US20080221243A1 - Fluidising composition - Google Patents
Fluidising composition Download PDFInfo
- Publication number
- US20080221243A1 US20080221243A1 US12/040,475 US4047508A US2008221243A1 US 20080221243 A1 US20080221243 A1 US 20080221243A1 US 4047508 A US4047508 A US 4047508A US 2008221243 A1 US2008221243 A1 US 2008221243A1
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- United States
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- formula
- admixture
- moiety
- coor
- coo
- 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.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims description 26
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 10
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001991 dicarboxylic acids Chemical class 0.000 claims abstract description 4
- 150000002763 monocarboxylic acids Chemical class 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 claims description 9
- 150000001768 cations Chemical class 0.000 claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000005507 spraying Methods 0.000 claims description 9
- 239000004568 cement Substances 0.000 claims description 8
- 125000005915 C6-C14 aryl group Chemical group 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical group 0.000 claims description 3
- 229960004106 citric acid Drugs 0.000 claims description 3
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 claims 2
- 125000006295 amino methylene group Chemical group [H]N(*)C([H])([H])* 0.000 claims 1
- 239000004567 concrete Substances 0.000 description 17
- 0 [2*]COCCCC Chemical compound [2*]COCCCC 0.000 description 15
- 238000012360 testing method Methods 0.000 description 12
- GXDHCNNESPLIKD-UHFFFAOYSA-N CCCCC(C)C Chemical compound CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VZHNMXZOSYOSLE-UHFFFAOYSA-N CC(C)C(C)C.CC1C(=O)[Y]C(=O)C1C Chemical compound CC(C)C(C)C.CC1C(=O)[Y]C(=O)C1C VZHNMXZOSYOSLE-UHFFFAOYSA-N 0.000 description 3
- VLJXXKKOSFGPHI-UHFFFAOYSA-N CCCC(C)CC Chemical compound CCCC(C)CC VLJXXKKOSFGPHI-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- PPOXWGYDXCXNDO-UHFFFAOYSA-N C.C[Si](C)(C)O[Si](C)(C)C Chemical compound C.C[Si](C)(C)O[Si](C)(C)C PPOXWGYDXCXNDO-UHFFFAOYSA-N 0.000 description 2
- CLIMHBDVWIGBML-UHFFFAOYSA-N CCC(C)(C)CC.CCC(C)C.CCC1(C)CC(=O)[Y]C1=O Chemical compound CCC(C)(C)CC.CCC(C)C.CCC1(C)CC(=O)[Y]C1=O CLIMHBDVWIGBML-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000007779 soft material Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QZZJUCRDPREUHK-SDNWHVSQSA-P CC(C)(/C=N/C)[SH+](C)(C)OC(C)(C)[SH+](C)(C)C Chemical compound CC(C)(/C=N/C)[SH+](C)(C)OC(C)(C)[SH+](C)(C)C QZZJUCRDPREUHK-SDNWHVSQSA-P 0.000 description 1
- HMGBVAAXFQFTMU-UHFFFAOYSA-N CCC(C)C.CCC(C)CC.CCC1(C)CC(=O)[Y]C1=O Chemical compound CCC(C)C.CCC(C)CC.CCC1(C)CC(=O)[Y]C1=O HMGBVAAXFQFTMU-UHFFFAOYSA-N 0.000 description 1
- UHHDQLYKBYYTTO-UHFFFAOYSA-N CCOC.CCOC.CNC#O(C)N(C)C(C)=O.CO(C)O(C)C Chemical compound CCOC.CCOC.CNC#O(C)N(C)C(C)=O.CO(C)O(C)C UHHDQLYKBYYTTO-UHFFFAOYSA-N 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N C[Si](C)(C)O[Si](C)(C)C Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 229920005682 EO-PO block copolymer Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 150000001399 aluminium compounds Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000011378 shotcrete Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/003—Phosphorus-containing compounds
-
- 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
- C04B24/2688—Copolymers containing at least three different monomers
-
- 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
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
-
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
-
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/32—Superplasticisers
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00146—Sprayable or pumpable mixtures
- C04B2111/00155—Sprayable, i.e. concrete-like, materials able to be shaped by spraying instead of by casting, e.g. gunite
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00146—Sprayable or pumpable mixtures
- C04B2111/00155—Sprayable, i.e. concrete-like, materials able to be shaped by spraying instead of by casting, e.g. gunite
- C04B2111/00172—Sprayable, i.e. concrete-like, materials able to be shaped by spraying instead of by casting, e.g. gunite by the wet process
Definitions
- the invention also provides a method of imparting flow to a cementitious composition, comprising the addition thereto of an admixture as hereinabove described.
