CA2148291A1 - Water-reducing admixtures for cementitious compositions - Google Patents
Water-reducing admixtures for cementitious compositionsInfo
- Publication number
- CA2148291A1 CA2148291A1 CA002148291A CA2148291A CA2148291A1 CA 2148291 A1 CA2148291 A1 CA 2148291A1 CA 002148291 A CA002148291 A CA 002148291A CA 2148291 A CA2148291 A CA 2148291A CA 2148291 A1 CA2148291 A1 CA 2148291A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- water
- hydrogenated
- sample
- pca
- 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 abstract description 34
- 229920005646 polycarboxylate Polymers 0.000 claims abstract description 73
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 50
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000005846 sugar alcohols Chemical class 0.000 claims abstract description 15
- 150000004676 glycans Chemical class 0.000 claims abstract description 6
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 6
- 239000005017 polysaccharide Substances 0.000 claims abstract description 6
- 229920002472 Starch Polymers 0.000 claims description 21
- 235000019698 starch Nutrition 0.000 claims description 21
- 239000008107 starch Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- -1 poly(acrylate salt-acrylate ester Chemical class 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 8
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- 239000004386 Erythritol Substances 0.000 claims description 3
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 3
- 229920002488 Hemicellulose Polymers 0.000 claims description 3
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 3
- 235000019414 erythritol Nutrition 0.000 claims description 3
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims description 3
- 229940009714 erythritol Drugs 0.000 claims description 3
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 239000000600 sorbitol Substances 0.000 claims description 3
- 235000010356 sorbitol Nutrition 0.000 claims description 3
- 239000000811 xylitol Substances 0.000 claims description 3
- 235000010447 xylitol Nutrition 0.000 claims description 3
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 3
- 229960002675 xylitol Drugs 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 229960005150 glycerol Drugs 0.000 claims description 2
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 2
- 229960002920 sorbitol Drugs 0.000 claims description 2
- 239000004567 concrete Substances 0.000 abstract description 22
- 230000003247 decreasing effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 24
- 239000004568 cement Substances 0.000 description 21
- 239000004570 mortar (masonry) Substances 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 19
- 239000000463 material Substances 0.000 description 18
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 239000000413 hydrolysate Substances 0.000 description 9
- 230000000740 bleeding effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 108010009736 Protein Hydrolysates Proteins 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000002195 synergetic effect Effects 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 229920001732 Lignosulfonate Polymers 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000000007 visual effect Effects 0.000 description 4
- 239000004117 Lignosulphonate Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 235000019357 lignosulphonate Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 2
- 239000011440 grout Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- FGRBYDKOBBBPOI-UHFFFAOYSA-N 10,10-dioxo-2-[4-(N-phenylanilino)phenyl]thioxanthen-9-one Chemical compound O=C1c2ccccc2S(=O)(=O)c2ccc(cc12)-c1ccc(cc1)N(c1ccccc1)c1ccccc1 FGRBYDKOBBBPOI-UHFFFAOYSA-N 0.000 description 1
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000002016 disaccharides Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000011372 high-strength concrete Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- AVFBYUADVDVJQL-UHFFFAOYSA-N phosphoric acid;trioxotungsten;hydrate Chemical compound O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O AVFBYUADVDVJQL-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 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
-
- 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
- C04B24/02—Alcohols; Phenols; Ethers
-
- 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
- C04B24/10—Carbohydrates or derivatives thereof
-
- 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
-
- 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
- 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
- C04B24/2647—Polyacrylates; Polymethacrylates 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
-
- 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
- C04B24/38—Polysaccharides or derivatives thereof
-
- 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
- C04B24/38—Polysaccharides or derivatives thereof
- C04B24/383—Cellulose or derivatives thereof
-
- 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
-
- 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
- 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
- C04B2103/302—Water reducers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
An admixture for decreasing the water demand of cementitious compositions such as concrete consists of (a) from 75-25% by weight of a water-reducing agent whose major component is a polycarboxylate; and (b) from 25-75% by weight of at least one saccharide component selected from hydrogenated saccharides and polyhydric alcohol adducts of saccharides.
The saccharide component is preferably a hydrogenated polysaccharide with a molecular weight distribution as follows:
(i) 70-30% by weight (on total weight of hydrogenated saccharides) have molecular weights in the range 180-300;
(ii) 30-70% by weight have molecular weights of from 300 up to 4,000; and (iii) 30% by weight maximum have molecular weights of 4,000 and over.
The saccharide component is preferably a hydrogenated polysaccharide with a molecular weight distribution as follows:
(i) 70-30% by weight (on total weight of hydrogenated saccharides) have molecular weights in the range 180-300;
(ii) 30-70% by weight have molecular weights of from 300 up to 4,000; and (iii) 30% by weight maximum have molecular weights of 4,000 and over.
Description
21~8291 Case 154-0252 WATER-REDUCING ADMIXTURES FOR CEMENTITIOUS COMPOSITIONS
This invention relates to an admixture for cementitious compositions such as grouts, mortars and concretes.
Increasing difficulty in and expense of obtaining high quality aggregate for usein cementitious compositions such as concrete has forced manufacturers to resort to S lower grade materials such as crushed stone, marine sand and even crushed concrete obtained from the demolition of old structures. This leads to problems with the concrete such as higher water demand, bleeding and lower workability and pumpability.
It has been attempted to overcome these problems by means of admixtures. Typical of such admixtures are those already well known in the art, such as lignosulphonates, naphthalene sulphonate-formaldehyde condensates and various saccharides. Such materials reduce water requirement but also delay setting of the concrete, something which is not always desirable.
It has now been found that a blend of particular materials can greatly decrease the quantity of water required for a given cementitious mix while not significantly lS increasing set time. In addition, the blend does not cause excessive aeration (a major problem with some known admixtures) and it inhibits bleeding and improves workability. The invention therefore provides an admixture for use in a cementitious composition, which admixture consists of (a) from 75-25% by weight of a water-reducing agent whose major component is a polycarboxylate; and (b) from 25-75% by weight of at least one saccharide component selected from hydrogenated saccharides and polyhydric alcohol adducts of saccharides.
The water-reducing agent has as a major component a polycarboxylate which is 21~8~91 -- 2 Case 154-0252 known to be a water-reducing agent in its own right. By "major component" is meant that the polycarboxylate or polycarboxylates (it is permissible to use more than one such material) is present in higher weight p~vpol~ion than any other individual component in the water-reducing agent. It is therefore possible for the polycarboxylate 5 to comprise less than 50% of the weight of the water-reducing agent, although it is preferable that it comprises at least 50%. More preferably, the water reducing agent comprises at least 60% by weight of polycarboxylate and most preferably it is 100%
polycarboxylate. Typical examples include poly(acrylate salt-acrylate ester) copolymers, poly(methacrylic acid-methacrylate) copolymers, poly(styrene- maleate salt) l0 copolymers, and poly(styrene-maleate ester) copolymers. Such materials are readily available commercially, for example, the SP-8 series of materials from NMB Ltd.
The water-reducing agent may additionally contain at least one other non-carboxylate water-reducing agent. Any known water-reducing agent is satisfactory and typical examples include lignosulphonates and naphthalene sulphonate-formaldehyde 15 condensates.
The hydrogenated saccharides which are one possibility for use in this inventionas a saccharide component as hereinabove mentioned may be derived from mono- or disaccharides, but are preferably derived from polysaccharides, more preferably starches. Examples of suitable saccharides which may be hydrogenated include starch 20 hydrolysates, glucose fermentation products, celluloses, cellulose hydrolysates, hemicelluloses and hemicellulose hydrolystes, starch hydrolysates being especially desirable. Commercial examples of suitable materials include D-Sorbit and PO-20 of Towa Kasei and SE-l00 of Nikken Kagaku. Other materials include hydrogenated oligosaccharides, for example, of the type described in United States Patent 4,073,658.
