WO1998051645A1 - Modification et modificateurs de rheologie - Google Patents

Modification et modificateurs de rheologie Download PDF

Info

Publication number
WO1998051645A1
WO1998051645A1 PCT/AU1998/000353 AU9800353W WO9851645A1 WO 1998051645 A1 WO1998051645 A1 WO 1998051645A1 AU 9800353 W AU9800353 W AU 9800353W WO 9851645 A1 WO9851645 A1 WO 9851645A1
Authority
WO
WIPO (PCT)
Prior art keywords
emulsion
associative thickener
acrylamide
emulsions
hydrophilic
Prior art date
Application number
PCT/AU1998/000353
Other languages
English (en)
Inventor
Simon Richard Biggs
Jennifer Liane Cleary
Anthony Martin Palmer
Jeremy Guy Breakwell Smith
Original Assignee
Orica Australia Pty. Ltd.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Orica Australia Pty. Ltd. filed Critical Orica Australia Pty. Ltd.
Priority to DE69827498T priority Critical patent/DE69827498T2/de
Priority to NZ500909A priority patent/NZ500909A/en
Priority to BR9809801-2A priority patent/BR9809801A/pt
Priority to AT98920397T priority patent/ATE282015T1/de
Priority to EP98920397A priority patent/EP1001917B1/fr
Priority to CA2289749A priority patent/CA2289749C/fr
Priority to APAP/P/1999/001706A priority patent/AP9901706A0/en
Priority to AU73259/98A priority patent/AU751545B2/en
Priority to JP54861998A priority patent/JP2001524065A/ja
Publication of WO1998051645A1 publication Critical patent/WO1998051645A1/fr
Priority to NO995560A priority patent/NO995560L/no

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
    • C06B47/145—Water in oil emulsion type explosives in which a carbonaceous fuel forms the continuous phase
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/001—Fillers, gelling and thickening agents (e.g. fibres), absorbents for nitroglycerine