- the material used is “MVA 2453 L/44%” ex Degussa.
Abstract
A fluidising admixture for use with sprayable cementitious compostions, the admixture consists of 2-phosphonobutane-1,2,4-tricarboxylic acid and at least one selected polymer derived from ethylenically-unsaturated mono- or dicarboxylic acids. Citric acid may optionally be present. The admixture has good fluidising properties and outstanding shelf-life.
Description
- This invention relates to the spraying of cementitious compositions and to admixtures for use in such spraying.
- The spraying of cementitious compositions such as concrete is regularly used in a number of applications, most notably in tunnelling. It is a requirement that such compositions be able to be easily conveyed (usually by pumping) to a spray nozzle. This can be achieved by the addition to the cementitious composition that is to be pumped and sprayed, at the mix stage, of an admixture which confers improved fluidity of the mix. There is a considerable variety of such admixtures known to and used by the art.
- It has now been found that an especially effective admixture may be prepared by the combination of particular selected components. The invention therefore provides a fluidising admixture for use with sprayable cementitious compostions, the admixture consisting of
-
- (1) 2-phosphonobutane-1,2,4-tricarboxylic acid;
- (2) optionally, citric acid; and
- (3) at least one polymer derived from ethylenically-unsaturated mono- or dicarboxylic acids, and characterised in that the polymer consists of
- a) 51-95 mole % of moieties of formula 1a and/or 1b and/or 1c
-
- wherein R1=hydrogen or a C1-20 aliphatic hydrocarbon residue;
- X=OaM, —O—(CmH2mO)n—R2, —NH—(CmH2mO)n—R2,
- M=hydrogen, a mono- or divalent metal cation, an ammonium ion or an organic amine residue;
- a=0.5 or 1;
- R2=hydrogen, C1-20 aliphatic hydrocarbon, C5-8 cycloaliphatic hydrocarbon or optionally substituted C6-14 aryl residue;
- Y=O, NR2;
- m=2-4; and
- n=0-200
- b) 1-48.9 mole % of moieties of the general formula II
- wherein R1=hydrogen or a C1-20 aliphatic hydrocarbon residue;
-
- wherein R3=hydrogen or C1-5 aliphatic hydrocarbon;
- p=0-3; and
- R2 has the meaning given previously;
- c) 0.1-5 mole % of moieties of Formulae IIIa or IIIb
- wherein R3=hydrogen or C1-5 aliphatic hydrocarbon;
-
- wherein S═H, —COOaM, —COOR5
-
- —W—R7
- —CO—[NH—(CH2)3]s—W—R7
- —CO—O—(CH2)z—W—R7
- —(CH2)z—V—(CH2)z—CH═CH—R2
- —COOR5 when S is —COOR5 or COOa M
- U1=—CO—NH—, —O—, —CH2O—
- U2=—NH—CO—, —O—, —OCH2—
- V=—O—CO—C6H4—CO—O— or —W—
-
- R4=H, CH3
- R5=H, C3-20 alphatic hydrocarbon residue, C5-C8 cycloaliphatic hydrocarbon residue or C6-14 aryl residue;
-
- wherein r=2-100
- s=1, 2
- x=1-150
- y=0-15
- z=0-4
- d) 0-47.9 mole % of moieties of the general formula IVa and or IVb:
- wherein r=2-100
-
- wherein a, M, X and Y have the significances hereinabove defined.