The polyhydric alcohol adducts of saccharides which are the other possibility for use as a saccharide component are materials wherein the saccharide has an average molecular weight of from 2,000 - l0,000, and they additionally comprise polyhydric alcohol residues added at the end of the saccharide chains. The preferred polyhydric alcohols are alkylene and polyalkylene glycols, glycerol, xylitol, erythritol and sorbitol, 2148~91 3 case 154-0252 most preferred being polyethylene glycol or polypropylene glycol present such that the number of mols of ethylene oxide or propylene oxide present per mol of saccharide is from l - lO0 - larger polyethylene and polypropylene glycols (especially the former) give rise to higher air-entraining properties, which is usually not desirable.
S When hydrogenated saccharides are used as the saccharide component, they are preferably present as a mixture of which (i) 70-30% by weight (on total weight of hydrogenated saccharides) have molecular weights in the range 180-300;
(ii) 30-70% by weight have molecular weight of from 300 up to 4,000; and (iii) 30% by weight maximum have molecular weights of 4,000 and over.
These proportions may have a considerable effect on the invention. For example, a pl`upollion of greater than 30% of material of molecular weight 4,000 and above results lS in a lowered workability and greater water demand. This also occurs when theproportion of the other molecular weight materials falls outside the stated proportions.
The excellent properties of the invention are not fully realized in this case when only one or the other of the two hydrogenated saccharides (i) and (ii) is used - the presence of both gives best results.
The dosage of the admixture of this invention is dependent on the cement composition used, but basically it will suffice for it to be in sufficient quantity to impart the desired water reduction and adequate workability to the composition. A typical quantity is O.OS to 3.00 percent of the admixture by weight of cement.
It is possible and permissible to use other admixtures in conjunction with the admixture of this invention to achieve particular results.Typical examples of suitable admixtures include air-entraining agents, shrinkage reducing agents, accelerating agents, retarding agents, foaming agents, defoaming agents, rust-inhibiting agents, quick-setting agents and water-soluble polymer substances.
21~82~1 - 4 case 154-0252 The admixture of this invention may be used in generally-used cement compositions such as cement, paste, mortar, grout, and concrete as a matter of course, but it is especially useful in the manufacture of cementitious compositions of comparatively high unit water contents due to the influence of the aggregate used, 5 cementitious compositions for which good workability cannot be obtained by other means, lean-mix concrete of low unit cement content with which good workability is difficult to obtain, pumped concrete, high-strength concrete, cement products, masonry mortar and injection grout.
The invention therefore also provides a method of reducing the water demand of 10 a cementitious composition by the addition thereto of an admixture as hereinabove defined. The components may be added individually to the composition, but it is preferred to add them simultaneously, and more preferably as a blend.
The invention additionally provides an cementitious composition which comprises an admixture as hereinabove defined.
The invention is further described with references to the following non-limitingexamples in which all parts are expressed by weight.
Manufacturing Example 1 Four hundred parts of starch hydroysate and 20 parts of xylitol are added to 100parts of anhydrous toluene and the mixture heated to 80C, at which point 10 parts of 20 tungstophosphoric acid is added and stirring is carried out for 30 minutes. Reaction is then stopped by adding distilled water. The mixture is neutralised and the solvent is removed. The mixture is purified, and all matter of molecular weight exceeding 10,000 is removed by ultrafiltration. The resulting product is designated Sample A.
Manufacturing Example 2 Four hundred parts of starch hydrolysate and 20 parts of erythritol are added to 100 21~82~1 case 154-0252 parts of anhydrous toluene, and the procedures of Manufacturing Example 1 are carried out. Sample B is obtained.
Manufacturing Example 3 Four hundred parts of starch hydrolysates and 20 parts of sorbitol are added to 100 5 parts of anhydrous toluene, and the procedures of Manufacturing Example 1 are carried out. Sample C is obtained.
Manufacturing Example 4 Four hundred parts of starch hydrolysates and 20 parts of glycerol are added to 100 parts of anhydrous toluene, and the procedures of Manufacturing Example 1 are carried 10 out. Sample D is obtained.
Manufactl-nng Example 5 Four hundred parts of starch hydrolysate and 5 parts of ethylene glycol (1 mol) are added to 100 parts of anhydrous toluene, and the procedures of Manufacturing Example 1 are carried out. Sample E is obtained.
15 Manufacturing Example 6 One hundred parts of starch hydrolysate and 20 parts of ethylene glycol (4 mols)are added to 100 parts of anhydrous toluene, and the procedures of ManufacturingExample 1 are carried out. Sample F is obtained.
20 Manufacturing Example 7 One hundred parts of starch hydrolysate and 60 parts of ethylene glycol (12 mols) are added to 100 parts of anhydrous toluene, and the procedures of ManufacturingExample 1 are carried out. Sample G is obtained.
6 Case 154-0252 Manufacturing Example 8 One hundred parts of starch hydrolysate and 120 parts of ehtylene glycol (24 mols) are added to l00 parts of anhydrous toluene, and the procedures of ManufacturingExample l are carried out. Sample H is obtained.
5 Manufacturing Example 9 One hundred parts of starch hydrolysate and 250 parts of ethylene glycol (50 mols) are added to l00 parts of anhydrous toluene, and the procedures of ManufacturingExample l are carried out. Sample I is obtained.
Manufacturing Example l0 One hundred parts of starch hydrolysate and 500 parts of ethylene glycol (l00 mols) are added to l00 parts of anhydrous toluene, and the procedures of Manufacturing Example l are carried out. Sample J is obtained.
Manufacturing Example l l One hundred parts of starch hydrolysate and l0 parts of propylene glycol (l mol)15 are added to l00 parts of anhydrous toluene, and the procedures of Manufacturing Example l are carried out. Sample K is obtained.
Manufacturing Example 12 One hundred parts of starch hydrolysate and 40 parts of propylene glycol (4 mols) are added to l00 parts of anhydrous toluene, and the procedures of 20 Manufacturing Example l are carried out. Sample L is obtained.
- 7 Case 154-0252 Mortar and Concrete Examples 1) Mix Proportions, Preparation and Materials of Mortar and Concrete 1-1) Mortar Mortar is designed for flow of 200 to 210 mm and target air content of 8.0 volume percent in accordance with the mix p,opollions of Table 1, and prepared with the respective materials measured for a yield as mixed of S litres, with mixing done for 120 seconds after introduction of all materials into an ASTM mortar mixer.
1-2) Concrete Concrete is designed for target slump of 18.0 + 0.5 cm and target air content of 4.5 + 0.5 volume percent in accordance with the mix proportions of Table 2, and prepared with the respective materials measured out for a yield as mixed of 80 liters, with mixing done for 90 seconds after introduction of all materials into a 100-liter pan-type power-driven blade mixer.
l S 1-3) Materials a) Fine aggregate:
Oi River system pit sand (specific gravity = 2.58, fineness modulus = 2.76);
b) Coarse aggregate:
Ohme graywacke crushed stone (specific gravity = 2.65, maximum size = 20 mm);
c) Cement:
Ordinary portland cement (specific gravity = 3.16, mixture in equal parts of cement manufactured by Onoda, Sumitomo, and Mitsubishi firms);
- 8 Case 154-0252 d) Water-reducing agent:
A polycarboxylate which is a copolymer of methacrylate salt and methacrylate ester (abbreviated as PCA in Table 3 and Table 4) Lignosulphonate (abbreviated as Lig in Table 3 and Table 4) Melamine sulphonate-formalin condensate (abbreviated as MS in Table 3 and Table 4) Naphthalene sulphonate-formalin condensate (abbreviated as BNS in Table 3 and Table 4);
A carboxylate which is a copolymer and maleate (abbreviated as SMA
in Table 3 and 4) e) Hydrogenated saccharide:
Hydrogenated hydrolysed starches, such as D-Sorbit and PO-20 manufactured by Towa Kasei Kogyo, and Sorbit C, SE-100 manufactured by Nikken Kagaku, designated bl, b2, and b3, obtained by fractioning to the molecular weights of 180-<300, >300 and >4,000 respectively by an ultrafiltration apparatus (a Lab Module Type 20 ex DDS Corp. Denmark).