Definitions

  • the present invention relates to explosives compositions and methods for modifying the rheology of explosives compositions using associative thickeners.
  • Water-in-oil emulsion explosive compositions were first disclosed by Bluhm in United States Patent 3,447,978 and comprise (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 oxidiser salt solution throughout the continuous organic phase.
  • these types of emulsions comprise very little water or adventitious water only in the discontinuous phase they are more correctly referred to as melt-in-fuel emulsion explosives.
  • emulsifiers are generally used to decrease interfacial tension between the aqueous and oil phases. Molecules of the emulsifier locate at the interface between the aqueous droplet and continuous hydrocarbon phase. The emulsifier molecules are oriented with the hydrophilic head group in the aqueous droplet and the lipophilic tail in the continuous hydrocarbon phase. Emulsifiers stabilise the emulsion, inhibiting coalescence of the aqueous droplets and phase separation. Emulsifiers also inhibit crystallisation of oxidiser salt in the aqueous droplets. Uncontrolled crystallisation can lead to emulsion breakdown and reduction in detonation sensitivity of the emulsion explosive composition.
  • the emulsions themselves are not detonable and in order to form an explosive composition, the emulsion must be mixed with sensitising agents such as a self explosive (e.g. trinitrotoluene or nitroglycerine) or a discontinuous phase of void agents.
  • sensitising agents such as a self explosive (e.g. trinitrotoluene or nitroglycerine) or a discontinuous phase of void agents.
  • Suitable void agents include glass microballoons, plastic microballoons, expanded polystyrene beads and gas bubbles including bubbles of entrained air.
  • Emulsions are often blended with ANFO-based explosive compositions to provide explosives which are commonly referred to as "heavy ANFO's".
  • Compositions comprising blends of emulsion and AN or ANFO are described for example in Australian Patent Application No. 29408/71 (Butterworth) and US Patents 3, 161,551 (Egly et al) and 4,357,184 (Binet et al).
  • Packaged explosives are manufactured at fixed site manufacturing facilities and the cartridges of packaged explosives are transported to the blast site and hand loaded into predrilled blastholes.
  • Bulk explosives are either manufactured at a manufacturing facility and transported in a specially designed truck to the mine or mixed on-site in manufacturing units located on trucks (called mobile manufacturing units or MMU's).
  • the transport trucks and MMU's are provided with the mechanised means of loading bulk explosive into blastholes.
  • the blasthole loading is usually carried out by either auguring, pouring, pumping or blow loading the bulk explosive into the blasthole, the loading method used depending on the physical characteristics of the type of bulk explosive used.
  • Loading by pu ⁇ ing is usually carried out by using a mechanical or pneumatic pump to push explosives compositions through a delivery hose into the blastholes.
  • Blow loading of an explosive composition typically involves the use of compressed gas to blow the explosive through a delivery hose into blastholes and is a commonly used delivery method.
  • MMU's and fixed manufacturing facilities store relatively large quantities of chemical components which can be mixed together to form explosives compositions.
  • MMU's comprise several large storage containers for storing fuel oil, emulsion, paniculate oxidiser salts, water and other explosive components. These components can be mixed in differing proportions to provide ANFO or various formulations of emulsion and heavy ANFO.
  • the manufacturing processes carried out using MMU's and fixed manufacturing facilities can provide various explosives formulations having various physical characteristics by precise control of the component flow rate, temperature and other physical parameters related to the manufacturing process.
  • emulsion rheology impacts on virtually every aspect of emulsion handling including the flow of the emulsion in pipes and hoses; adhesion to the walls of the tanks and conduits of the manufacturing system; ease of pumping; retention in upholes and cracked ground; and retention of voidage at low density.
  • explosives compositions which are very dense and viscous can only be pneumatically or mechanically pumped through short loading hoses; they cannot be pumped through long hoses without the use of excessively high pumping pressures or the hoses block up.
  • Associative thickeners have been previously used in technologies such as the coating industry.
  • United States Patent 5,521,235 (Redelius and Redelius) describes the use of hydrophobicaily modified urethane ethoxylates as associative nonionic type thickeners in cationic type bitumen emulsion for rods, roofing and waterproofing to allow thicker coating layers to be formed.
  • Canadian Patent 2079926 (Fistner) discloses an aqueous paint composition with high gloss for use on textiles, the paint comprising an associative thickener, preferably a polyurethane block copolymer or an alkali swellable acrylic polymer or an alkali soluble acrylic polymer.
  • Associative thickeners have also been used in thickening drilling muds, polishes, cleaners, personal care products such as cosmetics, food products and pharmaceuticals, hydraulic fluids and inks but not hitherto in explosives manufactured to control rheo logical characteristics.
  • associative thickeners may be used in emulsions for use in explosive compositions, which associative thickeners provide for rapid and reversible changes in emulsion viscosity.
  • Associative thickeners provide explosives emulsions having the desirable characteristics of (1) significant reduction in viscosity during pumping and (2) reestablishment of relatively high viscosity when pumping is terminated without damage to the emulsion components. It is believed that the associative thickener provides a network of physical linkages throughout the emulsion which network can be reversibly broken down.
  • the present invention provides an emulsion for use in emulsion explosives wherein said emulsion comprises an associated thickener.
  • an emulsion according to claim 1 wherein the emulsion has increased zero-shear viscosity relative to an emulsion absent the associative thickener and exhibits significant reduction in viscosity when subjected to applied shear force and reestablishes substantially the original viscosity when the applied shear force is removed.
  • an emulsion explosive composition comprising incorporating at least one associative thickener in an aqueous phase and subsequently emulsifying the aqueous phase in an oil phase to form a water-in-oil emulsion.
  • an emulsion explosive composition comprising incorporating at least one associative thickener in an oil phase and subsequently emulsifying an aqueous phase in the oil phase to form a water-in-oil emulsion.
  • associative thickeners may be used in the present invention. Suitable associative thickeners may be selected in accordance with their compatibility with the emulsion explosive in which they are incorporated.
  • the associative thickener of the present invention may be polymeric or non-polymeric and may act in either an aqueous or non-aqueous phase of the emulsion depending upon the chemical nature of the selected associative thickener.
  • the associative thickener may typically comprise a backbone or chain which is soluble in the organic, or alternatively the aqueous, phase of the emulsion. These associative thickeners additionally comprises a number of moieties which are insoluble in the phase in which the backbone is soluble. These moieties are preferably dispersed along the backbone with insoluble moieties present within or as pendent or terminal groups on the chain.
  • the associative thickener may be a polymer soluble in either the aqueous or oil phase and have insoluble moieties substituted thereto in substoichiometric amounts.
  • the associative thickener comprises blocks of hydrophilic polymers or copolymer prepared with small amounts of hydrophobic comonomer.
  • the hydrophilic polymer or copolymer is preferably prepared from monomers selected from the group consisting of vinylpyrrolidone, vinyl acetate, acrylamide, ethylene glycol, ethylene oxide, vinyl alcohol and propylene glycol and their hydrophilic derivatives.
  • the hydrophobic monomer may be any monomer polymerisable with the hydrophilic monomer and which contains hydrophobic moieties.
  • suitable hydrophobic monomers which will be known to those skilled in the art of associative thickeners.
  • the hydrophobic monomers selected from the group consisting of N- alkylacrylamides such as N-(4-ethylphenyl)acrylamide, N-(4-t-butylphenyl)acrylamide and the like.
