EP0198849A1 - Compositions de ciment mousse pour remblayage de cavites - Google Patents

Compositions de ciment mousse pour remblayage de cavites

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Publication number
EP0198849A1
EP0198849A1 EP85904834A EP85904834A EP0198849A1 EP 0198849 A1 EP0198849 A1 EP 0198849A1 EP 85904834 A EP85904834 A EP 85904834A EP 85904834 A EP85904834 A EP 85904834A EP 0198849 A1 EP0198849 A1 EP 0198849A1
Authority
EP
European Patent Office
Prior art keywords
clinker
cement
composition
weight
composition according
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.)
Withdrawn
Application number
EP85904834A
Other languages
German (de)
English (en)
Inventor
Gavin Crammond Gartshore
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Blue Circle Industries PLC
Original Assignee
Blue Circle Industries PLC
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 Blue Circle Industries PLC filed Critical Blue Circle Industries PLC
Publication of EP0198849A1 publication Critical patent/EP0198849A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/06—Aluminous cements
    • C04B28/065—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates

Definitions

  • This invention relates to compositions suitable for the production of quick-setting, low-density, foamed cements that are flowable materials and that can be pumped into cavities. Such foamed cements are especially useful for filling cavities in underground mines.
  • cavities cavities or porous surfaces
  • the natural presence of fissures, cavities or porous surfaces (herein collectively referred to as cavities) or their formation during the course of mining or drilling due to weaknesses in the strata can often adversely affect the economic recovery of minerals, oil and gas.
  • cavities may present a safety hazard and/or restrict the flow of materials along the access tunnel's.
  • a well cement pumped as a slurry is used to seal the annular space between the walls and the steel casing through which the material being extracted is carried, a significant quantity of cement may be lost to the strata.
  • materials such as expanded perlite, vermiculite, crushed coal or gilsonite (known collectively as loss circulation controllers) are often incorporated in the well cement slurry to help seal the surface and/or fill the cavity.
  • foamed cement which offers the advantages that less material is required to fill a given void or cavity; the weight of the filling medium is not excessive and is less likely to lead to the breakdown of other weak formations; the mixture is easily pumped; and if necessary the filling medium can be readily re- drilled.
  • foamed cements are produced by incorporating additives in the well cement that is being used to fill the annular space. The resultant foamed cementitious mixture is then pumped down the well in a similar way to the normal well cementing operation.
  • One way of producing a foamed cement is to add to the cementitious mix an active metal, such as aluminium or magnesium, which reacts with the cement slurry to generate hydrogen gas in situ.
  • an active metal such as aluminium or magnesium
  • Such a technique, together with the use of chemical inhibitors to control the release of gas, to produce a foamed well cement for sealing zones penetrated while drilling is described in British Patent Specification 2,104,055A.
  • Another way of producing a foamed cement is to add a "foaming agent", typically a surfactant., to the well cement slurry such that any air or gases introduced into the slurry are encapsulated and trapped in it.
  • a foaming agent typically a surfactant.
  • Both methods as described above for producing a foamed cement are particularly suited for use with the Basic Class G and Class H well cements as defined in American Petroleum Institute Specification 10 1982. These cements can be used to prepare a neat cement slurry on the surface for then pumping down to depths up to 8000 feet (2438 m) or they can be mixed with retarders and other additives such that they can be pumped to greater depths.
  • British Patent Specifications 1,387,075 and 1,497,670 disclose a quick setting, early strength cement suitable for use in the process described in British Patent Specification 1,362,954.
  • This cement comprises 7-90%, usually 10-70% and preferably 15-30%, by weight of the hydraulic constituents, of the calcium aluminate phase 12Ca0.7Al 0 3 , together with the other hydraulic phases commonly found in cements the bulk of which are calcium silicates.
  • the cement may also comprise calcium sulfate and small additions of a retarder, such as citric acid, and of an accelerator, such as potassium sulfate.
  • the ratio of the weight - 5 - of calcium aluminate to the weight of calcium sulfate is typically from 3:1 to 1:3 and the weight of the mixture of these components is generally from 10 to 75% of the weight of the Portland cement.
  • the preferred calcium aluminate is Ca0.Al 2 0 3 , which is readily available as High Alumina cement.
  • a typical cement slurry is said to comprise a cement mixture and water mixed in a ratio of 0.5:1 to 2:1 by weight where the cement mixture contains 66.65% ordinary Portland cement, 18.4% High Alumina cement, 14.7% anhydrous calcium sulphate and 0.25% citric acid, whereas a typical clay slurry comprises bentonite and sodium carbonate such that the bentonite is present in an amount of between 0.25% and 10% by weight of the water and the sodium carbonate is present in an amount equivalent to between 1% and 10% by weight of the cement in the cement slurry.
  • the final mix typically consists of the cement mixture, bentonite and water substantially in the proportions of 14%, 1% and 85% by volume.
  • a method of constructing packs similar to those described in British Patent Specification 2,058,037A is disclosed in British Patent Specification 2,123,808A, in which a first slurry comprising High Alumina Cement is mixed with a second slurry comprising beta-anhydrite and calcium oxide and/or calcium hydroxide, the second slurry usually also containing a clay, typically bentonite, and an accelerator of High Alumina cement, such as lithium carbonate.