- In a preferred embodiment of the invention, the polymer is characterised as follows—any moiety or group present in the polymer description hereinabove and not specifically mentioned in the following embodiment is absent from the embodiment, and any numerical value not specifically mentioned remains unaltered from that of the polymer description hereinabove;
-
- a) the moiety is according to formula Ia;
- R1, R2 are independently H or CH3;
- X=OaM, —O—(CmH2mO)n—R2
- M=H or a mono- or divalent metal cation;
- a=1;
- Y=O, NR2;
- m=2-3; and
- n=20-150;
- b) R2, R3 are independently H or CH3; and
- p=0-1;
- c) the moiety is according to formula IIIa;
- S=H, —COOaM, —COOR5
- a) the moiety is according to formula Ia;
-
- —CO—[NH—(CH2)3]s—W—R7
- —CO—O—(CH2)z—W—R7
- R4, R5 are independently H, CH3;
-
- wherein
-
- x=20-50;
- y=1-10; and
- z=0-2.
- In a further preferred embodiment, the polymer is characterised as follows—any moiety or group present in the description of the preferred embodiment hereinabove and not specifically mentioned in the following further preferred embodiment is absent from the further preferred embodiment, and any numerical value not specifically mentioned remains unaltered from that of the preferred embodiment description hereinabove;
-
- a) the moiety is according to formula Ia;
- R1=H;
- R2=CH3;
- X=OaM;
- M=a mono- or divalent metal cation;
- Y=O, NR2;
- m=2; and
- n=25-50;
- b) R2, R3=H; and
- p=0;
- c) the moiety is according to formula IIIa;
- S=H, —COOaM;
- a) the moiety is according to formula Ia;
-
- —CO—O—(CH2)z—W—R7
- R4, R5=H;
-
- wherein
- U1=—CO—NH—;
- U2=—NH—CO—, —O—, —OCH2—
- x=20-50;
- y=5-10; and
- z=1-2.
- wherein
- The polymers for use in this invention preferably have a weight-average molecular weight of from 5000-50000, preferably from 10000-40000.
- Typical examples of preferred polymers may be prepared by the reaction of methoxypolyethyleneglycol-monovinyl ether, maleic anhydride, amine-terminated ethylene oxide-propylene oxide block copolymer and acrylic acid. Examples of these materials and their preparation may be found in International Application WO 00/77058 the contents of which are incorporated herein by reference.
- The invention also provides a method of imparting flow to a cementitious composition, comprising the addition thereto of an admixture as hereinabove described.
- The invention also provides a method of spraying a cementitious composition by preparing a cementitious mix and conveying the mix to a spray nozzle, there being added to the mix at preparation an admixture as hereinabove described.
- The proportions of the solids of the three components in the admixture are as follows:
-
limits more preferred most preferred Component 1 1-40 2-20 4-12 Component 2 0-40 2-20 4-12 Component 3 5-60 10-40 20-30 - The admixture will always contain a proportion of water, and the admixture will never be 100% solids, as the “limits” and “more preferred” columns would seem to suggest is possible. However, the skilled person will be able to determine appropriate compositions in each case, by simple experimentation.
- The admixture is added to a cementitious mixture at a rate of from 0.2-2.0%, preferably from 0.5-0.8% by weight solids on cement.
- The admixture according to this invention may be used in conjunction with all the conventional admixtures used in the spraying of cementitious compositions, for example, the various accelerators commonly added at the spray nozzle. The admixture according to the invention works well with both the classic alkali types (such as aluminates, caustic alkalis and “water glass”) and the newer alkali-free, generally aluminium compound-based types.
- The admixture according to the invention performs at least as well as known fluidity-improving admixtures. It has the additional major practical advantage of having a very long shelf life. This means that it can be prepared well in advance of use and stored for several months without any segregation of ingredients. Moreover, it maintains this stability in the adverse conditions often found in tunnels, such as high temperatures, on exposure to which many conventional admixtures are no longer stable.
- The invention is further described with reference to the following examples.
- Preparation and testing of an admixture according to the invention.
- An admixture is prepared by mixing the following components
-
polymer (44% aqueous solution)1 50 parts by weight water 36 parts 2-phosphonobutane-1,2,4-tricarboxylic acid 7.8 parts (50% aqueous solution) citric acid monohydrate 7.1 parts 1The material used is “MVA 2453 L/44%” ex Degussa. - 1. The material used is “MVA 2453 L/44%” ex Degussa.
