demonstrates the improved storage stability of the explosive compositions of the present invention.
  • This Example illustrates the preparation of a water-in-oil emulsion explosive composition of the present invention.
  • a mixture of ammonium nitrate (2648 parts), sodium nitrate (529 parts), water (448 parts) was heated with stirring to a temperature of 90°C to give an aqueous solution.
  • the hot aqueous solution was added with stirring on speed 2 of a Hobart Mixer to a hot solution of sump oil (36 parts), paraffin wax (77 parts), microcrystalline wax (76 parts) and sorbitan mono-oleate (54 parts). After 2 minutes mixing on speed 2 the emulsion was refined by mixing for a further 5 minutes on speed 3 of the mixer.
  • C15/250 grade glass microballoons (132 parts) were added to the emulsion and thoroughly mixed therein. Samples of the composition were packaged into 25 mm diameter waxed paper cartridges and allowed to cool.
  • This Example demonstrates the improved sensitivity and storage stability of the explosive compositions of the present invention.
  • the explosive composition prepared as described in Example 8 was tested for detonation sensitivity by firing a fresh sample in a test cell at a temperature of 9°C and firing under the same conditions a sample which had been stored at a temperature of 35°C for a period of 3 months in accelerated storage trials.
  • Comparative 8 For the purpose of comparison an explosive composition not of the invention was prepared following the same procedure as that described in Example 8 but substituting paraffin oil for sump oil used in that Example. For convenience this comparative example will be referred to as Comparative 8. In order to evaluate its detonation sensitivity after storage samples of the explosive composition of this Comparative Example were stored and fired under the same conditions as the samples of the explosive composition of
  • an explosive composition not of the invention was prepared following the same procedure but substituting furnace oil for sump oil.
  • Comparative 14 For convenience this Comparative Example will be referred to as Comparative 14.
  • the viscosities of the above compositions was determined at 65°C using a Brookfield Viscometer (Trade Mark) and are reported in Table 6 below together with details on the emulsifier content and emulsion stability.
  • This Example demonstrates the continuous preparation of a water-in-oil emulsion explosive composition of the present invention using a hydraulically driven pin-mill.
  • aqueous oxidizer solution comprising ammonium nitrate (7577 parts), sodium nitrate (494 parts) and water (1832 parts) at a temperature of 80°C was blended with a cold oil phase comprising sump oil (402 parts), distillate (134 parts) and sorbitan mono-oleate (96 parts) in a pin-mill operating at 450 rpm.
  • the emulsion from the pin-mill was fed to a blender and mixed with sufficient aqueous sodium nitrite solution (33% w/w) to give the product a density of 1.06-1.10 g/ml and samples of the gassed emulsion were loaded into cylindrical plastic bags for testing.
  • Samples of the emulsion were fired successfully using 30 g "Anzomex" A primer with a velocity of detonation of 5.1 km/sec and a critical diameter of less than 30 mm.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Colloid Chemistry (AREA)

Claims (10)

