WO1991002703A1 - Use of copolymers as additives for cement mortar mixtures or for coating of cured or partially cured concrete - Google Patents

Use of copolymers as additives for cement mortar mixtures or for coating of cured or partially cured concrete Download PDF

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Publication number
WO1991002703A1
WO1991002703A1 PCT/NO1990/000131 NO9000131W WO9102703A1 WO 1991002703 A1 WO1991002703 A1 WO 1991002703A1 NO 9000131 W NO9000131 W NO 9000131W WO 9102703 A1 WO9102703 A1 WO 9102703A1
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WIPO (PCT)
Prior art keywords
copolymer
methyl
weight
cement mortar
hydrogen
Prior art date
Application number
PCT/NO1990/000131
Other languages
French (fr)
Inventor
Simon Philip John Dennington
Harald Justnes
Original Assignee
Borregaard Industries Limited
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 Borregaard Industries Limited filed Critical Borregaard Industries Limited
Publication of WO1991002703A1 publication Critical patent/WO1991002703A1/en

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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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2641—Polyacrylates; Polymethacrylates
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/48—Macromolecular compounds
    • C04B41/483—Polyacrylates
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61—Coating or impregnation
    • C04B41/62—Coating or impregnation with organic materials
    • C04B41/63—Macromolecular compounds