-
- This is added to a concrete mix of the following composition at a rate of 0.7% solids on cement:
-
Portland cement CEM I 42.5 450 kg/m3 Aggregate 0-4 mm 1165 kg/m3 4-8 mm 500 kg/m3 -
- having a water/cement ratio of 0.435.
- As a comparison, there is added to samples of the same concrete mix the same proportion of a high performance, commercially-available fluidising agent GLENIUM® T 803 ex MBT (Schweiz) AG. These mixes are tested by means of (a) a flow table, and (b) spraying.
- The flow table tests are as follows:
-
Composition GLENIUM of invention T 803 Water/cement ratio 0.435 0.441 Flow table spread [cm] 1 h 52 54 2 h 50 52 3 h 47 49 4 h 45 47 Air content [%] 3.0 2.6 - For the spray testing, there is added at the nozzle in both cases 7% by weight on cement of a commercially-available shotcrete accelerator, MEYCO® SA160 (ex MBT (Schweiz) AG. The compressive strength is measured in a variety of ways and over different times and the results are shown in the following table:
-
Composition GLENRIUM of invention T 803 Compressive. Strength [MPa] 3 min. (penetroneedle)2 0.12 0.06 6 min. (penetroneedle)2 0.18 0.09 15 min. (penetroneedle)2 0.19 0.20 30 min. (penetroneedle)2 0.36 0.27 1 h (penetroneedle)2 0.56 0.46 2 h (penetroneedle)2 0.90 0.68 4 h (penetroneedle)2 2.70* 0.90 1 d (nail gun)3 17.5 17.1 28 d (core)4 41.7 45.8 2A method for testing compressive strength, in which a metal needle is pushed into concrete and the resistance to its entry is measured. Suitable for relatively soft materials 3A method for testing compressive strength, in which a metal nail is fired into a concrete and its penetration measured. Suitable for concretes at a later stage after setting 4A method for testing compressive strength, in which a cylindrical core is drilled from a hardened concrete and tested on a testing apparatus. *This result had to be obtained by means of a nail gun, because the concrete is already too hard to use the penetroneedle method. On the other hand, the comparative example is too soft to allow use of the nail gun. This is an indication of the superior early strength development of a concrete utilising the admixture of the present invention. Early strength development is very important in spraying concrete applications. - 2. A method for testing compressive strength, in which a metal needle is pushed into concrete and the resistance to its entry is measured. Suitable for relatively soft materials.
- 3. A method for testing compressive strength, in which a metal nail is fired into a concrete and its penetration measured. Suitable for concretes at a later stage after setting.
- 4. A method for testing compressive strength, in which a cylindrical core is drilled from a hardened concrete and tested on a testing apparatus.
- * This result had to be obtained by means of a nail gun, because the concrete is already too hard to use the penetroneedle method. On the other hand, the comparative example is too soft to allow use of the nail gun. This is an indication of the superior early strength development of a concrete utilising the admixture of the present invention. Early strength development is very important in spraying concrete applications.
- The admixture according to the invention has performance characteristics comparable with those of the high performance commercial material.
- Stability testing of the admixture of Example 1.
- Samples of the admixture are tested in a mortar by flow table and for setting time. The mortar is a 1:3 blend of CEM I 42.5 Portland cement and CEM standard sand (according to DIN EN 196-1), and the admixture samples are added at a rate of 1% solids by weight on cement. Samples are also stored at 20° C., 30° C. and 40° C. for six months. At the end of the six months, the admixtures remained visually unaffected. The actual test results are shown in the following table:
-
Sample No. 1 2 3 4 Storage time [days] 1 180 180 180 Storage temperature [° C.] 20 20 30 40 W/C 0.42 0.42 0.42 0.42 Flow table [cm] 16.5 18.0 17.0 18.0 Initial setting [min.] 500 450 400 330 Final setting [min.] 920 850 740 740 - It can be seen that the properties are only slightly changed.