  • the associative thickener may be for example, a copolymer of acrylamide (a hydrophile) and N-4-(t-butyI)phenyl acrylamide (a hydrophobe) comprising less than 1 % mol % hydrophobic comonomer.
  • the associative thickener may alternatively comprise blocks of hydrophobic copolymer prepared with small amounts of hydrophilic comonomer.
  • micellar copolymerisation or from the chemical modification of a water-soluble precursor polymer.
  • the latter route has mainly been applied to cellulose derivatives, poly(acrylic acid) and ethoxylated urethane polymers.
  • the micellar copolymerisation process involves essentially acrylamide-based copolymers.
  • An additional synthetic route which utilises hydrophobic monomers with a built in surfactant character overcomes the need for the external surfactants used in the micellar technique.
  • Factors which influence the viscosifying ability of associative thickeners, in the absence of shear are many and varied. Included in these are the molecular weight of the copolymer, the copolymer micro structure (hydrophobe content and hydrophobe distribution along the polymer chain), the hydrophobicity of the hydrophobe, the presence of charge either in the polymer backbone or on the pendant hydrophobic groups, the copolymer concentration, the presence of additives (e.g. salt or surfactant) and temperature. Depending on the relative influence of each of these factors and the copolymer chain flexibility, both interchain and intrachain associations may occur.
  • additives e.g. salt or surfactant
  • the emulsion suitable for use as an explosives emulsion is a water-in-oil or melt-in-oil emulsion or melt-in-fuel emulsion.
  • the associative thickener is dissolved in the aqueous or organic phase prior to emulsion formation.
  • the emulsion comprises 0.1 % to 3% by weight of emulsion of associated thickener. More typically the associative thickener is present at a concentration of 0.2 to 2% by weight of emulsion.
  • Suitable oxygen releasing salts for use in the aqueous phase of the emulsion 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. More preferably the oxygen releasing salt comprises ammonium nitrate or a mixture of ammonium nitrate and sodium or calcium nitrates.
  • the oxygen releasing salt component of the compositions of the present 5 invention comprise from 45 to 95 % w/w and preferably from 60 to 90 % w/w of the total emulsion composition.
  • the oxygen releasing salt comprises a mixture of ammonium nitrate and sodium nitrate the preferred composition range for such a blend is from 5 to 80 parts of sodium nitrate for every 100 parts of ammonium nitrate.
  • the oxygen releasing salt component comprises from 10 45 to 90 % w/w (of the total emulsion composition), ammonium nitrate or mixtures of from 0 to 40 % w/w, sodium or calcium nitrates and from 50 to 90 % w/w ammonium nitrate.
  • the amount of water employed in the compositions of the present invention is in the range of from 0 to 30 % w/w of the total emulsion composition.
  • the 15 amount employed is from 4 to 25 % w/w and more preferably from 6 to 20 % w/w.
  • the water immiscible organic phase of the emulsion composition of the present invention comprises the continuous "oil" phase of the emulsion composition and is the fuel.
  • Suitable organic fuels include aliphatic, alicyclic and aromatic compounds and mixtures thereof which are in the liquid state at the formulation temperature.
  • Suitable organic fuels may be chosen from fuel oil, diesel oil, distillate, furnace oil, kerosene, naphtha, waxes such as microcrystalline wax, paraffin wax and slack wax, paraffin oils, benzene, toluene, xylenes, asphaltic materials, polymeric oils such as the low molecular weight polymers of
  • 25 olefines, animal oils, vegetable oils, fish oils and other mineral, hydrocarbon or fatty oils and mixtures thereof.
  • Preferred organic fuels are liquid hydrocarbons generally referred to as petroleum distillates such as gasoline, kerosene, fuel oils and paraffin oils.
  • the organic fuel or continuous phase of the emulsion comprises from 2 to 30 15 % w/w and preferably 3 to 10 % w/w of the total composition.
  • the emulsifier of the emulsion composition of the present invention may comprise emulsifiers chosen from the wide range of emulsifiers known in the art from the preparation of emulsion explosive compositions. It is particularly preferred that the emulsifier used in the emulsion composition of the present invention is one of the well known emulsifiers based on the reaction products of poly[alk(en)yl] succinic anhydrides and alkylamines, including the polyisobutylene succinic anhydride (PiBSA) derivatives of alkanolamines.
  • PiBSA polyisobutylene succinic anhydride
  • Suitable emulsifiers for use in the emulsion of the present invention include alcohol alkoxylates phenol 5 alkoxylates, poly (oly alky lene)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 amines, fatty acid amide alkoxylates, fatty amines, quaternary amines, alkyloxazolines, alkenyloxazolines, imidazolines, alkylsulphonates, alkylarylsulphonates, alkylsulphosuccinates, alkylarylsulpnonates, alkylsulphosuccinates, alkylphosphates, alkenylphosphates,
  • the emulsifier of the emulsion comprises up to 5 % w/w of the emulsion. Higher proportions of the emulsifying agent may be used and may serve as supplemental fuel for the composition but in general it is not necessary to add more than 5 % w/w of emulsifying agent to achieve the desired effect.
  • Stable emulsions can be formed using relatively low levels of emulsifier and for reasons of economy it is preferable to keep the amount of emulsifying agent used to the minimum required to form the emulsion.
  • the preferred level of emulsifying agent used is in the range of from 0.1 to 3.0 % w/w of the water-in-oil emulsion.
  • secondary fuels may be incorporated into the emulsion in addition to the water immiscible organic fuel phase.
  • examples of such 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.
  • examples of such 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 sulphur, aluminium, urea 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 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 urea and amines such as methylamine.
  • the optional secondary fuel component of the composition of the present invention comprises from 0 to 30 % w/w of the total composition.
  • the water-in-oil emulsion composition may be prepared by a number of different methods.
  • One preferred method of manufacture includes: dissolving said oxygen releasing salts in water at a temperature above the crystallization point of the salt solution, preferably at a temperature in the range from 20 to 110 °C to give an aqueous salt solution; combining an aqueous salt solution, a water immiscible organic phase, and an emulsifier with rapid mixing to form a water-in-oil emulsion; and mixing until the emulsion is uniform.
  • the emulsion may also be incorporated into the emulsion other substances or mixtures of substances which are oxygen releasing salts or which are themselves suitable as explosive materials.
  • the emulsion may be mixed with prilled or particulate ammonium nitrate or ammonium nitrate/fuel oil mixtures.
  • non-associative thickening agents or chemical thickening 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 associative thickner increases the zero-shear viscosity by the non-soluble moieties of different associative thickner molecules associating together in the solvent, giving localised points of linkage between the soluble backbones of the molecules.
  • These associations are believed to give rise to an extensive three-dimensional structure of the associative thickener molecules in the solvent, the 3-dimensional structure acting to hinder solvent flow and therefore raise the emulsion viscosity.
  • the points of association are not permanent as they are only formed through relatively weak physical forces. Under the influence of applied shearing force, the points of association can be disrupted and the emulsion can flow normally. However the disruption only subsists while the shearing force is applied. If the shearing force is removed the points of association can rapidly be re-formed, re-establishing the 3-dimensional network.
  • the driving force for formation of the associations has a primarily thermodynamic basis.
  • the associative thickener constitutes a hydrophobicaily modified water-soluble polymer
  • the driving force for the associations is a large entropic increase (accompanied by a small enthalpic change) arising from the breakdown of the ordered structure of water molecules around the hydrophobes as they are removed from solution. This aggregation is therefore favoured due to the large decrease in the free energy resulting from a net decrease in the number of hydrophobe-water contacts.
