WO2003018505A2 - Admixture for cementitious compositions and process for preparation thereof - Google Patents
Admixture for cementitious compositions and process for preparation thereof Download PDFInfo
- Publication number
- WO2003018505A2 WO2003018505A2 PCT/GB2002/003926 GB0203926W WO03018505A2 WO 2003018505 A2 WO2003018505 A2 WO 2003018505A2 GB 0203926 W GB0203926 W GB 0203926W WO 03018505 A2 WO03018505 A2 WO 03018505A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- admixture
- plasticiser
- mixture
- water
- viscosity modifying
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- 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
- 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
- C04B2111/00103—Self-compacting mixtures
Definitions
- the present invention relates to admixtures for cementitious compositions and, in particular, to a single dose admixture for cementitious compositions.
- the present invention also provides a method for preparing such admixtures .
- cementitious compositions refers to any cement, concrete, artificial or natural stone, mortar, grout, aggregate, slurry compositions or mixtures thereof.
- Preferred cementitious compositions include concrete such as self-compacting concrete, cementitious mortar or grout, or chalk slurries.
- Self-compacting concrete is particularly preferred.
- Concrete is comprised principally of cement, coarse aggregate, fine aggregate and water.
- the strength of the concrete is linked to the water cement ratio (w/c ratio) .
- a low w/c value corresponds to a high strength.
- a low strength aggregate will produce a lower strength concrete.
- Aggregates are classified according to their type, shape and particle size. They are embedded in a matrix of cement paste.
- aggregates examples include processed land based and marine gravels and crushed rocks such as limestones and granites.
- aggregates can be sub-divided into coarse and fine fractions and are combined proportionally to a desired overall particle distribution for a concrete mixture.
- the most commonly used cement is Portland cement; this is often blended or mixed with other hydraulic cement materials such as ground granulated blast furnace slag and pulverised fuel ash (fly-ash) to obtain specific concrete characteristics .
- Portland cement is made from a mixture of approximately 75% of a calcareous material such as limestone or chalk and 25% of a siliceous material such as clay or shale. Both materials are intimately mixed and together with some minor components are heated (burned) to a high temperature at which they fuse together. The resultant clinker is finely ground to form Portland Cement.
- Portland cement is a complex mixture of multi- component, mineral solid-solutions. Among these, are compounds of calcium silicate and calcium aluminate that hydrate in the presence of water.
- the essential binding component has been identified as calcium silicate hydrate (CSH) .
- CSH calcium silicate hydrate
- Most commercially produced concretes are specially designed mixes. These mixes are produced for specific applications or to have specific properties, for example for placing underwater and for placing by concrete pumping and for other purposes . These concrete types may incorporate small amounts of chemicals known as admixtures. Admixtures modify one or more specific properties of the fresh or hardened concrete .
- a retarding admixture will defer the setting of the concrete. This is useful when slow rates of placement are envisaged or for placing under high summer temperatures .
- admixtures are used to control properties such as water permeability, concrete consistence, water demand and resistance to freeze/thaw damage.
- the workability of concrete is related to the water: cement ratio and the mix constituents including the particle size distribution of aggregate and cement particles.
- the higher the water: cement ratio generally the more workable is the concrete.
- a high water: cement ratio can, however, adversely affect the strength of the concrete. For example, if excess free water is present, which has not been absorbed into the aggregate and cement or is not adsorbed and used in the hydration reaction, this leaves voids in the hardened concrete as it dries out. The result of this is lower strength and increased porosity leading to a potential reduction in the durability of the concrete in the structure. Additionally, excess water can result in segregation of the mix during placement .
- Plasticisers and superplasticisers impart increased workability when added to concrete, without the necessity of the addition of water to help achieve the effect.
- Plasticisers tend to .be formulated from modified lignosulphonates and hydroxycarboxylic acids.
- the lignosulphonates may be derived from fermented wood, for example, spruce.