Polyhydric alcohol adduct of saccharides Sample A: (Average molecular weight = 3,000) Sample B: (Average molecular weight = 3,100) Sample C: (Average molecular weight = 3,100) Sample D: (Average molecular weight = 3,000) Sample E: (Average molecular weight = 2,900) Sample F: (Average molecular weight = 3,100) Sample G: (Average molecular weight = 3,300) Sample H: (Average molecular weight = 3,800) Sample I: (Average molecular weight = 3,400) Sample J: (Average molecular weight = 9,800) Sample K: (Average molecular weight = 2,900) Sample L: (Average molecular weight = 3,100) 21~291 9 Case 154-0252 Sample M: (Polyethlene glycol adduct of 30-80, mfd, by Towa Kasei, average molecular weight = 3,200) Sample N: (Glycerol adduct of starch hydrolysate, mfd. by Towa Kasei, average molecular weight = 350) Sample O: (Propylene glycol adduct of starch hydrolysate, mfd. by Towa Kasei, average molecular weight = 250) Sample P: Polyethylene glycol adduct of starch hydrolysate, average molecular weight = 13,000, ethylene glycol 24-mol adduct) Sample Q: (Polyethylene glycol adduct of starch hydrolysate, average molecular weight = 5,100, ethylene glycol 120-mol adduct) 2) Methods of testing Mortar and Concrete 2-1) Mortar Water-reducing properties and air-entraining properties of mortar are evaluated measuring flow and air content.
a) Flow:
In accordance with JIS A 5201;
b) Air content:
In accordance with JIS A 1116;
c) Water-reducing property evaluation:
Water-reducing propelly is evaluated by the difference between flow when using the additive and flow of plain mortar;
d) Existence of synergistic improvement in water-reducing property:
It is indicated whether the increase in water-reducing property of the water-reducing agent is synergistically improved or is an aggregate sum.
The test results are given in Tables 3 and 4.
21~291 Case 154-0252 2-2) Concrete Concrete is evaluated by time of setting, bleeding, and visual observation of workability in accordance with the following criteria. Compressive strength at 28-day stage is also measured (see Table 5).
a) Slump:
In accordance with JIS A 1101;
b) Air content:
In accordance with JIS A 1128.
c) Compressive strength:
In accordance with JIS A 1118 and JIS A 1132.
d) Time of setting:
In accordance with Appendix 2, JIS A 6204.
e) Bleeding:
In accordance with JIS A 1123.
f) Visual observation:
Workability was evaluated by visual observation as described below.
A (good): The concrete flows smoothly, without any segregation of the aggregate being seen.
B (ordinary): Smooth flow, but with a degree of "crumbling"
(evident presence of coarse aggregate).
C (poor): Much coarse aggregate clearly visible poor flow or no flow at all.
21482~1 11 Case 154-0252 3) Test Results 3-1) Mortar The results of tests with mortar are given in Tables 3 (hydrogenated saccharide) and 4 (polyhydric alcohol adduct of saccharide). In Table 3, the test results of Examples 1 to 13, and the results of plain mortar completely free of water-reducing agents or other cement additives (Comparison Example 1), and mortars with addition of only water-reducing agent (Comparison Example 2), only hydrogenated saccharides (Comparison Examples 3 to 6), and hydrogenated saccharides mixed with water-reducing agent (Comparison Examples 7 to 13) are given.
As can be seen in the results given in Table 3, when the cement additive of this invention is used in mortar (Examples 1 to 12), the following observations may be made:
a) Water-reducing Properties Comparison Example 1 is a case of plain mortar in which there is completely no addition of admixture and the increase in water-reducing properties is evaluated with the flow value of this mortar as the basis.
Examples 1 to 5 are cases of the proportions of bl and b2 being varied. It can be seen that, when bl is in the range of 70 to 30 weight percent and b2 30 to 70 weight percent, the water-reducing properties of the admixture exceeds the aggregated individual water-reducing properties of the water-reducing agent, indicating a synergistic effect and a considerable and unexpected increase in water-reducing properties. In contrast, Comparison Examples 10 and 11 are cases where the mixture ratios of bl and b2 lie outside the abovementioned ranges of bl and b2. In these cases, the water-reducing properties of a combination of such materials is merely the aggregate of the water-reducing 21 i~29:~
12 Case 154-0252 plupel~ies of the individual components.
Examples 6 to 8 are cases wherein the proportion of b3 is varied. It can be seen that, when the quantity of b3 present is not more than 30 weight percent of the total quantity of hydrogenated saccharide, there is no coagulation, and the same synergistic water-reducing properties reported hereinabove are again observed. In contrast, Comparison Example 9 and Comparison Example 12 are cases where the proportions of b3 excee-ling 30 weight percent of the total quantity of hydrogenated saccharides and in these cases mortar will coagulate. In the case of Comparison Example 5 where b3 alone is used, coagulation is considerable.
Examples 9 and 10 are cases wherein the mixture proportions of water-reducing agent and hydrogenated saccharides are varied.
When the ranges of 75 to 25 weight percent water-reducing agent and 25 to 75 weight percent hydrogenated saccharides are used, the water-reducing properties of the combination exceeds the aggregate of the individual water-reducing properties of the water-reducing agent and the hydrogenated saccharides; the effect is synergistic, with considerable improvements in water-reducing properties. In contrast, Comparison Examples 13 and 14 are cases where the ranges of water-reducing agent and hydrogenated saccharides lie outside those given hereinabove. In these cases, the water-reducing plupellies of combination of the water-reducing agent and the hydrogenated saccharides are the aggregate of the individual water-reducing plopellies.
Examples 11 to 13 are cases of lignosulfonate (Lig), melamine sulfonate-formalin condensate (MS), and naphthalene sulfonate-formalin condensate (BNS) combined as other 21482gl - 13 Case 154-0252 ingredients with polycarboxylate (PCA) as the water-reducing agent. When these other water-reducing agents are combined with polycarboxylate, provided that the ratio of the polycarboxylate water-reducing agent and the hydrogenated S polysaccharide is kept within the limits of this invention, the synergistic effect previously reported is still given.
In Comparison Example 6, bl and b2 are combined at a ratio of 1:1, and in this case, the aggregate water-reducing properties of this combination is the aggregate of the individual water-reducing properties of bl and b2. Comparison Examples 7 and 8 are respectively examples of a water-reducing agent combined with bl or b2 alone, and in such cases only the aggregate of the water-reducing plupelLies of the individual components is given.
b) Air entraining Properties On comparing air contents in Examples 1 to 13, they are approximately of the same degree as in Comparison Example 2, and air is not excessively entrained.
Table 4 similarly shows the advantages of using polyhydric alcohol adducts of 20 saccharides.
3-2) Concrete The results of tests with concrete are given in Table 5. The concretes listed in Table 5 are all prepared such that they have slumps in the range 18.0 + 0.5 cm and air contents of 4.5 + 0.5%. In Table 5, the results of tests performed on Examples 33-38 (hydrogenated saccharide-cont~ining) and 3945 (polyhydric alcohol adduct of saccharide containing) and on concretes utilising water-reducing agents not combined with hydrogenated saccharides (Comparison Examples 21 to 24) comparing setting times, compressive strengths, - 14 Case 154-0252 bleeding, and workability are indicated.