  • the aggregation in aqueous solution of the hydrophobic groups on the polymer chains thus results in intermolecular associations, forming physical linkages between the chains. These linkages produce polymolecular structures with a high hydrodynamic volume and consequently, enhanced viscosification properties.
  • an associative thickener into an emulsion for use in an emulsion explosive composition provides a marked viscosifying effect, especially for emulsions having a dispersed phase with a small average droplet size.
  • the apparent viscosity of such an emulsion may display an increase of 150% or more.
  • the apparent viscosity when measured as a function of shear rate, demonstrated an apparent viscosity far greater than for emulsions unmodified by associative thickeners over relatively low shear rates.
  • the apparent viscosity of the emulsions comprising an associative thickener coincided with the apparent viscosities of an unmodified emulsion at higher shear rates.
  • emulsions comprising associative thickeners may be pumped, augured or otherwise transported as readily as standard emulsions yet may exhibit apparent viscosities far greater than for standard emulsions at low or zero shear such as when loaded in a bore hole.
  • the associative thickener When the associative thickener is incorporated into the dispersed phase of the emulsion, the droplets have been observed to be significantly harder to deform although at relatively high shear rates, the resistance to deformation is overcome.
  • the associative thickener is incorporated into the dispersed aqueous phase of a water-in-oil emulsion.
  • the emulsions incorporating the associative thickener demonstrate less rheopectic behaviour than would be expected with unmodified emulsions.
  • a copolymer of acrylamide and N-(4-t-butylphenyl) acrylamide was used as an associative thickener.
  • the associative thickener was synthesised using an aqueous micellar free radical polymerisation route.
  • the resultant copolymer contained no more than 1 % mol. of the hydrophobic monomer.
  • the effect of ammonium nitrate and sodium chloride on the solution properties of the associative thickener were investigated.
  • concentration of associative thickener was 0.50 % w/w with ammonium nitrate levels ranging from 10 % w/w to 60 % w/w.
  • the shear rate range was varied from 0.00186 S “1 to 1470 S "1 with a constant delay time of 5 sec and an integration time of 5 sec using a Bohlin VOR rheometer. The samples were examined as a function of shear rate and also as a function of shear time at a constant rate.
  • Figure 1 shows the apparent viscosity at 25 °C as a function of shear rate (sweep up and down) for 0.50 % w/w aqueous associative thickener solutions containing various levels of ammonium nitrate.
  • the arrows indicate the direction of sweep.
  • Figure 2 shows the apparent viscosity at 25 °C at a constant shear rate of 0.583 S "1 as a function of shear time for 0.50 % w/w aqueous associative thickener solutions containing various levels of ammonium nitrate.
  • Figure 3 shows the apparent viscosity at 25 °C at a shear rate of 0.583 S "1 as a function of the ammonium nitrate concentration for 0.50 % w/w aqueous associative thickener solutions.
  • the effect of sodium chloride on the solution properties of the associative thickener were investigated.
  • concentration of associative thickener of 0.50% w/w and 1.50% w/w with sodium chloride levels ranging from 5 % w/w to 25 % w/w.
  • the shear rate range was varied from 0.00186 S “1 to 1470 S "1 with a constant delay time of 5 sec and an integration time of 5 sec using a Bohlin VOR rheometer.
  • the samples were examined as a function of shear rate and also as a function of shear time at a constant rate.
  • Figure 4 shows the apparent viscosity at 25 °C as a function of shear rate (sweep up and down) for 0.50 % w/w aqueous associative thickener solutions containing various levels of sodium chloride.
  • the arrows indicate the direction of sweep.
  • Figure 5 shows the apparent viscosity at 25 °C at a constant shear rate of 0.583 1/s as a function of shear time for 0.50 % w/w aqueous associative thickener solutions containing various levels of sodium chloride.
  • Figure 6 shows the apparent viscosity at 25 °C at a shear rate of 0.583 S "1 as a function of the sodium chloride concentration for 0.50 % w/w aqueous associative thickener solutions.
  • the emulsifier was an uncondensed amide form of the reaction product of an alkanolamine and poly(isobutylene)succinic anhydride (PiBSA).
  • the emulsion was prepared by dissolving ammonium nitrate in the water at elevated temperature (98 °C) then adjusting the pH of the oxidiser solution so formed to 4.2.
  • the fuel phase was then prepared by mixing the emulsifier with the hydrocarbon oil.
  • the oxidiser phase was then added in a slow stream to the fuel phase at 98 °C with rapid stirring to form a homogeneous water-in-oil emulsion.
  • Emulsion of this formulation was suitable for use in forming an explosives emulsion.
  • a first portion of the water-in-oil emulsion was set aside as a control sample.
  • the associative thickener of Example 1 was incorporated at a concentration of 1.5 % w/w into the aqueous phase of a second test sample of the emulsion.
  • test sample A comparison of the test sample with the control sample showed that the associative thickener enhanced the zero shear viscosity of the test sample. Furthermore the test sample exhibited shear thinning as a function of applied shear rate, the test sample having the same viscosities as the control sample at higher shear rates. Upon relaxation of the shear force, the test sample immediately regained high zero shear viscosity .
  • the continuous phase (oil phase) for the comparative emulsions was prepared using
  • a Sunbeam Beatermix JM-040 five-speed electronic hand mixer with a whisk-type stirrer was employed in the preparation of the emulsions.
  • the speed setting used was dependent on the droplet size required for the emulsion.
  • the highly concentrated emulsions were prepared as follows: 94g of aqueous phase was slowly added to 6g of constantly mixing oil phase over a 5 minute time period.
  • Emulsification and refinement was then continued for a further specified period of time, with the emulsion vessel being moved in a circular motion during this time to ensure complete dispersion of the aqueous phase in the oil phase.
  • Emulsions of approximately 6 ⁇ m average droplet size were prepared using the highest speed setting (Speed 5) and a refinement time of 5 minutes.
  • An emulsion of approximately 12 ⁇ m average droplet size was prepared using the lowest speed setting (Speed 1) and a refinement time of 2.5 minutes.
  • An emulsion of approximately 18 ⁇ m average droplet size was prepared using the lowest speed setting (Speed 1) and a refinement time of 45 seconds.
  • Emulsion S6 Emulsion S6, Emulsion S12 and Emulsion S 18 respectively.
  • the acrylamide/N-(4-butylphenyl)acrylamide copolymer used to thicken the internal phase of the emulsions was obtained from a free-radical copolymerisation in an aqueous micellar medium.
  • This polymerisation technique produces a copolymer with an essentially block-like structure, with hydrophobic regions being dispersed along the hydrophilic polymer backbone. It is believed that the copolymer is polydisperse in nature, with polymer chain compositions ranging from hydrophobe rich to pure acrylamide.
  • the copolymer/ salt solution was prepared by dissolving 1.5% w/w of copolymer in a 25% w/w sodium chloride solution using gentle magnetic stirring at ambient temperature.
  • the thickened emulsions were prepared using essentially the same method as for standard emulsions. However, due to the increased viscosity of the dispersed phase, small amounts of the copolymer/salt solution were continuously added to the oil phase in the emulsion vessel until all of the dispersed phase had been added. This occurred over a 5 minute period.
  • Thickened emulsions of approximately 6 ⁇ m, 12 ⁇ m and 18 ⁇ m were prepared using refinement times of 40 minutes, 10 minutes and 4 minutes 45 seconds respectively. They will hereon be referred to as Emulsion T6, Emulsion T12 and Emulsion T18 respectively.
  • the measuring system utilised in all measurements was a Bohlin VOR rheometer with a stainless steel concentric cylinder (C14) geometry consisting of a cup of diameter 15.4 mm and a bob of diameter 14.0 mm.
  • the base of the bob was conical with cone angle 150°, the purpose of which was to minimise any end effects on the flow of the sample.
  • the 86.6 g.cm torsion bar was used for all shear time, shear rate sweep and flow/relaxation measurements, together with the oscillatory measurements of Emulsion T6.
  • the oscillatory measurements on the remaining emulsions employed the 18 g.cm torsion bar. Each was selected to ensure maximum sensitivity.