Definitions

  • copolymers as additives for cement mortar mixtures or for coating of cured or partially cured concrete.
  • cement-based mortar mixtures have been used for the preparation of construction materials for over 150 years. Such mixtures are in general satisfactory, but for certain applications they have deficiencies which it is desirable to rectify.
  • construction elements fabricated from such cement mortar mixtures are prone to corrosive attack in seawater.
  • polymers to reduce corrosion caused by the chloride in seawater in particular.
  • Another property that it has been found desirable to improve is the cement mortar mixture's fluidity, that is to say, that it should flow smoothly out when e.g. laying floors.
  • the polymers most usually used as concrete additives are largely based on styrene-butadiene or vinyl acetate, although other types have been used.
  • R is hydrogen or methyl
  • R 1 is hydrogen or methyl
  • R 2 is C ⁇ gal yl where the amount of one or two different A-units in the copolymer totals 5-10 weight% and the remainder consists mainly of one or more different B-units.
  • the copolymer is advantageously used in the form of a latex, and as well as being added to cement mortar mixtures it can be applied as a coating to cured or partially cured concrete.
  • Monomer A can be acrylic acid or methacrylic acid, and it is possible to use both of these in the same copolymer.
  • Monomer B comprises various esters of acrylic acid and methacrylic acid, and it is similarly possible to use several different esters in the same copolymer.
  • ester monomers B are those where R 1 is hydrogen or methyl, and R 2 is methyl or n-butyl.
  • An especially suitable acid monomer A is methacrylic acid, while especially suitable ester monomers B are butyl acrylate and methyl methacrylate.
  • Especially suitable copolymers are those where the amount of A monomer, especially methacrylic acid, is 6-8 weight %, and the remainder of the copolymer consists mainly of B monomers.
  • the B monomers are preferably butyl acrylate and methyl methacrylate in the ratio 50:50-70:30, especially 65:35, on a weight basis.
  • the copolymer used can also contain minor amounts, e.g. up to 10 weight%, of other ethylenically-unsaturated monomers, such as styrene.
  • the polymer latex used as an additive to cement mortar mixtures or applied to cured or partially cured concrete has preferentially a solids content of 10-60% weight%, especially 30-60 weight%.
  • a high water content in the latex will allow a corresponding reduction in the amount of water used to make the cement mortar mixture.
  • the amount of polymer latex to be added to a cement mortar mixture is preferably from 2 to 25 weight%, and especially from 5 to 15 weight%, expressed as weight of polymer solids/ weight of cement powder.
  • the test was carried out in the following manner: A steel reinforcing bar was cast inside a cylinder of cement mortar which was partially immersed in seawater with the exposed part of the reinforcing bar above the surface of the water. This reinforcing bar was used as the anode, and a metal electrode immersed in the seawater was used as the cathode. The voltage across the electrodes was 5 volts D.C. In the following tables the results of such tests are given as the number of days before chloride penetration caused the current through the cylinder to increase sharply. Testing was carried out with two different mortars having differing water/cement ratios. The polymer latex used contained 50 weight% of polymer. The quoted additions of polymer are calculated on the basis of dry weight of polymer solids/ weight of cement powder.
  • the polymer latexes used were as follows:
  • Polymer 1 Commercial latex based on the terpolymer vinylacetate/vinyl chloride/ethylene
  • Polymer 2 Commercial latex based on the copolymer vinyl acetate/"versatic" ester
  • Polymer 3 Commercial latex based on styrene/butadiene rubber
  • Polymer 4 50 weight% solids content latex consisting of a copolymer of 7% methacrylic acid, 60.5% butyl acrylate and 32.5% methyl methacrylate by weight according to this invention
  • a polymer latex for use in accordance with this invention was prepared as follows: 2 grams of sodiummetabisulphite dissolved in 4.9 litres of water was heated towards 80 °C in a reactor. When the temperature reached 70 °C a solution of 12.5 grams of potassium persulphate (initiator) in 125 millilitres of water was added to the reactor.
  • a pre-emulsion was prepared from 6.4 litres of water, 350 grams of "Berol 295" (surfactant) , 840 grams of "Disponil AES 60" (surfactant) , 7569 grams of butyl acrylate, 4075 grams of methyl methacrylate and 856 grams of methacrylic acid. 10% of this pre-emulsion was thereafter added to the reactor when the aqueous solution it contained had reached a temperature of 75 °C. When this first portion had reacted, the remainder of the pre-emulsion was added over a period of 2 hours, while the temperature of the reactor was maintained at 80 ⁇ 2 °C.
  • This latex is used either as an additive for cement mortar mixtures or for applying as a coating to cured or partially- cured concrete to reduce the ingress of chloride. It is also suitable as an additive to improve the fluidity and workability of cement mortar-based mixtures.
  • the rheological properties are comprised, among other things, of workability and fluidity.
  • Table III shows the results of adding a polymer latex used according to this invention to a cement mortar compared to an unmodified cement mortar and a polymer-cement mortar containing a commercial styrene-butadiene (SBR) latex.
  • SBR commercial styrene-butadiene
  • the polymer that was used according to this invention contained butyl acrylate (BA) and methyl methacrylate (MMA) in the specified weight ratio, with and without methacrylic acid (MAA) (expressed as the weight% of the total polymer) .
  • BA butyl acrylate
  • MMA methyl methacrylate
  • MAA methacrylic acid

Abstract

Use of a copolymer of monomers selected from among those of formula (A), where R is hydrogen or methyl, formula (B), where R1 is hydrogen or methyl and R2 is C1-C8alkyl, where the amount of one or two different A-units in the copolymer totals 5-10 weight % and the rest is mainly one or more various B-units, as an additive for cement mortar-based mixtures or for coating of cured or partially cured concrete. A cement mortar mixture as defined above, and latex containing a copolymer of methacrylic acid, butyl acrylate and methyl methacrylate.