As seen in the results given in Table 5, on e~min~tion of the cases wherein the admixture of this invention is used in concrete (Examples 3345 ), the following effects are observed:
a) Water-reducing Properties As is clear from comparing Examples 33 and 34 with Comparison Example 21, and Examples 35-38 with Comparison Examples 22-24, approximately the same slumps are obtained in the examples even when the dosages of admixtures are smaller than in the Comparison Examples, and it can be seen that water-reducing properties have been improved.
b) Air-entraining plopel~ies Air contents are found to be in the range of 4.5 + 0.5% (without using a defoaming agent) and the air-entraining properties are 1 5 low.
c) Bleeding As is clear on comparing with the Comparison Examples, bleeding is considerably reduced and segregation is inhibited.
d) Workability (Visual Observation) Comparison with the Comparison Examples shows that all examples exhibit good workability.
e) Setting Time As is clear on comparing with Comparison Examples, setting time is about 20 to 30 minutes faster than when using a water-reducing agent alone, and there is little or no set retardation.
- 15 2148291 case 154-0252 f) Compressive Strength (28-Day) As is clear on colllpaling with the Comparison Examples, there are attained compressive strengths of about the same degree as those given when using water-reducing agent alone.
21~8291 16 case 154-0252 Water- Sand- Unit Content (g) Cement Cement Ratio Ratio Water Cement Fine Aggregate 0.45 2.75 450 1,000 2,750 Water- Sand- Unit Content (g) Cement Aggregate Ratio Ratio Water Cement Aggregate % Fine Coarse 0.60 46.0 185 285 807 973 17 case 154-0252 Table 3 water reducing Hydrogenated Saccharide agent Dosage') Composition, wt % Dosage') Flow Air Flow Sy gi.llic (mm) (%) Increase Effect in (mm) Water Reduction Example 1 PCA 0.30 70 30 0 0.20 247 6.2 67 yes 2 PCA 0.30 60 40 0 0.20 247 6.1 67 yes 3 PCA 0.30 50 50 0 0.20 246 6.2 66 yes 4 PCA 0.30 40 60 0 0.20 245 6.2 65 yes S PCA 0.30 30 70 0 0.20 243 6.0 63 yes r~
6 PCA 0.30 50 40 10 0.20 246 6.1 66 yes ~a.
7 PCA 0.30 50 35 15 0.20 240 6.0 60 yes 8 PCA 0.30 40 40 20 0.20 238 5.9 58 yes ~_~
9 PCA 0.30 60 40 0 0.15 235 5.7 55 yes 10 PCA 0.30 50 50 0 0.15 235 5.6 55 yes Il PCA 0.25 60 40 0 0.20 247 6.3 67 yes Lig 0.05 12 PCA 0.25 60 40 0 0.20 248 6.0 68 yes MS 0o5 Table 3 (cont'd) 18 Case 154-0252 13 PCA 0.25 60 40 0 0.20 248 6.1 68 yes BNS 0.05 14 SMA 0.30 60 40 0 0.20 248 6.1 68 yes Compa- 1 - - - - - - 180 3.1 rison Example 2 PCA 0.30 - - - - 209 5.1 29 No 3 - - 100 - - 0.20 194 5.3 14 No 4 - - - 100 - 0.20 185 5.3 5 No - - - - 100 0.20 108 5.4 -72 No 6 - - 50 50 - 0.20 189 5.4 9 No 7 PCA 0.30 100 - - 0.20 221 6.1 41 No 8 PCA 0.30 - 100 - 0.20 211 6.1 31 No 9 PCA 0.30 - 100 0.20 145 6.0 -35 No 10 PCA 0.30 75 25 0 0.20 220 6.2 40 No 11 PCA 0.30 25 75 0 0.20 216 6.1 36 No 12 PCA 0.30 41 28 31 0.20 198 6.0 18 No 13 PCA 0.30 60 40 0 0.10 214 5.9 34 No 14 PCA 0.10 60 40 0 0.30 205 6.4 25 No Note 1) Dosage of cement additive by weight percent to weight of cement (in terms of solids).
Table 4 19 Case 154-0252 Water-reducing agent Polyhydric Alcohol Flow Adduct of Saccharide (mm) Air Flow in- Synergistic Effect in Kind Dosage ') Kind Dosage') (%) crease (mm) Water Reduction Example 15 PCA 0.30 Sample A 0.20 250 6.1 70 Yes 16 PCA 0.30 Sample B 0.20 250 5.9 70 Yes 17 PCA 0.30 Sample C 0.20 251 6.2 71 Yes 18 PCA 0.30 Sample D 0.20 250 6.0 70 Yes 19 PCA 0.30 Sample E 0.20 251 6.1 71 Yes PCA 0.30 Sample F 0.20 248 6.2 69 Yes 21 PCA 0.30 Sample G 0.20 250 6.0 70 Yes 22 PCA 0.30 Sample H 0.20 252 6.1 72 Yes 23 PCA 0.30 Sample I 0.20 248 6.5 68 Yes 24 PCA 0.30 Sample J 0.20 250 7.0 70 Yes PCA 0 30 Sample K 0.20 251 6.0 71 Yes 2~
26 PCA 0.30 Sample L 0.20 253 6.1 73 Yes ~. "
27 PCA 0.30 Sample M 0.20 254 5.9 74 Yes 28 PCA 0.30 Sample N 0.20 253 6.0 73 Yes 29 PCA 0.30 Sample O 0.20 253 6.0 73 Yes SMA 0.30 Sample P 0.20 253 6.0 73 Yes 31 PCA 0.25 Sample Q 0.20 253 6.0 73 Yes BNS 0.05 Table 4 (cont'd) 20 Case 154-0252 32 PCA 0.25 Sample G 0.20 253 6.0 73 Yes MS 0.05 Comparison 15 - - Sample A 0.20 193 5.4 13 No Example 16 - - Sample D 0.28 183 5.8 13 No 17 - - Sample C 0.20 193 5.4 15 No 18 - - Sample G 0.20 199 5.5 19 No 19 PCA 0.30 Sample P 0.20 160 6.0 -20 No PCA 0.30 Sample Q 0.30 243 13.5 63 Yes Note 1) Dosage of cement additive by weight percent to weight of cement (in terms of solids).
21 case 154-0252 Table 5 water- Hydrogenated Saccharide Polyhydric Alcohol Setting Time Co.l.~ ive Bleeding Workability reducing Composition, wt % Adduct of (hr-min) Evaluation agent Saccharide Strength (cm3 / cm2) (28-Day) ge') Dosage Kind Dos- Initial Final (kgf/cm2) Example 33 PCA 0.15 60 40 0 0.10 - - 6-10 8-10 327 0.25 A
34 PCA 0.15 50 30 10 0.10 - - 6-15 8-20 330 0.26 A
35 PCA 0.10 60 40 0 0.10 - - 6-40 8-45 325 0.28 A
Lig 0.05 36 PCA 0.10 60 40 0 0.10 - - 6-00 8-00 328 0.26 A
MS 0.05 37 PCA 0.10 60 40 0 0.10 - - 6-20 8-20 326 0.27 A ~_~
BNS 0.05 38 SMA O 15 60 40 0 0.10 - - 6-15 8-25 322 0.25 A C~
39 PCA 0.15 - Sample B 0.10 6-10 8-10 327 0.25 A
40 PCA 0.15 - Sample B 0.10 6-15 8-20 330 0.26 A
41 PCA 0.10 - - - - Sample B 0.10 6-35 8-40 326 0.26 A
Lig 0.05 42 PCA 0.10 - - - - Sample B 0,1O 6-05 8-05 329 0.24 A
MS 0.05 43 PCA 0.10 - - - - Sample B 0.10 6-15 8-15 327 0.25 A
BNS 0.05 22 Case 154-0252 44 SMA 0.15 - - - - Sample B 0.10 6-15 8-25 322 0.25 A
45 PCA 0.15 60 30 10 0.05 Sample B o.o5 6-15 8-25 322 0.25 A
Com- 21 PCA 0.30 - - - - - - 6-45 8-55 322 0.35 Bparison Example 22 PCA 0.20 - - - - - - 6-50 8-50 324 0.37 C
Lig 0.10 23 PCA 0.20 - - - - - - 6-30 8-30 322 0.35 C
MS 0.10 24 PCA 0.20 - - - - - - 6-40 8.35 322 0.34 B
BNS 0.10 Note 1) Dosage of cement additive by weight percent to weight of cement (in terms of solids) C;:3
This invention relates to an admixture for cementitious compositions such as grouts, mortars and concretes.