  • the available method of measurement enabled the shearing of the emulsion sample at each particular shear rate for a specified time, prior to the measurement at that shear rate being taken. This initial period of pre-shear is known as the delay time. Taking the measurement at a particular shear rate involved averaging a number of instantaneous torque readings taken over a specified time period to produce the reported data value. This period of measurement is known as the integration time.
  • the torque signal was zeroed manually prior to the start of each measurement.
  • shear time The apparent viscosity as a function of time was recorded in what will be referred to as "shear time” measurements.
  • shear time The apparent viscosity as a function of time was recorded in what will be referred to as "shear time” measurements.
  • the sample was continuously sheared at a single fixed shear rate and data collected at fixed intervals.
  • the initial shear time measurement on each emulsion was performed within 15 minutes of manufacture and the apparent viscosity was monitored over a 5000 second time period. This measurement gave an indication of the structure formation and relaxation of the emulsions immediately after manufacture.
  • the apparent viscosity of each emulsion was then monitored over time (days), with one shear time measurement being taken at the beginning of the day of interest, with the duration of the measurement being 500 seconds.
  • Shear rate sweeps were performed over the full shear rate range of 0.00186 S “1 to 1470 S “1 . Two types of shear rate sweep measurements were conducted.
  • Emulsion S6 only "Down-Up” experiments, in which the shear rate was sequentially decreased then increased in a step-wise fashion, were also conducted, enabling the comparison of Up-Down and Down-Up measurements. These measurements were conducted over five shear rate ranges, namely 0.00186 S “1 to 0.116 S “1 , 1.16 S “ ⁇ 11.6 S 1 , 116 S “1 and 1160 S “1 respectively. These measurements gave an indication of the shear rate range over which most destructuration of the emulsion occurs.
  • the second type of shear rate sweep measurement which will be referred to as a "shear rate sweep under continuous measurement"
  • These measurements were conducted in each of the three rheometer gears, namely Gear 0 (18.2 S 1 to 1460 S 1 ), Gear 1 (0.182 S 1 to 14.6 S “1 ) and Gear 2 (0.00182 S “1 to 0.146 S “1 ).
  • the selected sweep time was 600 seconds, with the entire measurement involving an increase in shear rate over 600 seconds followed by a decrease in shear rate over a further 600 seconds (1200 seconds in total).
  • Row/relaxation, or stress relaxation, experiments involve shearing the emulsion at a specified shear rate for a specified period of time, thus applying an accumulated strain to the emulsion, and monitoring the decay of the torque on the bob for a specified period of time following the cessation of shear. The measurement gave information about the recovery of the emulsion after shear.
  • Emulsion S6 The flow/relaxation behaviour of Emulsion S6 was studied most thoroughly. For this emulsion, shear rates of 0.116 S ⁇ 0.581 S 1 , 1.16 S 1 , 4.61 S 1 , 11.6 S ⁇ 46 S ' ⁇ 116 S 1 461 S “1 and 1160 S “1 were employed together with shear times of 30 seconds and 600 seconds. The relaxation was monitored for 100 seconds. The relaxation curves were then normalised by dividing all shear stresses in each curve by the value of the first shear stress recorded, allowing further comparison of relaxation behaviour.
  • shear rates of 0.116 S ' ⁇ 1.16 S “1 , 11.6 S “1 and 116 S “1 with shear times of 30 seconds and 600 seconds were used. The relaxation was monitored over a 200 second time period and normalised curves were also produced.
  • the first known as an "Oscillation Test", measured various dynamic variables, including G' (storage modulus), G" (loss modulus) and phase angle ⁇ , over a frequency range of 0.004 Hz to 20Hz. Amplitudes of 10%, 20%, 30% and 40%, corresponding to strains of 0.0206, 0.0412, 0.0618 and 0.0823 respectively, were employed for these measurements. Oscillation of the sample occurred only during measurement at each frequency.
  • strain Sweep The second type of measurement, known as a "Strain Sweep", measured the dynamic variables over a range of strains, namely 0.000206 to 0.206 (0.1 % to 100% amplitude). Frequencies of 0.1 Hz 1 Hz 10 Hz and 20 Hz were employed.
  • Droplet sizing of each emulsion was performed using a Malvern Masterizer and a magnetically stirred cell.
  • the general procedure for analysing an emulsion was as follows. The cell was filled with paraffin oil and a background reading taken. A small sample of emulsion was collected on the end of a Pasteur pipette. The magnetic stirrer was then switched on and emulsion added to the paraffin oil by shaking the pipette in the oil until a sufficient concentration had been obtained. After allowing the sample to stir for a short time (around 10 seconds), the stirrer was switched off and a measurement immediately taken.
  • Emulsions S6 and T6 are very closely matched. Thus any differences in rheological behaviour as discussed below may be attributed predominantly to the incorporation of the associative thickener into the dispersed phase droplets.
  • Emulsions S12 and T12 while possessing similar average droplet sizes, it can be seen in Figure 7 that the droplet size distributions of these two emulsions are significantly different, with the thickened emulsion displaying a wider distribution.
  • Emulsions S18 and T18 exhibit similar average droplet size but significantly different droplet size distributions.
  • any observed differences in the rheological behaviour of the corresponding pairs of standard and thickened emulsions may be partly due to this difference in droplet size distribution, in addition to the incorporation of associative thickener into the internal phase droplets.
  • Table 1 clearly shows that incorporation of associative thickener into the internal phase droplets of an emulsion has a marked viscosifying effect, especially for the emulsions of approximately 6 ⁇ m average droplet size.
  • the standard and thickened emulsions display similar behaviour under steady shear flow, with both sets of emulsions exhibiting shear thinning and thixotropic behaviour in their apparent viscosities as a function of shear rate.
  • the emulsions of larger average droplet size, both thickened and unthickened display some rheopectic behaviour, especially when long delay times are employed.
  • Emulsions S6 and T6 as a function of shear rate are given in Figure 8.
  • the displayed curves were obtained using a 60 second delay time and 5 second integration time and is representative of the curves produced using all five delay times for each of the three emulsion droplet sizes.
  • the figure clearly illustrates that the sweep up curve for the thickened emulsion lies above that of the standard emulsion for the majority of the shear rate sweep up, with the curves merging at the highest shear rates. This behaviour is believed to be attributed to the relative deformability of the droplets of the standard and thickened emulsions.
  • the standard and thickened emulsions generally show very similar behaviour under dynamic shear flow. Both sets of emulsions display significant Maxwellian behaviour, with consideration of tan ⁇ as a function of frequency at several amplitudes revealing that the transition from flow to oscillatory behaviour for the emulsions occurs at higher frequency for increasing amplitude.
  • Tan ⁇ as a function of frequency at 30% amplitude is shown in Figure 10 for all emulsions prepared in this study. It can be clearly seen from the figure that the frequency at which the transition from predominantly viscous to primarily elastic behaviour occurs is significantly decreased for the thickened relative to the corresponding standard emulsions. This was the case for all amplitudes studied. In fact, for the thickened emulsions, the value of tan ⁇ remains below unity over the entire frequency range studied in many cases, that is, the thickened emulsions display predominantly elastic behaviour over the whole frequency range.
  • Tan ⁇ as a function of strain at a frequency of 0.1 Hz is shown in Figure 11 for Emulsions S6, S12, T6 and T12. It can be clearly seen from the figure that the aforementioned transition point occurs at higher strains for the thickened relative to the standard emulsions. This appears to be the general trend for all pairs of corresponding emulsions at all frequencies studied. These observations again imply that the thickened emulsions show increased elastic behaviour relative to that of the standard emulsions.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Colloid Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Detergent Compositions (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