Claims (15)
1-5. (canceled)
6. A method of imparting flow to a cementitious composition, comprising the addition thereto of an admixture comprising:
(1) 2-phosphonobutane-1,2,4-tricarboxylic acid;
(2) optionally, citric acid or citric acid monohydrate; and
(3) at least one polymer derived from ethylenically-unsaturated mono- or dicarboxylic acids, and characterised in that the polymer comprises:
a) 51-95 mole % of moieties of formula 1a and/or 1b and/or 1c
wherein R1=hydrogen or a C1-20 aliphatic hydrocarbon residue;
X=OaM, —O—(CmH2mO)n—R 2, —NH—(CmH2mO)n—R2,
M=hydrogen, a mono- or divalent metal cation, an ammonium ion or an organic amine residue;
a=0.5 or 1;
R2=hydrogen, C1-20 aliphatic hydrocarbon, C5-8 cycloaliphatic hydrocarbon or optionally substituted C6-14 aryl residue;
Y=O, NR2;
m=24; and
n=0-200;
b) 1-48.9 mole % of moieties of the general formula II
wherein R3=hydrogen or C1-5 aliphatic hydrocarbon;
p=0-3; and
R2 has the meaning given previously;
c) 0.1-5 mole % of moieties of Formulae IIIa or IIIb
—W—R7
—CO—[NH—CH2)3]s—W—R7
—CO—O—(CH2)z—W—R7
—(CH2)z—V—(CH 2)z—CH═CH—R2
—COOR5 when S is —COOR5 or COOaM
U1=—CO—NH—, —O—, —CH2O—
U2=—NH—CO—, —O—, —OCH2—
V=—O—CO—C6H4—CO—O— or —W—
R4=H, CH3
R5=H, C3-20 alphatic hydrocarbon residue, a C5-C8 cycloaliphatic hydrocarbon residue or a C6-14 aryl residue;
wherein r=2-100
s=1, 2
z=0-4
x=1-150
y=0-15; and
d) 0-47.9 mole % of moieties of the general formula IVa and/or IVb:
7. The method according to claim 6 , in which:
a) the moiety is according to formula Ia;
R1, R2 are independently H or CH3;
X=OaM, —O—(CmH2mO)n—R2
M=H or a mono- or divalent metal cation;
a=1;
Y=O, NR2;
m=2-3; and
n=20-150;
b) R2, R3 are independently H or CH3; and
p=0-1;and
c) the moiety is according to formula IIIa;
S=H, —COOaM, —COOR5
8. The method according to claim 7 , in which:
a) the moiety is according to formula Ia;
R1=H;
R2=CH3;
X=OaM;
M=a mono- or divalent metal cation;
Y=O, NR2;
m=2; and
n=25-50;
b) R2, R3=H; and
p=0; and
c) the moiety is according to formula IIIa;
S=H, —COOaM;
9. The method of claim 6 wherein the polymer has a weight-average molecular weight of from about 5,000 to about 50,000.
10. The method of claim 6 wherein the polymer has a weight-average molecular weight of from about 10,000 to about 40,000.
11. The admixture of claim 6 wherein the proportions of the solids of the three components are:
Component 1—about 1% to about 40%;
Component 2—0 to about 40%; and
Component 3—about 5% to about 60%.
12. The method of claim 6 wherein the admixture is added at a rate of from about 0.2% to about 2% by weight solids of cement.