Description

Use of copolymers as additives for cement mortar mixtures or for coating of cured or partially cured concrete.
Cement-based mortar mixtures have been used for the preparation of construction materials for over 150 years. Such mixtures are in general satisfactory, but for certain applications they have deficiencies which it is desirable to rectify. One example is that construction elements fabricated from such cement mortar mixtures are prone to corrosive attack in seawater. There have been many attempts to reduce this corrosion by various means, among other things there has been much work involving the addition of polymers to reduce corrosion caused by the chloride in seawater in particular. Another property that it has been found desirable to improve is the cement mortar mixture's fluidity, that is to say, that it should flow smoothly out when e.g. laying floors.
The polymers most usually used as concrete additives are largely based on styrene-butadiene or vinyl acetate, although other types have been used.
It has now been found possible to produce cement mortar mixtures with greatly improved resistance to corrosion caused by seawater by adding to the cement mortar mixture a copolymer consisting of monomers chosen from among those of formula
A. CH2=C COOH
where R is hydrogen or methyl
B. CH5=^C —COOR^
R
where R1 is hydrogen or methyl, and R2 is C^ gal yl where the amount of one or two different A-units in the copolymer totals 5-10 weight% and the remainder consists mainly of one or more different B-units. The copolymer is advantageously used in the form of a latex, and as well as being added to cement mortar mixtures it can be applied as a coating to cured or partially cured concrete.
Monomer A can be acrylic acid or methacrylic acid, and it is possible to use both of these in the same copolymer. Monomer B comprises various esters of acrylic acid and methacrylic acid, and it is similarly possible to use several different esters in the same copolymer.
Especially suitable ester monomers B are those where R1 is hydrogen or methyl, and R2 is methyl or n-butyl.
An especially suitable acid monomer A is methacrylic acid, while especially suitable ester monomers B are butyl acrylate and methyl methacrylate.
Especially suitable copolymers are those where the amount of A monomer, especially methacrylic acid, is 6-8 weight %, and the remainder of the copolymer consists mainly of B monomers. The B monomers are preferably butyl acrylate and methyl methacrylate in the ratio 50:50-70:30, especially 65:35, on a weight basis.
In general, the higher the content of hydrophobic ester monomer, the higher the content of acid monomer in the copolymer should be. Normally it will similarly be possible to use somewhat less acrylic acid than methacrylic acid to acheive the same effect.
In addition to the monomers A and B, the copolymer used can also contain minor amounts, e.g. up to 10 weight%, of other ethylenically-unsaturated monomers, such as styrene.
The polymer latex used as an additive to cement mortar mixtures or applied to cured or partially cured concrete, has preferentially a solids content of 10-60% weight%, especially 30-60 weight%. A high water content in the latex will allow a corresponding reduction in the amount of water used to make the cement mortar mixture. The amount of polymer latex to be added to a cement mortar mixture is preferably from 2 to 25 weight%, and especially from 5 to 15 weight%, expressed as weight of polymer solids/ weight of cement powder.
The chloride ingress/corrosion which occurs in concrete in seawater is especially serious because it is followed by corrosion of the steel reinforcing bars when the chloride ions reach these. Corrosion of the reinforcing bars leads to expansion and resulting cracking of the concrete. To illustrate the improvement achieved by this invention compared to the use of other polymers, an accelerated test of chloride penetration in cured cement mortar was carried out.
The test was carried out in the following manner: A steel reinforcing bar was cast inside a cylinder of cement mortar which was partially immersed in seawater with the exposed part of the reinforcing bar above the surface of the water. This reinforcing bar was used as the anode, and a metal electrode immersed in the seawater was used as the cathode. The voltage across the electrodes was 5 volts D.C. In the following tables the results of such tests are given as the number of days before chloride penetration caused the current through the cylinder to increase sharply. Testing was carried out with two different mortars having differing water/cement ratios. The polymer latex used contained 50 weight% of polymer. The quoted additions of polymer are calculated on the basis of dry weight of polymer solids/ weight of cement powder.