Il a été observé qu'il était possible d'utiliser des épaississants dans des émulsions prévues pour des compositions explosives. Ces épaississants assurent des changements rapides et réversibles de la viscosité des émulsions. L'utilisation d'épaississants permet d'obtenir des émulsions explosives présentant les caractéristiques requises de (1) réduction significative de la viscosité au cours du pompage et (2) rétablissement d'une viscosité relativement élevée une fois le pompage terminé sans endommager les composants de l'émulsion. Il semblerait que l'utilisation d'épaississants permette d'obtenir un réseau de liaisons physiques dans l'émulsion, qui peut être rompu de manière réversible.
PCT/AU1998/000353 1997-05-15 1998-05-15 Modification et modificateurs de rheologie WO1998051645A1 (fr)

Priority Applications (10)

Application Number Priority Date Filing Date Title
DE69827498T DE69827498T2 (de) 1997-05-15 1998-05-15 Rheologieänderung und rheologiemodifiziermittel
NZ500909A NZ500909A (en) 1997-05-15 1998-05-15 Explosive compositions using associate thickeners with high viscosity (block co-polymers derived from monomers such as propylene glycol)
BR9809801-2A BR9809801A (pt) 1997-05-15 1998-05-15 Emulsão, composição de explosivo em emulsão, explosivo em emulsão, e, processo de fabricação de uma composição de explosivo em emulsão
AT98920397T ATE282015T1 (de) 1997-05-15 1998-05-15 Rheologieänderung und rheologiemodifiziermittel
EP98920397A EP1001917B1 (fr) 1997-05-15 1998-05-15 Modification et modificateurs de rheologie
CA2289749A CA2289749C (fr) 1997-05-15 1998-05-15 Modification et modificateurs de rheologie
APAP/P/1999/001706A AP9901706A0 (en) 1997-05-15 1998-05-15 Rheology modification.
AU73259/98A AU751545B2 (en) 1997-05-15 1998-05-15 Rheology modification and modifiers
JP54861998A JP2001524065A (ja) 1997-05-15 1998-05-15 レオロジー変性および変性剤
NO995560A NO995560L (no) 1997-05-15 1999-11-12 Reologimodifisering og modifiseringsmidler