  • the resultant cement composition will usually contain High Alumina cement and beta- anhydrite in a ratio of from 3:7 to 4:1 by weight, whereas the calcium oxide and/or calcium hydroxide added will preferably range from 2 to 8.5%, typically 3.5 to 5%, by weight.
  • compositions of the bentonite mix will be such that when mixed with the cementitious mix the quantity of bentonite will usually be between 10 and 25% by weight of the beta-anhydrite, whereas the quantity of lithium carbonate will usually be up to 1%, typically between 0.05 and 0.2%, by weight of the High Alumina cement.
  • Such quick-setting cementitious compositions as disclosed in British Patent Specifications 1,387,025; 1,497,670; 2,058,037A and 2,123,808A would be ideally suited for use with a foaming agent to produce a light ⁇ weight foamed cement that could be used to fill cavities in underground mining. Indeed, the use of compositions as disclosed in British Patent Specification 2,058,037A together with a foaming agent for such "purposes is already being practised in some collieries in the United Kingdom.
  • an object .of the present invention is to provide a means of foaming cementitious compositions in order that they can be used to form a durable* light weight filling medium which can be used for filling cavities in underground mining.
  • a further object of the present invention is to provide a means of foaming cementitious compositions which is comparatively cheap, which produces a stable foam even with a quick-setting cement, which can produce a foam with a good structure (especially with discrete, uniformly sized gas bubbles) and which permits the production of a filling medium that has good properties even in a wet environment.
  • the present invention provides a composition suitable for the production of a foamed cement, said composition comprising (a) a ground, mineral clinker selected from (i) hydraulic cement clinkers, (ii) potentially hydraulic mineral clinkers and (iii) mixtures thereof, (b) calcium sulfate, (c) an air-entraining agent and (d) a stabilising agent.
  • the composition of this invention comprises (a) from 20 to 99% of the mineral clinker, in particular 40 to 99% (especially when a mixture (iii) is employed) , and typically 65 to 99% of a cement clinker (i) or 40-60% of a mineral clinker (ii), (b) from 1 to 76%, typically from 1 to 20%, of calcium sulfate, (c) from 0.02 to 1%, typically from 0.05 to 0.1%, of air-entraining agent and (d) from 0.05 to 3%, typically from 0.1 to 2%, of stabilising agent, the stated amounts of components (a)- (d) being relative to the total composition on a dry weight basis.
  • the composition may also contain one or more addition- al components, for example extenders, clays and setting accelerators.
  • a setting retarder e.g. citric acid
  • the compositions of the present invention will be made up with water.
  • the resultant aqueous compositions are quick-setting, flowable and capable of being formed into foams that have a stable structure of discrete, uniformly sized bubbles and that are suitable for use as low-density filling media.
  • the present invention also provides a method of forming a foamed cement, characterised in that a composition according to this invention is mixed with water and a gas is introduced into the aqueous mixture to form a foam.
  • a cavity may be filled by introducing such a foam into the cavity (either by injecting the foam into the cavity or by forming the foam in situ) and - 8 -
  • Component (a) of the cementitious composition of this invention may be High Alumina cement clinker, preferably in the presence of an inorganic salt such as lithium carbonate (which salt will act as a setting accelerator) as disclosed in British Patent Specification 2,123,808A (the teaching of which is incorporated herein by reference).
  • the composition may include calcium oxide and/or calcium hy . droxide, prefer ⁇ ably in an amount to ensure that lime and alumina are present in appro ⁇ priate molecular proportions to form ettringite during hydration.
  • Component (a) may alternatively be a mixture of ordinary Portland cement clinker and High Alumina cement clinker, preferably in the presence of an inorganic salt such as sodium carbonate (which salt will act as a setting accelerator) , as disclosed in British Patent Specification 2,058,037A (the teaching of which is incorporated herein by reference). In preferred embodiments, however, component (a) will comprise a ground clinker that is rich in 12Ca0.7Al p 0 3 (usually abbreviated to C 1 A- 7 ).
  • Such a clinker is described in detail in British Patent Specification 1,387,075 (the teaching of which is incorporated herein by reference) and may be produced by fusing or sintering, generally at a temperature above 1250°C, a mixture of siliceous material (e.g. a kaolinitic clay such as china clay, ball clay or fire clay) , calcareous material (e.g. chalk or limestone) and aluminous material (e.g. bauxite) proportioned to yield a product rich in
  • siliceous material e.g. a kaolinitic clay such as china clay, ball clay or fire clay
  • calcareous material e.g. chalk or limestone
  • aluminous material e.g. bauxite
  • a 7 -rich clinker may be underlimed, an underlimed clinker being one in which the lime limitation factor (LLF) is less than unity, where
  • the said substance effective to increase the basicity of the cement may be a metal oxide, e.g. MgO or FeO, present in the C. p A 7 -rich clinker in solid solution in substitution for CaO in the lattices of major phases.
  • the said substance effective to increase the basicity may be a source of calcium ions, e.g. calcium chloride, calcined lime or calcium hydroxide, added to the cement.