Table I
Control (water/cement = 0.55) 3±1 days (1:3 mortar without polymer)
Figure imgf000005_0001
* Leakage current established
# Only one of two parallels failed + Testing discontinued after 1 year
Table II
Control (water/cement 0.40) 105±35 days (1:3 mortar without polymer)
Figure imgf000006_0001
* Still no current increase when table compiled
* Only one of two parallels failed
The polymer latexes used were as follows:
Polymer 1 = Commercial latex based on the terpolymer vinylacetate/vinyl chloride/ethylene
Polymer 2 = Commercial latex based on the copolymer vinyl acetate/"versatic" ester
Polymer 3 = Commercial latex based on styrene/butadiene rubber
Polymer 4 = 50 weight% solids content latex consisting of a copolymer of 7% methacrylic acid, 60.5% butyl acrylate and 32.5% methyl methacrylate by weight according to this invention
From the results it can be seen that Polymer 4 used in accordance with this invention resulted in considerably greater resistance to chloride penetration than the other commonly used latexes.
A polymer latex for use in accordance with this invention was prepared as follows: 2 grams of sodiummetabisulphite dissolved in 4.9 litres of water was heated towards 80 °C in a reactor. When the temperature reached 70 °C a solution of 12.5 grams of potassium persulphate (initiator) in 125 millilitres of water was added to the reactor.
A pre-emulsion was prepared from 6.4 litres of water, 350 grams of "Berol 295" (surfactant) , 840 grams of "Disponil AES 60" (surfactant) , 7569 grams of butyl acrylate, 4075 grams of methyl methacrylate and 856 grams of methacrylic acid. 10% of this pre-emulsion was thereafter added to the reactor when the aqueous solution it contained had reached a temperature of 75 °C. When this first portion had reacted, the remainder of the pre-emulsion was added over a period of 2 hours, while the temperature of the reactor was maintained at 80 ± 2 °C. Addition of a solution of 12.5 gram potassium persulphate in 900 millilitres of water was started at the same time as commencement of addition of the remainder of the pre-emulsion, and completed over 3 hours. The reactor temperature was maintained at 80 °C for a further 1 hour after the addition of the potassium persulphate solution was finished, then cooled down. 50 grams of the antifoaming agent "FOAM-MASTER ENA 224" were added at 65 °C. On final cooling to room temperature a 50 weight% solids content polymer latex was obtained, with particle size 100 - 200 nm.
This latex is used either as an additive for cement mortar mixtures or for applying as a coating to cured or partially- cured concrete to reduce the ingress of chloride. It is also suitable as an additive to improve the fluidity and workability of cement mortar-based mixtures.
Rheological properties.
The rheological properties are comprised, among other things, of workability and fluidity. Table III (below) shows the results of adding a polymer latex used according to this invention to a cement mortar compared to an unmodified cement mortar and a polymer-cement mortar containing a commercial styrene-butadiene (SBR) latex.
The polymer that was used according to this invention contained butyl acrylate (BA) and methyl methacrylate (MMA) in the specified weight ratio, with and without methacrylic acid (MAA) (expressed as the weight% of the total polymer) .
Table III Rheological properties of polymer-cement mortars with and without the addition of various latexes.
Figure imgf000008_0001
Ref.mortar 3.7 3.2 145(15)
Ref.mortar + SBR 8.0< 9.5 220(15)
Ref.mortar + latex 50/50 10.5 9.5 160 (0) 205 (6)
Ref.mortar + latex 50/50 3.7 >11.5 >225 (0)
a) Measured at 0.50 atm. instead of 1.0 atm. , and the result multiplied by 1.5
■°) The figures in brackets are the number of impacts to the flow-board necessary to achieve the given spread. The fewer the impacts, the better the flow.
It can be seen that the best result was achieved using the polymer containing BA/MMA in the ratio 50/50 and a MAA content of 7%, all expressed on a weight basis.