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPO6792A AUPO679297A0 (en) 1997-05-15 1997-05-15 Rheology modification and modifiers
AUPO6792 1997-05-15

Publications (1)

Publication Number Publication Date
WO1998051645A1 true WO1998051645A1 (fr) 1998-11-19

Family

ID=3801083

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU1998/000353 WO1998051645A1 (fr) 1997-05-15 1998-05-15 Modification et modificateurs de rheologie

Country Status (14)

Country Link
EP (1) EP1001917B1 (fr)
JP (1) JP2001524065A (fr)
KR (1) KR20010012599A (fr)
CN (1) CN1255911A (fr)
AP (1) AP9901706A0 (fr)
AT (1) ATE282015T1 (fr)
AU (1) AUPO679297A0 (fr)
BR (1) BR9809801A (fr)
CA (1) CA2289749C (fr)
DE (1) DE69827498T2 (fr)
NO (1) NO995560L (fr)
NZ (1) NZ500909A (fr)
WO (1) WO1998051645A1 (fr)
ZA (1) ZA984130B (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002028804A1 (fr) * 2000-10-04 2002-04-11 Orica Explosives Technology Pty Ltd Explosif a emulsion
WO2003027046A2 (fr) * 2000-11-02 2003-04-03 The Lubrizol Corporation Composition d'emulsion eau dans huile energetique stabilisee
WO2016128382A1 (fr) * 2015-02-10 2016-08-18 Maxamcorp Holding, S.L. Suspension explosive à base d'eau

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104557348B (zh) * 2015-02-05 2017-04-19 内蒙古鄂托克旗盛安九二九化工有限责任公司 一种含水铵油炸药及其制备工艺
WO2017103635A1 (fr) * 2015-12-16 2017-06-22 Rhodia Poliamida E Especialidades Ltda Système émulsifiant pour des émulsions explosives
US11953306B2 (en) * 2018-03-16 2024-04-09 Dyno Nobel Asia Pacific Pty Limited External homogenization systems and methods related thereto
CN110511311A (zh) * 2019-06-25 2019-11-29 西安理工大学 用于炸药改性的高分子材料及其制备方法和炸药改性方法
KR102121045B1 (ko) * 2019-11-07 2020-06-09 주식회사 석성발파건설 전단농화유체를 이용한 발파 공법 및 이를 위한 전단농화유체를 이용한 장약공 밀장전용 패커
CN111943790A (zh) * 2020-07-31 2020-11-17 宜兴市阳生化工有限公司 一种新型地下矿用胶状乳化炸药

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3919016A (en) * 1974-06-02 1975-11-11 Nalco Chemical Co Thickening of solvent explosives systems
GB2129415A (en) * 1982-09-15 1984-05-16 Nitro Nobel Ab Emulsion explosive
US4453989A (en) * 1982-04-05 1984-06-12 Atlas Powder Company Solid sensitizers for water-in-oil emulsion explosives
US4705582A (en) * 1986-11-03 1987-11-10 Aubert Stephen A Desensitized explosive composition
GB2199575A (en) * 1986-12-12 1988-07-13 Iel Ltd Improved water-in-oil emulsion explosive compositions
EP0276934A2 (fr) * 1987-01-30 1988-08-03 Ici Australia Operations Proprietary Limited Composition explosive
EP0297740A2 (fr) * 1987-06-29 1989-01-04 Aeci Limited Explosif
CA2011419A1 (fr) * 1989-03-04 1990-09-04 Zhongji Peng Emulsion explosive et procede de fabrication
AU5237590A (en) * 1989-03-31 1990-10-04 Norsk Hydro A.S Explosive comprising a mixture of a nitrate-oil explosive and a water-in-oil emulsion explosive, and a method for its manufacture
AU2121392A (en) * 1991-08-21 1993-02-25 Orica Explosives Technology Pty Ltd Vegetable oil emulsion explosive
WO1996041781A1 (fr) * 1995-06-09 1996-12-27 The Burwood Corporation Limited Composition emulsifiante contenant un emulsifiant et un stabilisant polymerique soluble dans l'huile

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1523958A (en) * 1977-06-21 1978-09-06 Secr Defence Slurry explosives
GB2129414B (en) * 1982-10-21 1986-05-29 Indian Explosives Ltd Improved water-in-oil emulsion explosive and a method of preparing it
NZ206243A (en) * 1982-12-03 1987-03-31 Dulux Australia Ltd Non-ionic surfactants based on polyalkylene oxides having at least one double bond
EP0352396B1 (fr) * 1988-07-27 1992-12-16 Union Espanola De Explosivos S.A. Procédé de préparation de compositions explosives du type émulsion

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3919016A (en) * 1974-06-02 1975-11-11 Nalco Chemical Co Thickening of solvent explosives systems
US4453989A (en) * 1982-04-05 1984-06-12 Atlas Powder Company Solid sensitizers for water-in-oil emulsion explosives
GB2129415A (en) * 1982-09-15 1984-05-16 Nitro Nobel Ab Emulsion explosive
US4705582A (en) * 1986-11-03 1987-11-10 Aubert Stephen A Desensitized explosive composition
GB2199575A (en) * 1986-12-12 1988-07-13 Iel Ltd Improved water-in-oil emulsion explosive compositions
EP0276934A2 (fr) * 1987-01-30 1988-08-03 Ici Australia Operations Proprietary Limited Composition explosive
EP0297740A2 (fr) * 1987-06-29 1989-01-04 Aeci Limited Explosif
CA2011419A1 (fr) * 1989-03-04 1990-09-04 Zhongji Peng Emulsion explosive et procede de fabrication
AU5237590A (en) * 1989-03-31 1990-10-04 Norsk Hydro A.S Explosive comprising a mixture of a nitrate-oil explosive and a water-in-oil emulsion explosive, and a method for its manufacture
AU2121392A (en) * 1991-08-21 1993-02-25 Orica Explosives Technology Pty Ltd Vegetable oil emulsion explosive
WO1996041781A1 (fr) * 1995-06-09 1996-12-27 The Burwood Corporation Limited Composition emulsifiante contenant un emulsifiant et un stabilisant polymerique soluble dans l'huile