  • the hydraulic clinker constituting component (a) of the present composition may contain a mixture of the C 12 A 7 ⁇ rich clinker with, for example, Portland cement, especially ordinary Portland cement.
  • a cement mixture may be formed conveniently by intergrinding the C. p A 7 -rich clinker and ordinary Portland cement clinker, usually together with a source of sulfate, a small quantity of a retarder known as such, e.g. a sugar, a lignosulfonate or, especially, citric acid, and a small quantity of inorganic salt.
  • Suitable inorganic salts include known accelerators of cement such as halides, nitrites, nitrates, borates, hydroxides, bicarbonates, carbonates and sulfates
  • the calcium sulfate present as component (b) including the alkali metal (e.g. lithium, sodium or potassium), alkaline earth metal (e.g. calcium or magnesium) and aluminium salts.
  • alkali metal e.g. lithium, sodium or potassium
  • alkaline earth metal e.g. calcium or magnesium
  • aluminium salts are alkali metal carbonates, alkali metal sulfates and calcium chloride. Potassium carbonate and, especially, sodium carbonate are particularly preferred.
  • the substance effective to increase the basicity of the cement may be a source of calcium ions provided in the form of uncombined lime in the Portland cement clinker.
  • component (a) may be selected from potentially hydraulic mineral clinkers, that is to say clinkers that require the presence of one or more activating agents before they will exhibit a significant hydraulic activity.
  • Preferred clinkers of this type are based upon the mineral phase 4Ca0.3Al 2 0 3 .S0 3 (which may be abbreviated to C ⁇ s) , which is commonly known as Klein's compound, a particularly preferred mineral clinker being one that contains at least 25% by weight of C 4 A 3 s, not more than 1% by weight of free lime, less than 5% by weight of CAont and not more than 10% by weight of C 12 A ? .
  • the ground clinker may be set by mixing it with water in the presence of a source of alkali metal or alkaline earth metal under alkaline conditions.
  • a source of alkali metal or alkaline earth metal under alkaline conditions.
  • Such conditions in use are preferably obtained using calcium oxide and/or calcium hydroxide, it being convenient to incorporate such an activator or activators in the initial dry composition.
  • the mineral clinker (activated, if necessary) should be such that when the composition is made up as a slurry containing water in an amount of 80 to 350% by weight of component (a) the initial setting time of that slurry is preferably 30 minutes or less, typically 15 minutes or less.
  • the amount of calcium sulfate present as component (b) of the present composition is calculated as the anhydrous material.
  • the preferred form of calcium sulfate is the dihydrate form, CaS0 4 .2H 2 0, which can be either natural gypsum or a synthetic gypsum such as the by-product from an acid-producing plant, although if the latter is used account must be taken of the effect that any trace impurities in the synthetic gypsum, such as fluorine or phosphorus, may have on the setting and hydration of the cement.
  • calcium sulfate may be employed; for example, it may be preferred to use beta- anhydrite when High Alumina cement clinker is employed as component (a) in the presence of calcium oxide and/or calcium hydroxide.
  • sulfate may be used in the preparation of the hydraulic cement clinker. Any calcium sulfate introduced in this manner is regarded as part of component (b), rather than component (a), for the purpose of determining the amounts of the components.
  • the air-entraining agent (c) can be, for example, an animal or vegetable fat or oil, a natural wood resin or an alkali metal salt thereof, a sulfated or sulfonated organic compound (usually in the form of an alkali metal or ammonium salt), or an amphoteric surfactant such as an alkyl imidazoline derivative.
  • a sulfated or sulfonated organic compound usually in the form of an alkali metal or ammonium salt
  • an amphoteric surfactant such as an alkyl imidazoline derivative.
  • foaming agents are preferred.
  • anionic surfactants for example the sulfated or sulfonated organic compounds, especially alcohol sulfates, ether sulfates and alkyl benzene sulfonates.
  • the stabilising agent (d) can be, for example, a gelatine, a starch (which term includes starch derivatives) or a cellulose ether.
  • the cellulose ethers are preferred, amongst which may be mentioned hydroxyethyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose and (sodium) carboxymethyl cellulose.
  • the cellulose ethers will usually have a Brookfield viscosity of 1,000 to 10,000- mPa.s, typically 2,500 to 7,500 mPa.s (as measured on a 2% aqueous solution at 25°C).
  • the composition comprise an anionic surfactant selected from sulfated or sulfonated organic compounds as component (c) in combination with a cellulose ether as component (d), the most favoured combination at present being an alcohol sulfate or ethoxy sulfate foaming agent with methyl hydroxy ⁇ ethyl cellulose.
  • anionic surfactant selected from sulfated or sulfonated organic compounds as component (c) in combination with a cellulose ether as component (d)
  • the most favoured combination at present being an alcohol sulfate or ethoxy sulfate foaming agent with methyl hydroxy ⁇ ethyl cellulose.
  • composition of the present invention may optionally contain (e) an extender, for example a granulated blast furnace slag or another latently hydraulic material such as pulverised fuel ash, a natural pozzolana or a synthetically produced pozzolanic material.
  • an extender for example a granulated blast furnace slag or another latently hydraulic material such as pulverised fuel ash, a natural pozzolana or a synthetically produced pozzolanic material.
  • an extender for example a granulated blast furnace slag or another latently hydraulic material such as pulverised fuel ash, a natural pozzolana or a synthetically produced pozzolanic material.