Claims

Claims
1. Use of a copolymer of monomers selected from among those of formula
Figure imgf000009_0001
where R is hydrogen or methyl
Figure imgf000009_0002
where R1 is hydrogen or methyl, and R2 is C^-galkyl
where the amount of one or two different A-units in the copolymer totals 5-10 weight% and the rest is mainly one or more various B-units, as an additive for cement mortar-based mixtures or for coating of cured or partially cured concrete.
2. Use according to claim 1 of a copolymer in which
R in A is hydrogen or methyl
R1 in B is hydrogen or methyl, and
R2 in B is methyl or n-butyl.
3. Use according to claim 2 of a copolymer of a monomer A in which R is methyl and two monomers B in which respectively R1 is hydrogen and R2 is n-butyl, and R1 and R2 are both methyl.
4. Use according to one of the claims 1-3 of a copolymer in which the amount of A-monomer(s) is 6-8 weight% and the remainder consists mainly of B-monomer(s) .
5. Use according to one of the claims 1-4 of a copolymer which besides units of A-monomer(s) and B-monomer(s) also contains up to 10 weight% of another ethylenically-unsaturated monomer.
6. Use according to one of the claims 1-5 in order to reduce chloride ingress in concrete.
7. Use of a copolymer according to one of the claims 1-6 in the form of a latex.
8. A cement mortar mixture, characterised in that it contains a copolymer of monomers as defined in one of the claims 1-5.
9. A copolymer latex characterised in that the disperse phase cosists of a copolymer of methacrylic acid, butyl acrylate, and methyl methacrylate.
10. A copolymer latex according to claim 9, characterised in that the copolymer consists of 6-8 weight% methacrylic acid, the rest being butyl acrylate and methyl methacrylate in the weight ratio 50/50 - 70/30, especially about 65/35.
PCT/NO1990/000131 1989-08-21 1990-08-17 Use of copolymers as additives for cement mortar mixtures or for coating of cured or partially cured concrete WO1991002703A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NO893344A NO171308C (en) 1989-08-21 1989-08-21 APPLICATION OF COPOLYMERS AS ADDITIVE FOR CEMENT MORTAL MIXTURES, CEMENT MORTAL MIXTURES, AND COPOLYMER DISPERSION
NO893344 1989-08-21

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5873413A (en) * 1997-08-18 1999-02-23 Halliburton Energy Services, Inc. Methods of modifying subterranean strata properties
EP0930279A1 (en) * 1998-01-20 1999-07-21 Nippon Shokubai Co., Ltd. Cement additive and cement composition using same
US6006835A (en) * 1998-02-17 1999-12-28 Halliburton Energy Services, Inc. Methods for sealing subterranean zones using foamed resin
US6006836A (en) * 1997-08-18 1999-12-28 Halliburton Energy Services, Inc. Methods of sealing plugs in well bores
US6012524A (en) * 1998-04-14 2000-01-11 Halliburton Energy Services, Inc. Remedial well bore sealing methods and compositions
US6059035A (en) * 1998-07-20 2000-05-09 Halliburton Energy Services, Inc. Subterranean zone sealing methods and compositions
US6098711A (en) * 1998-08-18 2000-08-08 Halliburton Energy Services, Inc. Compositions and methods for sealing pipe in well bores
US6124246A (en) * 1997-11-17 2000-09-26 Halliburton Energy Services, Inc. High temperature epoxy resin compositions, additives and methods
US6231664B1 (en) 1998-06-30 2001-05-15 Halliburton Energy Services, Inc. Well sealing compositions and methods
US6234251B1 (en) 1999-02-22 2001-05-22 Halliburton Energy Services, Inc. Resilient well cement compositions and methods
US6244344B1 (en) 1999-02-09 2001-06-12 Halliburton Energy Services, Inc. Methods and compositions for cementing pipe strings in well bores
US6454006B1 (en) 2000-03-28 2002-09-24 Halliburton Energy Services, Inc. Methods and associated apparatus for drilling and completing a wellbore junction
FR2836141A1 (en) * 2002-02-18 2003-08-22 Atofina Extrudable or pressable hydraulic binding compound contains rheological control agent and chain length regulator