1. Wasser-in-ÖI-Emulsionssprengstoffzusammensetzung, dadurch gekennzeichnet, daß sie eine diskontinuierliche, wässrige Phase mit mindestens einem Sauerstoff-frei-setzenden Salz, eine kontinuierliche nicht mit Wasser mischbare, organische Phase mit Sumpföl und einen Emulgator umfaßt.
2. Emulsionssprengstoffzusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß das Sauerstoff-freisetzende Salz aus der Gruppe von Alkalimetall-, Erdalkalimetall-, Ammoniumsalzen, Nitraten, Chloraten und Perchloraten und deren Mischungen ausgewählt ist.
3. Emulsionssprengstoffzusammensetzung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Bestandteil mit dem Sauerstoff freisetzenden Salz 60 bis 95 Gew.-% der Gesamtzusammensetzung umfaßt.
4. Emulsionssprengstoffzusammensetzung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die kontinuierliche, nicht mit Wasser mischbare, organische Phase zusätzlich zu dem Sumpföl mindestens einen weiteren, nicht mit Wasser mischbaren, organischen Brennstoff umfaßt.
5. Emulsionssprengstoffzusammensetzung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die kontinuierliche, nicht mit Wasser mischbare, organische Phase 2 bis 15 Gew.-% der Gesamtzusammensetzung umfaßt.
6. Emulsionssprengstoffzusammensetzung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß der Emulgator ausgewählt ist aus: Alkoholalkoxylaten, Phenolalkoxylaten, Poly(oxyalken) glykolen, Poly(oxyalken)fettsäureestern, Aminoalkoxylaten, Fettsäureestern von Sorbit und Glycerin, Fettsäuresalzen, Sorbitestern, Poly(oxyalken) sorbitestern, Fettaminoalkoxylaten, Poly(oxyalken)-glycolestern, Fettsäureamiden, Fettsäureamidalkoxylaten, Fettaminen, quaternen Aminen, Alkyloxyzolinen, Alkenyloxazolinen, Imidazolinen, Alkylsulfonaten, Alkylarylsulfonaten, Alkylsulfosuczinaten, Alkylphosphaten, Alkenylphosphaten, Phosphatestern, Lecithin, Copolymeren von Poly(oxyalken)glykolen und Poly-12-hydroxystearinsäure und deren Mischungen.
7. Emulsionssprengstoffzusammensetzung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß der Emulgator 0,1 bis 2 Gew.-% der Gesamtzusammensetzung umfaßt.
8. Emulsionssprengstoffzusammensetzung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die wässrige Phase eine Wassermenge von 2 bis 30 Gew.-% der Gesamtzusammensetzung umfaßt.
9. Emulsionssprengstoffzusammensetzung nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß sie ein Dichte herabsetzendes Mittel enthält.
10. Verfahren zur Herstellung einer Emulsionssprengstoffzusammensetzung, enthaltend eine diskontinuierliche, wässrige Phase mit mindestens einem Sauerstoff-frei-setzenden Salz, eine kontinuierliche, nicht mit Wasser mischbare, organische Phase mit Sumpföl und einem Emulgator, dadurch gekennzeichnet, daß man:
a) die Sauerstoff-freisetzenden Salze in Wasser bei einerTemperatur oberhalb des Entmischungspunkt der wässrigen Salzlösung auflöst,
b) die wässrige Salzlösung, die nicht mit Wasser mischbare, organische Phase und den Emulgator bei schnellem Vermischen unter Bildung einer Wasser-in-Öl-Emulsion vereinigt,
c) die Emulsion vermischt, bis sie einheitlich ist,
d) gegebenenfalls irgendwelche festen Bestandteile und/oder Dichte-herabsetzenden Mittel in die Emulsion einmischt.
EP19830303340 1982-06-11 1983-06-09 Explosive Wasser-in-Öl-Emulsion-Zusammensetzung und Verfahren zu ihrer Herstellung Expired EP0097030B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83303340T ATE23985T1 (de) 1982-06-11 1983-06-09 Explosive wasser-in-oel-emulsion-zusammensetzung und verfahren zu ihrer herstellung.

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AU4411/82 1982-06-11
AU15619/83A AU551923B2 (en) 1982-06-11 1982-06-11 Emulsion (water in oil) explosives
AUPF441182 1982-06-11

Publications (3)

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EP0097030A2 EP0097030A2 (de) 1983-12-28
EP0097030A3 EP0097030A3 (en) 1985-04-03
EP0097030B1 true EP0097030B1 (de) 1986-12-03

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5017251A (en) * 1989-12-26 1991-05-21 Ireco Incorporated Shock-resistant, low density emulsion explosive
GB9003613D0 (en) * 1990-02-16 1990-04-11 Explosives Tech Eti Method of reducing the overloading of a borehole and explosive composition used therefor
IN179760B (de) * 1991-02-11 1997-11-29 Tech Resources Pty Ltd

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3447978A (en) * 1967-08-03 1969-06-03 Atlas Chem Ind Ammonium nitrate emulsion blasting agent and method of preparing same
US4111727A (en) * 1977-09-19 1978-09-05 Clay Robert B Water-in-oil blasting composition

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AU1561983A (en) 1983-12-15
EP0097030A2 (de) 1983-12-28
AU551923B2 (en) 1986-05-15
EP0097030A3 (en) 1985-04-03

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