- Superplasticisers fall generally into the categories of sulphonated melamine-formaldehyde (SMF) condensates,- sulphonated naphthalene- formaldehyde (SNF) condensates; modified lignosulphonates; acid amide/polysaccharide mixtures and other high molecular weight hydroxylated polymers and copolymers .
- SMF sulphonated melamine-formaldehyde
- SNF sulphonated naphthalene- formaldehyde
- SMF and SNF superplasticisers are thought to operate by the action of electrostatic repulsion, which results in rapid dispersion of cement particles. This increases the mobility of the cement paste requiring no additional water for a significant increase in concrete workability.
- SCC Self Compacting Concrete
- SCC can be placed in the same way as ordinary concrete but without the need for any vibration.
- Pseudo-plastic in nature SCC passes around reinforcement, without segregation or bleeding, and at the same time expels entrapped air and so reduces excess voids and honeycombing.
- An important advantage of SCC is that it obviates compaction.
- SCC properties are obtained by using admixtures in conjunction with careful mix design.
- the main admixture used in SCC is a superplasticiser, and this may be supplemented with a viscosity modifying agent (A/MA) .
- A/MA viscosity modifying agent
- Superplasticisers are used to achieve high fluidity and reduce the water: cement ratio.
- PCE polycarboxylic ethers
- a viscosity modifying agent may be incorporated to enhance the yield value and viscosity of the mixture, hence reducing bleeding, segregation and settlement .
- viscosity modifying agents include polysaccharides and nanosilica.
- the usual polysaccharide is welan gum, which is added as a powder or as a suspension in oil in very small quantities .
- the present invention provides a process for the preparation of an admixture for a cementitious composition, said admixture comprising water, at least one viscosity modifying agent, and at least one plasticiser, the process comprising the steps of:
- step (ii) mixing the pre-mixture from step (i) with a second portion of plasticiser.
- the plasticiser in the pre-mixture of step (i) will generally be the same as the plasticiser mixed with the pre-mixture in step (ii) , although a different plasticiser may be used in step (ii) ; also, the plasticiser used in step (i) may be a blend of two or more plasticisers.
- plasticiser means any admixture, which, without affecting the consistence, permits a reduction in the water content of a given concrete mix, or which, without affecting the water content, increases the slump/flow or produces both effects simultaneously. Admixtures that increase the slump/flow without affecting the water content are preferred.
- the plasticiser is preferably a water reducing admixture that meets the requirements as defined by the British Standards, BS5075, Part 1, 1982.
- the plasticiser. is a superplasticiser.
- the term "superplasticiser” means any admixture, which, without affecting the consistence, permits a high reduction in the water content of a given concrete mix or which, without affecting the water content, increases the slump/flow considerably or produces both effects simultaneously. Admixtures that considerably increase the slump/flow without affecting the water content are preferred.
- the superplasticiser is preferably an admixture meeting the requirements as defined by the British Standards, BS 5075, Part 3, 1985.
- Suitable superplasticisers include polycarboxylate polymers, SMF condensates, SNF condensates, modified lignosulfates and amid/polysaccharide mixtures, their derivatives and mixtures thereof, and other high molecular weight hydroxylated polymers and copolymers, such as those described by Ramachandran et al , "Superplasticisers: properties and applications in concrete.”
- the superplasticisers are polycarboxylate polymers such as those described by Bradley et al , Cem. Concr. Aggr., 8 : 68-75 (1986); in particular, polyacrylate copolymers and derivatives thereof comprising (co) -polymerized units of acrylic acid and/or maleic acid or derivatives thereof are preferred.
- said (co) -polymerized units include a poly-ether side chain such as polyethylene oxide.
- Polycarboxylic ethers (PCE) and derivatives thereof are preferred; polycarboxylate from the Sokalan TM range such as Sokalan TM HP ' 80, manufactured by BASF are particularly suitable.
- Sokalan HP 80 TM is an aqueous solution of PCE, having a solids content of approximately 39 wt . % .