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US4089999A (en) * 1975-07-17 1978-05-16 Hoechst Aktiengesellschaft Impregnation and primer coating of absorptive substrates with plastics dispersions
US4229224A (en) * 1978-02-22 1980-10-21 Imperial Chemical Industries Limited Cementitious compositions
EP0069586A2 (en) * 1981-07-07 1983-01-12 Marley Tile AG Polymer-modified cement mortars and concretes and processes for the production thereof
EP0145685A1 (en) * 1983-11-03 1985-06-19 Polyrand AB A cement mortar and concrete with a reduced water absorption and a method for manufacture thereof

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Title
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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6006836A (en) * 1997-08-18 1999-12-28 Halliburton Energy Services, Inc. Methods of sealing plugs in well bores
US5875844A (en) * 1997-08-18 1999-03-02 Halliburton Energy Services, Inc. Methods of sealing pipe strings in well bores
US5875846A (en) * 1997-08-18 1999-03-02 Halliburton Energy Services, Inc. Methods of modifying subterranean strata properties
US5875845A (en) * 1997-08-18 1999-03-02 Halliburton Energy Services, Inc. Methods and compositions for sealing pipe strings in well bores
US5911282A (en) * 1997-08-18 1999-06-15 Halliburton Energy Services, Inc. Well drilling fluids containing epoxy sealants and methods
US5873413A (en) * 1997-08-18 1999-02-23 Halliburton Energy Services, Inc. Methods of modifying subterranean strata properties
US5957204A (en) * 1997-08-18 1999-09-28 Halliburton Energy Services, Inc. Method of sealing conduits in lateral well bores
US5969006A (en) * 1997-08-18 1999-10-19 Halliburton Energy Services, Inc. Remedial well bore sealing methods
US6124246A (en) * 1997-11-17 2000-09-26 Halliburton Energy Services, Inc. High temperature epoxy resin compositions, additives and methods
US6165262A (en) * 1998-01-20 2000-12-26 Nippon Shokubai Co., Ltd. Cement additive and cement composition using same
EP0930279A1 (en) * 1998-01-20 1999-07-21 Nippon Shokubai Co., Ltd. Cement additive and cement composition using same
US6069117A (en) * 1998-02-17 2000-05-30 Halliburton Energy Services, Inc. Foamed resin compositions for sealing subterranean zones
US6006835A (en) * 1998-02-17 1999-12-28 Halliburton Energy Services, Inc. Methods for sealing subterranean zones using foamed resin
US6012524A (en) * 1998-04-14 2000-01-11 Halliburton Energy Services, Inc. Remedial well bore sealing methods and compositions
US6231664B1 (en) 1998-06-30 2001-05-15 Halliburton Energy Services, Inc. Well sealing compositions and methods
US6059035A (en) * 1998-07-20 2000-05-09 Halliburton Energy Services, Inc. Subterranean zone sealing methods and compositions
US6098711A (en) * 1998-08-18 2000-08-08 Halliburton Energy Services, Inc. Compositions and methods for sealing pipe in well bores
US6244344B1 (en) 1999-02-09 2001-06-12 Halliburton Energy Services, Inc. Methods and compositions for cementing pipe strings in well bores
US6234251B1 (en) 1999-02-22 2001-05-22 Halliburton Energy Services, Inc. Resilient well cement compositions and methods
US6454006B1 (en) 2000-03-28 2002-09-24 Halliburton Energy Services, Inc. Methods and associated apparatus for drilling and completing a wellbore junction
US6786283B2 (en) 2000-03-28 2004-09-07 Halliburton Energy Services, Inc. Methods and associated apparatus for drilling and completing a wellbore junction
FR2836141A1 (en) * 2002-02-18 2003-08-22 Atofina Extrudable or pressable hydraulic binding compound contains rheological control agent and chain length regulator
WO2003070658A1 (en) * 2002-02-18 2003-08-28 Atofina Extrudable binder composition

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NO893344D0 (en) 1989-08-21
NO893344L (en) 1991-02-22
NO171308C (en) 1993-02-24
NO171308B (en) 1992-11-16

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