Increasing difficulty in and expense of obtaining high quality aggregate for usein cementitious compositions such as concrete has forced manufacturers to resort to S lower grade materials such as crushed stone, marine sand and even crushed concrete obtained from the demolition of old structures. This leads to problems with the concrete such as higher water demand, bleeding and lower workability and pumpability.
It has been attempted to overcome these problems by means of admixtures. Typical of such admixtures are those already well known in the art, such as lignosulphonates, naphthalene sulphonate-formaldehyde condensates and various saccharides. Such materials reduce water requirement but also delay setting of the concrete, something which is not always desirable.
It has now been found that a blend of particular materials can greatly decrease the quantity of water required for a given cementitious mix while not significantly lS increasing set time. In addition, the blend does not cause excessive aeration (a major problem with some known admixtures) and it inhibits bleeding and improves workability. The invention therefore provides an admixture for use in a cementitious composition, which admixture consists of (a) from 75-25% by weight of a water-reducing agent whose major component is a polycarboxylate; and (b) from 25-75% by weight of at least one saccharide component selected from hydrogenated saccharides and polyhydric alcohol adducts of saccharides.
The water-reducing agent has as a major component a polycarboxylate which is 21~8~91 -- 2 Case 154-0252 known to be a water-reducing agent in its own right. By "major component" is meant that the polycarboxylate or polycarboxylates (it is permissible to use more than one such material) is present in higher weight p~vpol~ion than any other individual component in the water-reducing agent. It is therefore possible for the polycarboxylate 5 to comprise less than 50% of the weight of the water-reducing agent, although it is preferable that it comprises at least 50%. More preferably, the water reducing agent comprises at least 60% by weight of polycarboxylate and most preferably it is 100%
polycarboxylate. Typical examples include poly(acrylate salt-acrylate ester) copolymers, poly(methacrylic acid-methacrylate) copolymers, poly(styrene- maleate salt) l0 copolymers, and poly(styrene-maleate ester) copolymers. Such materials are readily available commercially, for example, the SP-8 series of materials from NMB Ltd.
The water-reducing agent may additionally contain at least one other non-carboxylate water-reducing agent. Any known water-reducing agent is satisfactory and typical examples include lignosulphonates and naphthalene sulphonate-formaldehyde 15 condensates.
The hydrogenated saccharides which are one possibility for use in this inventionas a saccharide component as hereinabove mentioned may be derived from mono- or disaccharides, but are preferably derived from polysaccharides, more preferably starches. Examples of suitable saccharides which may be hydrogenated include starch 20 hydrolysates, glucose fermentation products, celluloses, cellulose hydrolysates, hemicelluloses and hemicellulose hydrolystes, starch hydrolysates being especially desirable. Commercial examples of suitable materials include D-Sorbit and PO-20 of Towa Kasei and SE-l00 of Nikken Kagaku. Other materials include hydrogenated oligosaccharides, for example, of the type described in United States Patent 4,073,658.
The polyhydric alcohol adducts of saccharides which are the other possibility for use as a saccharide component are materials wherein the saccharide has an average molecular weight of from 2,000 - l0,000, and they additionally comprise polyhydric alcohol residues added at the end of the saccharide chains. The preferred polyhydric alcohols are alkylene and polyalkylene glycols, glycerol, xylitol, erythritol and sorbitol, 2148~91 3 case 154-0252 most preferred being polyethylene glycol or polypropylene glycol present such that the number of mols of ethylene oxide or propylene oxide present per mol of saccharide is from l - lO0 - larger polyethylene and polypropylene glycols (especially the former) give rise to higher air-entraining properties, which is usually not desirable.
S When hydrogenated saccharides are used as the saccharide component, they are preferably present as a mixture of which (i) 70-30% by weight (on total weight of hydrogenated saccharides) have molecular weights in the range 180-300;
(ii) 30-70% by weight have molecular weight of from 300 up to 4,000; and (iii) 30% by weight maximum have molecular weights of 4,000 and over.
These proportions may have a considerable effect on the invention. For example, a pl`upollion of greater than 30% of material of molecular weight 4,000 and above results lS in a lowered workability and greater water demand. This also occurs when theproportion of the other molecular weight materials falls outside the stated proportions.
The excellent properties of the invention are not fully realized in this case when only one or the other of the two hydrogenated saccharides (i) and (ii) is used - the presence of both gives best results.
The dosage of the admixture of this invention is dependent on the cement composition used, but basically it will suffice for it to be in sufficient quantity to impart the desired water reduction and adequate workability to the composition. A typical quantity is O.OS to 3.00 percent of the admixture by weight of cement.
It is possible and permissible to use other admixtures in conjunction with the admixture of this invention to achieve particular results.Typical examples of suitable admixtures include air-entraining agents, shrinkage reducing agents, accelerating agents, retarding agents, foaming agents, defoaming agents, rust-inhibiting agents, quick-setting agents and water-soluble polymer substances.
21~82~1 - 4 case 154-0252 The admixture of this invention may be used in generally-used cement compositions such as cement, paste, mortar, grout, and concrete as a matter of course, but it is especially useful in the manufacture of cementitious compositions of comparatively high unit water contents due to the influence of the aggregate used, 5 cementitious compositions for which good workability cannot be obtained by other means, lean-mix concrete of low unit cement content with which good workability is difficult to obtain, pumped concrete, high-strength concrete, cement products, masonry mortar and injection grout.
The invention therefore also provides a method of reducing the water demand of 10 a cementitious composition by the addition thereto of an admixture as hereinabove defined. The components may be added individually to the composition, but it is preferred to add them simultaneously, and more preferably as a blend.
The invention additionally provides an cementitious composition which comprises an admixture as hereinabove defined.
The invention is further described with references to the following non-limitingexamples in which all parts are expressed by weight.
Manufacturing Example 1 Four hundred parts of starch hydroysate and 20 parts of xylitol are added to 100parts of anhydrous toluene and the mixture heated to 80C, at which point 10 parts of 20 tungstophosphoric acid is added and stirring is carried out for 30 minutes. Reaction is then stopped by adding distilled water. The mixture is neutralised and the solvent is removed. The mixture is purified, and all matter of molecular weight exceeding 10,000 is removed by ultrafiltration. The resulting product is designated Sample A.
Manufacturing Example 2 Four hundred parts of starch hydrolysate and 20 parts of erythritol are added to 100 21~82~1 case 154-0252 parts of anhydrous toluene, and the procedures of Manufacturing Example 1 are carried out. Sample B is obtained.
Manufacturing Example 3 Four hundred parts of starch hydrolysates and 20 parts of sorbitol are added to 100 5 parts of anhydrous toluene, and the procedures of Manufacturing Example 1 are carried out. Sample C is obtained.