  • the present composition may also contain, if required, (f) a clay, for example a hectorite, benionite, smectite or kaolinite clay, amongst which bentonite (e.g. the calcium form or, especially, sodium-activated bentonite) is preferred. If used, the clay will usually be present in an amount of from 0.5 to 10%, preferably from 4 to 6%, relative to the total composition on a dry weight basis. As indicated above, the composition of the present invention may also contain (g) an inorganic sa t (other than the calcium sulfate component), especially as a setting accelerator for the cement component.
  • a clay for example a hectorite, benionite, smectite or kaolinite clay, amongst which bentonite (e.g. the calcium form or, especially, sodium-activated bentonite) is preferred. If used, the clay will usually be present in an amount of from 0.5 to 10%,
  • the inorganic salt preferably an alkali metal salt, especially a carbonate
  • the inorganic salt will usually be present in an amount of from 2 to 10%, preferably from 4 to 6%, relative to the total composition on a dry weight basis, as dis ⁇ closed in British Patent Application No.8513786 (the teaching of which is incorporated by reference).
  • the cement clinker component is as described in British Patent Specification No.1,387,075, No.1,497,670, No.2,058,037A or No.2,123,808A, then it may be advantageous to adopt the recommendations in the relevant specification with regard to the nature and the amount of the inorganic salt.
  • each of the components (a) to (g) may be constituted by a mixture of suitable compounds, if desired.
  • the composition may comprise (h) calcium oxide, calcium hydroxide or a mixture thereof. It is preferred that these bases, if used, should be present in a total amount not exceeding 20%, relative to the total composition on a dry weight basis.
  • the composition of the present invention will be made up with water and with a gas, usually air, preferably by mixing and pumping in a foam-generating machine which will allow a controlled amount of the gas to be encapsulated in the composition.
  • a typical suitable foam-generating machine consists of a two-speed mono-pump placing machine in which the dry components are fed into a mixing trough with water.
  • the resultant slurry is then pumped to the point of application along a hose into which is sucked the surrounding gas, usually air.
  • the amount of air encapsulated in the foam and thus its resultant density and strength can be adjusted to give the desired results.
  • the water content of the foamed aqueous composition is preferably from 80 to 350% by weight of the clinker component (a).
  • the amount of gas encapsulated in such foamed aqueous compositions may typically be in the range of from 86 to 95% when expressed on a volume basis; as a result, the dry density of the foamed cement when set will typically be in the range of from 150 to 400 kg per cubic metre.
  • the -quick-setting foamed cements of the present invention are ideally suited in coal mines for filling cavities in the coal face area, above roadways, at the heads of roadways, where falls have occurred and for
  • Example 1 A composition comprising 70.66% ordinary Portland cement clinker, 4.14% gypsum, 25% C 12 A 7 -rich clinker, 0.1% of the foaming agent Fenopon CD-128 (an ethoxy sulfate, ammonium salt, from G.A.F. (Great Britain) Ltd.) and 0.1% of the cellulose ether thickening agent Tylose P60002 (an hydroxypropyl methyl cellulose; Brookfield viscosity
  • the resultant cement was mixed at time intervals of 1, 2 and 5 minutes with 80, 90 and 100% by weight of water on the dry mix in a Hobart mixer with whisk at the speed setting 2, made into 100 mm cubes and cured at 20°C and 100% relative humidity.
  • the specimens were tested for comparative strength at 7 days and after breaking were measured for dry density.
  • a composition comprising 55.84% ordinary Portland cement clinker, 3.96% gypsum, 20% C 12 A 7 -rich clinker, 20% pulverised fly ash, 0.1% Fenopon CD-128 and 0.1% Tylose P60002 was prepared and tested in the same way as that in Example 1 to give the following results:
  • a mineral clinker was prepared from a raw feed mix comprising bauxite, limestone and anhydrite, which raw mix was slurried in water and fed to a coal-fired rotary kiln in which it was sintered at 1450°C. A small amount of coal ash was incorporated into the material during sintering.
  • the resultant clinker had the following chemical analysis: Si0 2 5.4%, A1 2 0 3 45.5%, Fe 2 0 3 1.3%, CaO 38.2%, MgO 0.4%, Mn 2 0 3 less than 0.01%, P 2 0 5 0.13%, Ti0 2 2.1% , total S (expressed as S0 3 ) 6.3%, K 2 0 0.23% and loss on ignition 0.1%.
  • composition of the mineral clinker was calculated to be: C 4 A 3 s 48%, CA 15.7%, C 12 A ? 2.5%, CgAS 24.6%, C 4 AF
  • the mineral clinker was mixed with 0.25% citric acid and 0.3% guar gum and was then ground to a specific
  • citric acid 0.1 part citric acid and 50 parts of a mixture consisting of 76.1% synthetic anhydrite, 18.0 parts calcium hydroxide
  • the resultant cement was mixed at time intervals of 0.5, 1 and 3 minutes with, in each case, 150% by weight of water on the dry mix, the mixing and the subsequent testing being - 19 -
  • a cement composition was prepared by mixing 50 parts of the ground mineral clinker described in Example 4 with 50 parts of a mixture of synthetic anhydrite, Hydralime, bentonite, sodium carbonate and lithium carbonate, also as described in Example 4, in the presenceof 0.2 part of Tylose P 60002 and 0.1 part of Arquad 18-50% (a commerically available surfactant based on an alkyl quaternary ammonium chloride).
  • the resultant cement was mixed with 200% by weight of water on the dry mix in the manner described in Example 1.
  • the foam produced was clearly unstable and the cement composition was therefore deemed to be un ⁇ suitable for the industrial production of foamed cement.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