- Other suitable products may include other products from the Sokalan range such as CP5 (maleic acid - acrylic acid co-polymer, Na salt) , CP7 (maleic acid - acrylic acid co-polymer, Na salt) , CP9 (maleic acid - olefin co-polymer co-polymer, Na salt) , CP10 (modified polyacrylic acid, Na salt) , PA20 (polyacrylic acid, Na salt) , PA40 (polyacrylic acid, Na salt) , PM101 (maleic acid co-polymer, Na salt) , or products based on phosphate ethers such as Marphos TS615P, also available from BASF.
- CP5 maleic acid - acrylic acid co-polymer, Na salt
- CP7 maleic acid - acrylic acid co-polymer,
- Narlex LD 36V a sodium salt of a modified polycarboxylate
- Mighty ES a sodium salt of a modified polycarboxylate
- the PCE solution can also contain an integral defoamer.
- part of PCE may be replaced by a conventional superplasticiser, for example sulfonated naphthalene formaldehyde, such as Galoryl LH220 ® .
- Viscosity modifying agents useful in the practice of the present invention include polysaccharides and/or nanosilica.
- welan gum is used as the viscosity modifying agents.
- Welan gum is a heteropolysaccharide, which can be used as a powder such as Kelco-Crete K1C376 supplied by CP Kelco UK Limited. If appropriate, additional ingredients such as defoamer, usually used in connection with plasticisers to ensure or improve plasticising properties may be required.
- plasticiser from 2 to 30 wt . % of plasticiser, said percentage being expressed with reference to the plasticiser' s solids content, is comprised in the pre-mixture of step (i) , with the remaining 98 to 70 wt . % being mixed with the pre-mixture in step (ii) .
- a 39% suspension such as Sokalan HP 80
- from 3 to 7 wt . % of the superplasticiser' s solids content is comprised in the pre-mixture of step (i) , with the remaining 97 to 93 wt . % of the superplasticiser' s solids content being mixed with the pre-mixture in step (ii) .
- the admixture may contain one or more additional ingredients, for example one or more of a dispersing agent, a defoamer, a buffer, a retarder, a pH adjuster, a biocide, a preservative, a base, an accelerator, and/or an air entrainer.
- a dispersing agent for example one or more of a dispersing agent, a defoamer, a buffer, a retarder, a pH adjuster, a biocide, a preservative, a base, an accelerator, and/or an air entrainer.
- a preferred dispersing agent is mono- propylene glycol.
- step (i) preferably satisfies the following relationship:
- the solids content in the final admixture product is preferably from 15 to 40.0 wt.%, more preferably from 19 to 37.0 wt.%, still more preferably from 25 to 35 wt.%.
- the weight percentage of the viscosity modifying agent to the final product is preferably from 0.1% to 2%, more preferably from 0.25% to 1%.
- the present invention also provides a process for the preparation of a cementitious composition, wherein an admixture as herein defined is added to the composition in a single dose (i.e. "one shot").
- the cementitious composition may be concrete, preferably a self compacting concrete.
- the present invention further provides an admixture for a cementitious composition
- a cementitious composition comprising an aqueous solution of:
- the plasticiser is in the form of an aqueous solution
- the figures recited in (a) which refer to the plasticisers' solid content correspond to approximately 80 to 90%, when expressed with reference to the suspension of plasticiser.
- the admixtures have been prepared for the first time. Stability may be assessed having regard to the tendency of the constituents to separate out of solution while the admixture is standing.
- the viscosity modifying agent tends to drop out of suspension.
- the admixtures according to the present invention show little or substantially no separation over a period of time under ambient conditions.
- the admixtures are stable typically for at least 24 hours, more typically at least 2 days, still more typically at least 7 days. Indeed, the admixtures may be stable for 6 months or longer.
- the plasticiser is a superplasticiser as defined above.