Manufacturing Example 4 Four hundred parts of starch hydrolysates and 20 parts of glycerol are added to 100 parts of anhydrous toluene, and the procedures of Manufacturing Example 1 are carried 10 out. Sample D is obtained.
Manufactl-nng Example 5 Four hundred parts of starch hydrolysate and 5 parts of ethylene glycol (1 mol) are added to 100 parts of anhydrous toluene, and the procedures of Manufacturing Example 1 are carried out. Sample E is obtained.
15 Manufacturing Example 6 One hundred parts of starch hydrolysate and 20 parts of ethylene glycol (4 mols)are added to 100 parts of anhydrous toluene, and the procedures of ManufacturingExample 1 are carried out. Sample F is obtained.
20 Manufacturing Example 7 One hundred parts of starch hydrolysate and 60 parts of ethylene glycol (12 mols) are added to 100 parts of anhydrous toluene, and the procedures of ManufacturingExample 1 are carried out. Sample G is obtained.
6 Case 154-0252 Manufacturing Example 8 One hundred parts of starch hydrolysate and 120 parts of ehtylene glycol (24 mols) are added to l00 parts of anhydrous toluene, and the procedures of ManufacturingExample l are carried out. Sample H is obtained.
5 Manufacturing Example 9 One hundred parts of starch hydrolysate and 250 parts of ethylene glycol (50 mols) are added to l00 parts of anhydrous toluene, and the procedures of ManufacturingExample l are carried out. Sample I is obtained.
Manufacturing Example l0 One hundred parts of starch hydrolysate and 500 parts of ethylene glycol (l00 mols) are added to l00 parts of anhydrous toluene, and the procedures of Manufacturing Example l are carried out. Sample J is obtained.
Manufacturing Example l l One hundred parts of starch hydrolysate and l0 parts of propylene glycol (l mol)15 are added to l00 parts of anhydrous toluene, and the procedures of Manufacturing Example l are carried out. Sample K is obtained.
Manufacturing Example 12 One hundred parts of starch hydrolysate and 40 parts of propylene glycol (4 mols) are added to l00 parts of anhydrous toluene, and the procedures of 20 Manufacturing Example l are carried out. Sample L is obtained.
- 7 Case 154-0252 Mortar and Concrete Examples 1) Mix Proportions, Preparation and Materials of Mortar and Concrete 1-1) Mortar Mortar is designed for flow of 200 to 210 mm and target air content of 8.0 volume percent in accordance with the mix p,opollions of Table 1, and prepared with the respective materials measured for a yield as mixed of S litres, with mixing done for 120 seconds after introduction of all materials into an ASTM mortar mixer.
1-2) Concrete Concrete is designed for target slump of 18.0 + 0.5 cm and target air content of 4.5 + 0.5 volume percent in accordance with the mix proportions of Table 2, and prepared with the respective materials measured out for a yield as mixed of 80 liters, with mixing done for 90 seconds after introduction of all materials into a 100-liter pan-type power-driven blade mixer.
l S 1-3) Materials a) Fine aggregate:
Oi River system pit sand (specific gravity = 2.58, fineness modulus = 2.76);
b) Coarse aggregate:
Ohme graywacke crushed stone (specific gravity = 2.65, maximum size = 20 mm);
c) Cement:
Ordinary portland cement (specific gravity = 3.16, mixture in equal parts of cement manufactured by Onoda, Sumitomo, and Mitsubishi firms);
- 8 Case 154-0252 d) Water-reducing agent:
A polycarboxylate which is a copolymer of methacrylate salt and methacrylate ester (abbreviated as PCA in Table 3 and Table 4) Lignosulphonate (abbreviated as Lig in Table 3 and Table 4) Melamine sulphonate-formalin condensate (abbreviated as MS in Table 3 and Table 4) Naphthalene sulphonate-formalin condensate (abbreviated as BNS in Table 3 and Table 4);
A carboxylate which is a copolymer and maleate (abbreviated as SMA
in Table 3 and 4) e) Hydrogenated saccharide:
Hydrogenated hydrolysed starches, such as D-Sorbit and PO-20 manufactured by Towa Kasei Kogyo, and Sorbit C, SE-100 manufactured by Nikken Kagaku, designated bl, b2, and b3, obtained by fractioning to the molecular weights of 180-<300, >300 and >4,000 respectively by an ultrafiltration apparatus (a Lab Module Type 20 ex DDS Corp. Denmark).
Polyhydric alcohol adduct of saccharides Sample A: (Average molecular weight = 3,000) Sample B: (Average molecular weight = 3,100) Sample C: (Average molecular weight = 3,100) Sample D: (Average molecular weight = 3,000) Sample E: (Average molecular weight = 2,900) Sample F: (Average molecular weight = 3,100) Sample G: (Average molecular weight = 3,300) Sample H: (Average molecular weight = 3,800) Sample I: (Average molecular weight = 3,400) Sample J: (Average molecular weight = 9,800) Sample K: (Average molecular weight = 2,900) Sample L: (Average molecular weight = 3,100) 21~291 9 Case 154-0252 Sample M: (Polyethlene glycol adduct of 30-80, mfd, by Towa Kasei, average molecular weight = 3,200) Sample N: (Glycerol adduct of starch hydrolysate, mfd. by Towa Kasei, average molecular weight = 350) Sample O: (Propylene glycol adduct of starch hydrolysate, mfd. by Towa Kasei, average molecular weight = 250) Sample P: Polyethylene glycol adduct of starch hydrolysate, average molecular weight = 13,000, ethylene glycol 24-mol adduct) Sample Q: (Polyethylene glycol adduct of starch hydrolysate, average molecular weight = 5,100, ethylene glycol 120-mol adduct) 2) Methods of testing Mortar and Concrete 2-1) Mortar Water-reducing properties and air-entraining properties of mortar are evaluated measuring flow and air content.
a) Flow:
In accordance with JIS A 5201;
b) Air content:
In accordance with JIS A 1116;
c) Water-reducing property evaluation:
Water-reducing propelly is evaluated by the difference between flow when using the additive and flow of plain mortar;
d) Existence of synergistic improvement in water-reducing property:
It is indicated whether the increase in water-reducing property of the water-reducing agent is synergistically improved or is an aggregate sum.
The test results are given in Tables 3 and 4.
21~291 Case 154-0252 2-2) Concrete Concrete is evaluated by time of setting, bleeding, and visual observation of workability in accordance with the following criteria. Compressive strength at 28-day stage is also measured (see Table 5).
a) Slump:
In accordance with JIS A 1101;
b) Air content:
In accordance with JIS A 1128.
c) Compressive strength:
In accordance with JIS A 1118 and JIS A 1132.
d) Time of setting:
In accordance with Appendix 2, JIS A 6204.
e) Bleeding:
In accordance with JIS A 1123.
f) Visual observation:
Workability was evaluated by visual observation as described below.
A (good): The concrete flows smoothly, without any segregation of the aggregate being seen.
B (ordinary): Smooth flow, but with a degree of "crumbling"
(evident presence of coarse aggregate).
C (poor): Much coarse aggregate clearly visible poor flow or no flow at all.
21482~1 11 Case 154-0252 3) Test Results 3-1) Mortar The results of tests with mortar are given in Tables 3 (hydrogenated saccharide) and 4 (polyhydric alcohol adduct of saccharide). In Table 3, the test results of Examples 1 to 13, and the results of plain mortar completely free of water-reducing agents or other cement additives (Comparison Example 1), and mortars with addition of only water-reducing agent (Comparison Example 2), only hydrogenated saccharides (Comparison Examples 3 to 6), and hydrogenated saccharides mixed with water-reducing agent (Comparison Examples 7 to 13) are given.