Des compositions appropriées pour la production de ciments mousses comprennent un clinker de ciment hydraulique (par exemple, un mélange de ciment Portland ordinaire avec du ciment alumineux ou un clinker riche en 12CaO-7Al2O3), du sulfate de calcium, un entraîneur d'air ou un agent moussant (spécialement un agent tensio-actif organique anionique sulfaté ou sulfoné) et un agent stabilisateur (spécialement un éther de cellulose). Un clinker minéral potentiellement hydraulique peut être utilisé à la place du clinker de ciment hydraulique, en présence d'un activant, par exemple de l'oxyde et/ou de l'hydroxyde de calcium. La composition peut également comprendre un extendeur (par exemple du laitier de haut-fourneau), une argile (par exemple de la bentonite) et des accélérateurs de la prise, par exemple des sels inorganiques des carbonates de métaux alcalins par exemple). Les compositions peuvent être préparées avec de l'eau et ensuite rendues moussantes par l'introduction d'un gaz, de l'air par exemple, le ciment mousse qui en résulte étant particulièrement utile pour remplir des cavités dans des mines souterraines.
EP85904834A 1984-09-12 1985-09-12 Compositions de ciment mousse pour remblayage de cavites Withdrawn EP0198849A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB848423076A GB8423076D0 (en) 1984-09-12 1984-09-12 Foamed cement compositions
GB8423076 1984-09-12