13. A method of spraying a cementitious composition comprising preparing a cementitious mix and conveying the mix to a spray nozzle, there being added to the mix at preparation an admixture comprising:
(1) 2-phosphonobutane-1,2,4-tricarboxylic acid;
(2) optionally, citric acid or citric acid monohydrate; and
(3) at least one polymer derived from ethylenically-unsaturated mono- or dicarboxylic acids, and characterised in that the polymer comprises:
a) 51-95 mole % of moieties of formula 1a and/or 1b and/or 1c
wherein R1=hydrogen or a C 1-20 aliphatic hydrocarbon residue;
X=OaM, —O—(CmH2mO)n—R2, —NH—(CmH2mO)n—R2,
M=hydrogen, a mono- or divalent metal cation, an ammonium ion or an organic amine residue;
a=0.5 or 1;
R2=hydrogen, C1-20 aliphatic hydrocarbon, C5-8 cycloaliphatic hydrocarbon or optionally substituted C6-14 aryl residue;
Y=O, NR2;
m=2-4; and
n=0-200;
b) 1-48.9 mole % of moieties of the general formula II
wherein R3=hydrogen or C1-5 aliphatic hydrocarbon;
p=0-3; and
R2 has the meaning given previously;
c) 0.1-5 mole % of moieties of Formulae IIIa or IIIb
—W—R7
—CO—[NH—(CH2)3]s—W—R7
—CO—O—(CH2)z—W—R7
—(CH2)z—V—CH2)z—CH═CH—R2
—COOR5 when S is —COOR5 or COOaM
U1=—CO—NH—, —O—, —CH2O—
U2=—NH—CO—, —O—, —OCH2—
V=—O—CO—C6H4—CO—O— or —W—
R4=H, CH3
R5=a C3-20 alphatic hydrocarbon residue, a C5-C8 cycloaliphatic hydrocarbon residue or a C6-14 aryl residue;
wherein r=2-100
s=1, 2
z=0-4
x=1-150
y=0-15; and
d) 0-47.9 mole % of moieties of the general formula IVa and/or IVb:
14. The method according to claim 13 , in which:
a) the moiety is according to formula Ia;
R1, R2 are independently H or CH3
X=OaM, —O—(CmH2mO)n—R2
M=H or a mono- or divalent metal cation;
a=1;
Y=O, NR2;
m=2-3; and
n=20-150;
b) R2, R3 are independently H or CH3; and
p=0-1;and
c) the moiety is according to formula IIIa;
S=H, —COOaM, —COOR5
15. The method according to claim 14 , in which:
a) the moiety is according to formula Ia;
R1=H;
R2=CH3;
X=OaM;
M=a mono- or divalent metal cation;
Y=O, NR2;
m=2; and
n=25-50;
b) R2, R3=H; and
p=0; and
c) the moiety is according to formula IIIa;
S=H, —COOaM;
16. The method of claim 13 wherein the polymer has a weight-average molecular weight of from about 5,000 to about 50,000.
17. The method of claim 13 wherein the polymer has a weight-average molecular weight of from about 10,000 to about 40,000.
18. The admixture of claim 13 wherein the proportions of the solids of the three components are:
Component 1—about 1% to about 40%;
Component 2—0 to about 40%; and
Component 3—about 5% to about 60%.
19. The method of claim 13 wherein the admixture is added at a rate of from about 0.2% to about 2% by weight solids of cement.
Priority Applications (2)
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US12/040,475 US20080221243A1 (en) | 2002-09-09 | 2008-02-29 | Fluidising composition |
US12/694,796 US8177905B2 (en) | 2002-09-09 | 2010-01-27 | Fluidising composition |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US10/524,466 US20060155019A1 (en) | 2002-09-09 | 2002-09-09 | Fluidising composition |
PCT/EP2002/010045 WO2004024646A1 (en) | 2002-09-09 | 2002-09-09 | Fluidising composition |
US12/040,475 US20080221243A1 (en) | 2002-09-09 | 2008-02-29 | Fluidising composition |
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US10524466 Continuation | 2002-09-09 | ||
US10/524,466 Continuation US20060155019A1 (en) | 2002-09-09 | 2002-09-09 | Fluidising composition |
PCT/EP2002/010045 Continuation WO2004024646A1 (en) | 2002-09-09 | 2002-09-09 | Fluidising composition |
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US12/694,796 Continuation US8177905B2 (en) | 2002-09-09 | 2010-01-27 | Fluidising composition |
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US20080221243A1 true US20080221243A1 (en) | 2008-09-11 |
Family
ID=31984988
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US10/524,466 Abandoned US20060155019A1 (en) | 2002-09-09 | 2002-09-09 | Fluidising composition |