As can be seen in the results given in Table 3, when the cement additive of this invention is used in mortar (Examples 1 to 12), the following observations may be made:
a) Water-reducing Properties Comparison Example 1 is a case of plain mortar in which there is completely no addition of admixture and the increase in water-reducing properties is evaluated with the flow value of this mortar as the basis.
Examples 1 to 5 are cases of the proportions of bl and b2 being varied. It can be seen that, when bl is in the range of 70 to 30 weight percent and b2 30 to 70 weight percent, the water-reducing properties of the admixture exceeds the aggregated individual water-reducing properties of the water-reducing agent, indicating a synergistic effect and a considerable and unexpected increase in water-reducing properties. In contrast, Comparison Examples 10 and 11 are cases where the mixture ratios of bl and b2 lie outside the abovementioned ranges of bl and b2. In these cases, the water-reducing properties of a combination of such materials is merely the aggregate of the water-reducing 21 i~29:~
12 Case 154-0252 plupel~ies of the individual components.
Examples 6 to 8 are cases wherein the proportion of b3 is varied. It can be seen that, when the quantity of b3 present is not more than 30 weight percent of the total quantity of hydrogenated saccharide, there is no coagulation, and the same synergistic water-reducing properties reported hereinabove are again observed. In contrast, Comparison Example 9 and Comparison Example 12 are cases where the proportions of b3 excee-ling 30 weight percent of the total quantity of hydrogenated saccharides and in these cases mortar will coagulate. In the case of Comparison Example 5 where b3 alone is used, coagulation is considerable.
Examples 9 and 10 are cases wherein the mixture proportions of water-reducing agent and hydrogenated saccharides are varied.
When the ranges of 75 to 25 weight percent water-reducing agent and 25 to 75 weight percent hydrogenated saccharides are used, the water-reducing properties of the combination exceeds the aggregate of the individual water-reducing properties of the water-reducing agent and the hydrogenated saccharides; the effect is synergistic, with considerable improvements in water-reducing properties. In contrast, Comparison Examples 13 and 14 are cases where the ranges of water-reducing agent and hydrogenated saccharides lie outside those given hereinabove. In these cases, the water-reducing plupellies of combination of the water-reducing agent and the hydrogenated saccharides are the aggregate of the individual water-reducing plopellies.
Examples 11 to 13 are cases of lignosulfonate (Lig), melamine sulfonate-formalin condensate (MS), and naphthalene sulfonate-formalin condensate (BNS) combined as other 21482gl - 13 Case 154-0252 ingredients with polycarboxylate (PCA) as the water-reducing agent. When these other water-reducing agents are combined with polycarboxylate, provided that the ratio of the polycarboxylate water-reducing agent and the hydrogenated S polysaccharide is kept within the limits of this invention, the synergistic effect previously reported is still given.
In Comparison Example 6, bl and b2 are combined at a ratio of 1:1, and in this case, the aggregate water-reducing properties of this combination is the aggregate of the individual water-reducing properties of bl and b2. Comparison Examples 7 and 8 are respectively examples of a water-reducing agent combined with bl or b2 alone, and in such cases only the aggregate of the water-reducing plupelLies of the individual components is given.
b) Air entraining Properties On comparing air contents in Examples 1 to 13, they are approximately of the same degree as in Comparison Example 2, and air is not excessively entrained.
Table 4 similarly shows the advantages of using polyhydric alcohol adducts of 20 saccharides.
3-2) Concrete The results of tests with concrete are given in Table 5. The concretes listed in Table 5 are all prepared such that they have slumps in the range 18.0 + 0.5 cm and air contents of 4.5 + 0.5%. In Table 5, the results of tests performed on Examples 33-38 (hydrogenated saccharide-cont~ining) and 3945 (polyhydric alcohol adduct of saccharide containing) and on concretes utilising water-reducing agents not combined with hydrogenated saccharides (Comparison Examples 21 to 24) comparing setting times, compressive strengths, - 14 Case 154-0252 bleeding, and workability are indicated.
As seen in the results given in Table 5, on e~min~tion of the cases wherein the admixture of this invention is used in concrete (Examples 3345 ), the following effects are observed:
a) Water-reducing Properties As is clear from comparing Examples 33 and 34 with Comparison Example 21, and Examples 35-38 with Comparison Examples 22-24, approximately the same slumps are obtained in the examples even when the dosages of admixtures are smaller than in the Comparison Examples, and it can be seen that water-reducing properties have been improved.
b) Air-entraining plopel~ies Air contents are found to be in the range of 4.5 + 0.5% (without using a defoaming agent) and the air-entraining properties are 1 5 low.
c) Bleeding As is clear on comparing with the Comparison Examples, bleeding is considerably reduced and segregation is inhibited.
d) Workability (Visual Observation) Comparison with the Comparison Examples shows that all examples exhibit good workability.
e) Setting Time As is clear on comparing with Comparison Examples, setting time is about 20 to 30 minutes faster than when using a water-reducing agent alone, and there is little or no set retardation.
- 15 2148291 case 154-0252 f) Compressive Strength (28-Day) As is clear on colllpaling with the Comparison Examples, there are attained compressive strengths of about the same degree as those given when using water-reducing agent alone.
21~8291 16 case 154-0252 Water- Sand- Unit Content (g) Cement Cement Ratio Ratio Water Cement Fine Aggregate 0.45 2.75 450 1,000 2,750 Water- Sand- Unit Content (g) Cement Aggregate Ratio Ratio Water Cement Aggregate % Fine Coarse 0.60 46.0 185 285 807 973 17 case 154-0252 Table 3 water reducing Hydrogenated Saccharide agent Dosage') Composition, wt % Dosage') Flow Air Flow Sy gi.llic (mm) (%) Increase Effect in (mm) Water Reduction Example 1 PCA 0.30 70 30 0 0.20 247 6.2 67 yes 2 PCA 0.30 60 40 0 0.20 247 6.1 67 yes 3 PCA 0.30 50 50 0 0.20 246 6.2 66 yes 4 PCA 0.30 40 60 0 0.20 245 6.2 65 yes S PCA 0.30 30 70 0 0.20 243 6.0 63 yes r~
6 PCA 0.30 50 40 10 0.20 246 6.1 66 yes ~a.
7 PCA 0.30 50 35 15 0.20 240 6.0 60 yes 8 PCA 0.30 40 40 20 0.20 238 5.9 58 yes ~_~
9 PCA 0.30 60 40 0 0.15 235 5.7 55 yes 10 PCA 0.30 50 50 0 0.15 235 5.6 55 yes Il PCA 0.25 60 40 0 0.20 247 6.3 67 yes Lig 0.05 12 PCA 0.25 60 40 0 0.20 248 6.0 68 yes MS 0o5 Table 3 (cont'd) 18 Case 154-0252 13 PCA 0.25 60 40 0 0.20 248 6.1 68 yes BNS 0.05 14 SMA 0.30 60 40 0 0.20 248 6.1 68 yes Compa- 1 - - - - - - 180 3.1 rison Example 2 PCA 0.30 - - - - 209 5.1 29 No 3 - - 100 - - 0.20 194 5.3 14 No 4 - - - 100 - 0.20 185 5.3 5 No - - - - 100 0.20 108 5.4 -72 No 6 - - 50 50 - 0.20 189 5.4 9 No 7 PCA 0.30 100 - - 0.20 221 6.1 41 No 8 PCA 0.30 - 100 - 0.20 211 6.1 31 No 9 PCA 0.30 - 100 0.20 145 6.0 -35 No 10 PCA 0.30 75 25 0 0.20 220 6.2 40 No 11 PCA 0.30 25 75 0 0.20 216 6.1 36 No 12 PCA 0.30 41 28 31 0.20 198 6.0 18 No 13 PCA 0.30 60 40 0 0.10 214 5.9 34 No 14 PCA 0.10 60 40 0 0.30 205 6.4 25 No Note 1) Dosage of cement additive by weight percent to weight of cement (in terms of solids).