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DERWENT ABSTRACT, Accession No. 82-44682E/22, Class A95, K04; & JP,A,57 067 096 (NIPPON KAYAKU KK) 23 April 1982. *
DERWENT ABSTRACT, Accession No. 94-342417/43, Class A95, K04, (A17); & CA,A,2 107 966 (ICI EXPLOSIVES USA INC) 25 June 1994. *
DERWENT ABSTRACT, Accession No. 97-228625/21, Class K04; & EP,A,769 483 (DYNAMIT NOBEL GMBH EXPLOSIVSTOFF UND SYSTEMTECHNIK) 23 April 1997. *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002028804A1 (fr) * 2000-10-04 2002-04-11 Orica Explosives Technology Pty Ltd Explosif a emulsion
US6942744B2 (en) 2000-10-04 2005-09-13 Orica Explosives Technology Pty Ltd. Emulsion explosive
WO2003027046A2 (fr) * 2000-11-02 2003-04-03 The Lubrizol Corporation Composition d'emulsion eau dans huile energetique stabilisee
WO2003027046A3 (fr) * 2000-11-02 2003-11-06 Lubrizol Corp Composition d'emulsion eau dans huile energetique stabilisee
US6929707B2 (en) 2000-11-02 2005-08-16 The Lubrizol Corporation Stabilized energetic water-in-oil emulsion composition
WO2016128382A1 (fr) * 2015-02-10 2016-08-18 Maxamcorp Holding, S.L. Suspension explosive à base d'eau
US10793485B2 (en) 2015-02-10 2020-10-06 Maxamcorp Holding, S.L. Water-based explosive suspension

Also Published As

Publication number Publication date
CA2289749A1 (fr) 1998-11-19
EP1001917B1 (fr) 2004-11-10
ATE282015T1 (de) 2004-11-15
BR9809801A (pt) 2000-06-27
EP1001917A1 (fr) 2000-05-24
ZA984130B (en) 1998-11-20
CA2289749C (fr) 2011-09-27
NZ500909A (en) 2001-06-29
DE69827498T2 (de) 2005-11-10
NO995560L (no) 2000-01-11
DE69827498D1 (de) 2004-12-16
KR20010012599A (ko) 2001-02-15
CN1255911A (zh) 2000-06-07
NO995560D0 (no) 1999-11-12
EP1001917A4 (fr) 2000-05-24
JP2001524065A (ja) 2001-11-27
AUPO679297A0 (en) 1997-06-05
AP9901706A0 (en) 1999-12-31

Similar Documents

Publication Publication Date Title
US4736683A (en) Dry ammonium nitrate blasting agents
US6165297A (en) Process and apparatus for the manufacture of emulsion explosive compositions
EP1001917B1 (fr) Modification et modificateurs de rheologie
CA1330395C (fr) Polymere contenant une composition explosive soluble dans la phase organique, comportant des groupes fonctionnels associatifs
JP2942265B2 (ja) フェノール系乳化剤誘導体を含有するエマルジョン爆薬
US5507892A (en) Explosive composition suitable for cartridging in paper and its method of manufacture
AU2016217971B2 (en) Water-based explosive suspension
AU751545B2 (en) Rheology modification and modifiers
GB2224501A (en) Aromatic hydrocarbon-based emulsion explosive composition.
MXPA99010502A (en) Rheology modification and modifiers
AU2009329835B2 (en) Amine reacted alpha, beta-unsaturated carbonyl compound thickened explosive emulsions
WO1991001800A1 (fr) Emulsion dont la rheologie est regulee
WO2002028804A1 (fr) Explosif a emulsion
US6702909B2 (en) High energy explosive containing cast particles
CA1081965A (fr) Composition d'explosif a consistance mousseuse et epaisse, a stabilite amelioree
AU605625B2 (en) Method for preparing explosive composition
JP2001172096A (ja) 固形エマルション爆薬組成物及びその製造方法
JPH0393690A (ja) 油中水滴型エマルジョン爆薬
JP2001221600A (ja) 爆薬装填方法
AU1133897A (en) Process & apparatus for the manufacture of emulsion explosive compositions
AU2001291515A1 (en) Emulsion explosive

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 98805084.6

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE GH GM GW HU ID IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 500909

Country of ref document: NZ

WWE Wipo information: entry into national phase

Ref document number: 73259/98

Country of ref document: AU

ENP Entry into the national phase

Ref document number: 2289749

Country of ref document: CA

Ref document number: 2289749

Country of ref document: CA

Kind code of ref document: A

Ref document number: 1998 548619

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 1019997010558

Country of ref document: KR

Ref document number: PA/a/1999/010502

Country of ref document: MX

Ref document number: 1998920397

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWE Wipo information: entry into national phase

Ref document number: 09423520

Country of ref document: US

WWP Wipo information: published in national office

Ref document number: 1998920397

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1019997010558

Country of ref document: KR

WWG Wipo information: grant in national office

Ref document number: 73259/98

Country of ref document: AU

WWW Wipo information: withdrawn in national office

Ref document number: 1019997010558

Country of ref document: KR

WWG Wipo information: grant in national office

Ref document number: 1998920397

Country of ref document: EP