Publications (1)

Publication Number Publication Date
EP0198849A1 true EP0198849A1 (fr) 1986-10-29

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EP85904834A Withdrawn EP0198849A1 (fr) 1984-09-12 1985-09-12 Compositions de ciment mousse pour remblayage de cavites

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EP (1) EP0198849A1 (fr)
JP (1) JPS62500167A (fr)
AU (1) AU4866985A (fr)
GB (2) GB8423076D0 (fr)
WO (1) WO1986001795A1 (fr)
ZA (1) ZA857000B (fr)

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US10322971B1 (en) 2016-04-21 2019-06-18 MK1 Construction Services Fast-setting flowable fill compositions, and methods of utilizing and producing the same
US10851016B1 (en) 2017-02-28 2020-12-01 J&P Invesco Llc Trona accelerated compositions, and methods of utilizing and producing the same
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US10919807B1 (en) 2018-04-25 2021-02-16 J&P Invesco Llc High-strength flowable fill compositions
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GB8423076D0 (en) 1984-10-17
AU4866985A (en) 1986-04-08
GB2164328A (en) 1986-03-19
ZA857000B (en) 1987-05-27
WO1986001795A1 (fr) 1986-03-27
GB8522618D0 (en) 1985-10-16
GB2164328B (en) 1988-05-25
JPS62500167A (ja) 1987-01-22

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