Table 4 19 Case 154-0252 Water-reducing agent Polyhydric Alcohol Flow Adduct of Saccharide (mm) Air Flow in- Synergistic Effect in Kind Dosage ') Kind Dosage') (%) crease (mm) Water Reduction Example 15 PCA 0.30 Sample A 0.20 250 6.1 70 Yes 16 PCA 0.30 Sample B 0.20 250 5.9 70 Yes 17 PCA 0.30 Sample C 0.20 251 6.2 71 Yes 18 PCA 0.30 Sample D 0.20 250 6.0 70 Yes 19 PCA 0.30 Sample E 0.20 251 6.1 71 Yes PCA 0.30 Sample F 0.20 248 6.2 69 Yes 21 PCA 0.30 Sample G 0.20 250 6.0 70 Yes 22 PCA 0.30 Sample H 0.20 252 6.1 72 Yes 23 PCA 0.30 Sample I 0.20 248 6.5 68 Yes 24 PCA 0.30 Sample J 0.20 250 7.0 70 Yes PCA 0 30 Sample K 0.20 251 6.0 71 Yes 2~
26 PCA 0.30 Sample L 0.20 253 6.1 73 Yes ~. "
27 PCA 0.30 Sample M 0.20 254 5.9 74 Yes 28 PCA 0.30 Sample N 0.20 253 6.0 73 Yes 29 PCA 0.30 Sample O 0.20 253 6.0 73 Yes SMA 0.30 Sample P 0.20 253 6.0 73 Yes 31 PCA 0.25 Sample Q 0.20 253 6.0 73 Yes BNS 0.05 Table 4 (cont'd) 20 Case 154-0252 32 PCA 0.25 Sample G 0.20 253 6.0 73 Yes MS 0.05 Comparison 15 - - Sample A 0.20 193 5.4 13 No Example 16 - - Sample D 0.28 183 5.8 13 No 17 - - Sample C 0.20 193 5.4 15 No 18 - - Sample G 0.20 199 5.5 19 No 19 PCA 0.30 Sample P 0.20 160 6.0 -20 No PCA 0.30 Sample Q 0.30 243 13.5 63 Yes Note 1) Dosage of cement additive by weight percent to weight of cement (in terms of solids).
21 case 154-0252 Table 5 water- Hydrogenated Saccharide Polyhydric Alcohol Setting Time Co.l.~ ive Bleeding Workability reducing Composition, wt % Adduct of (hr-min) Evaluation agent Saccharide Strength (cm3 / cm2) (28-Day) ge') Dosage Kind Dos- Initial Final (kgf/cm2) Example 33 PCA 0.15 60 40 0 0.10 - - 6-10 8-10 327 0.25 A
34 PCA 0.15 50 30 10 0.10 - - 6-15 8-20 330 0.26 A
35 PCA 0.10 60 40 0 0.10 - - 6-40 8-45 325 0.28 A
Lig 0.05 36 PCA 0.10 60 40 0 0.10 - - 6-00 8-00 328 0.26 A
MS 0.05 37 PCA 0.10 60 40 0 0.10 - - 6-20 8-20 326 0.27 A ~_~
BNS 0.05 38 SMA O 15 60 40 0 0.10 - - 6-15 8-25 322 0.25 A C~
39 PCA 0.15 - Sample B 0.10 6-10 8-10 327 0.25 A
40 PCA 0.15 - Sample B 0.10 6-15 8-20 330 0.26 A
41 PCA 0.10 - - - - Sample B 0.10 6-35 8-40 326 0.26 A
Lig 0.05 42 PCA 0.10 - - - - Sample B 0,1O 6-05 8-05 329 0.24 A
MS 0.05 43 PCA 0.10 - - - - Sample B 0.10 6-15 8-15 327 0.25 A
BNS 0.05 22 Case 154-0252 44 SMA 0.15 - - - - Sample B 0.10 6-15 8-25 322 0.25 A
45 PCA 0.15 60 30 10 0.05 Sample B o.o5 6-15 8-25 322 0.25 A
Com- 21 PCA 0.30 - - - - - - 6-45 8-55 322 0.35 Bparison Example 22 PCA 0.20 - - - - - - 6-50 8-50 324 0.37 C
Lig 0.10 23 PCA 0.20 - - - - - - 6-30 8-30 322 0.35 C
MS 0.10 24 PCA 0.20 - - - - - - 6-40 8.35 322 0.34 B
BNS 0.10 Note 1) Dosage of cement additive by weight percent to weight of cement (in terms of solids) C;:3
Claims (10)
1. An admixture for use in a cementitious composition, which admixture consists of (a) from 75-25% by weight of a polycarboxylate water-reducing agent whose major component is a polycarboxylate; and (b) from 25-75% by weight of at least one saccharide component selected from the group consisting of hydrogenated saccharides and polyhydric alcohol adducts of saccharides.
2. An admixture according to claim 1, wherein the water reducing agent comprises at least 60% by weight of polycarboxylate.
3. An admixture according to claim 1, wherein the polycarboxylate is selected from the group consisting of poly(acrylate salt-acrylate ester) copolymers, poly(methacrylic acid-methacrylate) copolymers, poly(styrene-maleate salt) copolymers, and poly(styrene-maleate ester) copolymers.
4. An admixture according to claim 1, wherein the saccharide component comprises hydrogenated saccharide in which (i) 70-30% by weight (on total weight of hydrogenated saccharides) have molecular weights in the range 180-300;
(ii) 30-70% by weight have molecular weight of from 300 up to 4,000; and (iii) 30% by weight maximum have molecular weights of 4,000 and over.
(ii) 30-70% by weight have molecular weight of from 300 up to 4,000; and (iii) 30% by weight maximum have molecular weights of 4,000 and over.
5. An admixture according to claim 1, wherein the hydrogenated saccharide is a polysaccharide.
6. An admixture according to claim 5, wherein the polysaccharide is a hydrogenated hemicellulose or a hydrogenated hydrolysed starch.
7. An admixture according to claim 1, wherein the polyhydric alcohol from which the polyhydric alcohol adduct of a polysaccharide is derived is selected from the group consisting of alkylene and polyalkylene glycols, glycerol, xylitol, erythritol and sorbitol.
8. An admixture according to claim 7, wherein the polyhydric alcohol is selected from the group consisting of polyethylene glycol or polypropylene glycol present suchthe number of mols of ethylene oxide or propylene oxide present per mol of saccharide is from 1 - 100.
9. A method of reducing the water demand of a cementitious composition by the addition thereto of an admixture according to claim 1.
10. A cementitious composition which comprises an admixture according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002148291A CA2148291A1 (en) | 1995-05-01 | 1995-05-01 | Water-reducing admixtures for cementitious compositions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002148291A CA2148291A1 (en) | 1995-05-01 | 1995-05-01 | Water-reducing admixtures for cementitious compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2148291A1 true CA2148291A1 (en) | 1996-11-02 |
Family
ID=4155755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002148291A Abandoned CA2148291A1 (en) | 1995-05-01 | 1995-05-01 | Water-reducing admixtures for cementitious compositions |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2148291A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7883577B2 (en) | 2003-04-25 | 2011-02-08 | Construction Research And Technology Gmbh | Rheology stabilizer for cementitious compositions |
-
1995
- 1995-05-01 CA CA002148291A patent/CA2148291A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7883577B2 (en) | 2003-04-25 | 2011-02-08 | Construction Research And Technology Gmbh | Rheology stabilizer for cementitious compositions |
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