US12/040,475 Abandoned US20080221243A1 (en) | 2002-09-09 | 2008-02-29 | Fluidising composition |
US12/694,796 Expired - Fee Related US8177905B2 (en) | 2002-09-09 | 2010-01-27 | Fluidising composition |
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US10/524,466 Abandoned US20060155019A1 (en) | 2002-09-09 | 2002-09-09 | Fluidising composition |
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US12/694,796 Expired - Fee Related US8177905B2 (en) | 2002-09-09 | 2010-01-27 | Fluidising composition |
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US (3) | US20060155019A1 (en) |
EP (1) | EP1537058B1 (en) |
JP (1) | JP4547261B2 (en) |
CN (1) | CN100497233C (en) |
AT (1) | ATE397572T1 (en) |
AU (1) | AU2002331110B2 (en) |
BR (1) | BR0215861B1 (en) |
CA (1) | CA2495828C (en) |
DE (1) | DE60227010D1 (en) |
ES (1) | ES2307785T3 (en) |
MX (1) | MXPA05002629A (en) |
NO (1) | NO338998B1 (en) |
PT (1) | PT1537058E (en) |
WO (1) | WO2004024646A1 (en) |
Cited By (1)
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CN109311754A (en) * | 2016-06-21 | 2019-02-05 | 竹本油脂株式会社 | Concrete composition and concrete cured product |
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WO2013001038A1 (en) * | 2011-06-29 | 2013-01-03 | Sika Technology Ag | Skin layer reduction in calcium sulfate based binder compositions |
CN115650656A (en) * | 2022-11-11 | 2023-01-31 | 上海城建市政工程(集团)有限公司 | Working time adjustable ultra-high performance concrete |
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2002
- 2002-09-09 CA CA2495828A patent/CA2495828C/en not_active Expired - Fee Related
- 2002-09-09 AT AT02767476T patent/ATE397572T1/en not_active IP Right Cessation
- 2002-09-09 PT PT02767476T patent/PT1537058E/en unknown
- 2002-09-09 DE DE60227010T patent/DE60227010D1/en not_active Expired - Lifetime
- 2002-09-09 ES ES02767476T patent/ES2307785T3/en not_active Expired - Lifetime
- 2002-09-09 WO PCT/EP2002/010045 patent/WO2004024646A1/en active IP Right Grant
- 2002-09-09 JP JP2004535029A patent/JP4547261B2/en not_active Expired - Fee Related
- 2002-09-09 MX MXPA05002629A patent/MXPA05002629A/en active IP Right Grant
- 2002-09-09 EP EP02767476A patent/EP1537058B1/en not_active Expired - Lifetime
- 2002-09-09 BR BRPI0215861-2A patent/BR0215861B1/en not_active IP Right Cessation
- 2002-09-09 CN CNB028295838A patent/CN100497233C/en not_active Expired - Fee Related
- 2002-09-09 US US10/524,466 patent/US20060155019A1/en not_active Abandoned
- 2002-09-09 AU AU2002331110A patent/AU2002331110B2/en not_active Ceased
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2005
- 2005-04-08 NO NO20051747A patent/NO338998B1/en not_active IP Right Cessation
-
2008
- 2008-02-29 US US12/040,475 patent/US20080221243A1/en not_active Abandoned
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2010
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Also Published As
Publication number | Publication date |
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AU2002331110B2 (en) | 2010-09-09 |
CN100497233C (en) | 2009-06-10 |
CA2495828A1 (en) | 2004-03-25 |
DE60227010D1 (en) | 2008-07-17 |
NO20051747D0 (en) | 2005-04-08 |
MXPA05002629A (en) | 2005-05-27 |
JP4547261B2 (en) | 2010-09-22 |
ES2307785T3 (en) | 2008-12-01 |
NO20051747L (en) | 2005-04-08 |
US20100130647A1 (en) | 2010-05-27 |
BR0215861A (en) | 2005-07-05 |
JP2005538024A (en) | 2005-12-15 |
NO338998B1 (en) | 2016-11-07 |
EP1537058B1 (en) | 2008-06-04 |
US20060155019A1 (en) | 2006-07-13 |
ATE397572T1 (en) | 2008-06-15 |
US8177905B2 (en) | 2012-05-15 |
CN1668547A (en) | 2005-09-14 |
CA2495828C (en) | 2011-01-11 |
PT1537058E (en) | 2008-08-27 |
BR0215861B1 (en) | 2011-11-29 |
WO2004024646A1 (en) | 2004-03-25 |
EP1537058A1 (en) | 2005-06-08 |
AU2002331110A1 (en) | 2004-04-30 |
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