- the admixture comprises from 15 to 40 wt.% of one or more plasticisers, said percentage being expressed with reference to the plasticiser' s solids content, from 0.1 to 2 wt . % of one or more viscosity modifying agents, up to 7 wt.% (preferably up to 5 wt.%) of one or more of a dispersing agent, a defoamer, a buffer, a retarder, a pH adjuster, a biocide, a preservative, preservatives, a base, a buffer, an accelerator, and/or an air entrainer, and the balance water.
- the admixture comprises from 19 to 37 wt.% of a polycarboxylic ether, said percentage being expressed with reference to the plasticiser' s solids content, from 0.5 to 1 wt.% of welan gum, up to 5 wt.% of one or more of a dispersing agent, a defoamer, a buffer, a retarder, an accelerator, a pH adjuster, a biocide, a preservative, a base and/or an air entrainer, and the balance water, wherein the pH is from 6.5 to 9.5.
- the present invention also provides a cementitious composition which comprises an
- the cementitious composition may be concrete, for example a self compacting concrete.
- the present invention still further provides a method of reducing separation in an admixture for a cementitious composition, said admixture comprising water, at least one viscosity modifying agent, and at least one plasticiser, the method comprising the steps of: (i) providing a pre-mixture comprising water, viscosity modifying agent, and a first portion of plasticiser,
- step (ii) mixing the pre-mixture from step (i) with a second portion of plasticiser.
- the present invention also provides for the use of mono-propylene glycol as a dispersing agent in an admixture for a cementitious mixture.
- the present invention also provides a polysaccharide suspension comprising mono-propylene glycol .
- the plasticiser is a superplasticiser as defined above.
- the mixture according to the present invention may, if desired, include one or more additional ingredients.
- additional ingredients include the following:
- Retarders such as sodium gluconate and other major retarders such as sugars and phosphates .
- the defoamers may also help to buffer the suspension. Suitable defoamers include
- Lumiten EL manufactured by BASF
- Pluronic PE9200 manufactured by BASF
- Degressal SD20 manufactured by BASF
- Foamaster manufactured by Henkel
- TBP manufactured by Bayer
- Preservatives such as biocides, including Glutaraldehyde (manufactured by BDH) , Nippacide TBX (manufactured by Nipa Laboratories Ltd) , Preventol D2 (manufactured by Bayer) .
- Bases such as sodium hydroxide (NaOH) , which helps to breakdown any flocks of viscosity modifying agent formed.
- Dispersing agents to aid the dispersion of the viscosity modifying agent.
- Dispersing agent herein refers to any agent to promote uniform and maximum separation of solid particles in a suspending medium. It has surprisingly been found that monopropylene glycol is a particularly efficient dispersing agent, in particular for dispersing polysaccharides and more specifically welan gum; - Accelerators to increase the rate of stiffening or setting of the concrete or to increase the rate of hardening and early strength again.
- Usual accelerators include calcium chloride (although generally not used in concrete containing embedded metal) and a range of chloride free accelerators (CFA) , such as calcium nitrate, calcium fornate or calcium thiocyanate.
- the present invention also provides a process for the preparation of a pre-mixture as herein described, the process comprising mixing water, a plasticiser, and a viscosity modifying, agent, wherein the amount of plasticiser is such that the total solids content of the premix expressed as a percentage of the premix is from 9 to 25 wt.%, more preferably from 10 to 17%.
- the solids contents of the premix is approximately 15%.
- the plasticiser is a superplasticiser as defined above.
- stabilized suspensions may be achieved by preparing, in a first step, a pre-mixture of a small amount of the superplasticiser with all or substantially all of the viscosity modifying agent. While not wishing to be bound by theory, it is believed that this process enables the viscosity modifying agent to be partially hydrated, thereby resulting in greater stability.
- a stabilized pre-mixture is preferably achieved by mixing part plasticiser and the viscosity modifying agent; the plasticiser dosage required to give the required solids content in the premix can be determined in accordance with the following formula:
- the solids content of the premix is within the above specified range, then this allows the supplementation of an additional amount of plasticiser, as required, to produce a stable, usable suspension. More particularly, if the solids content of the premix is from 12 to 17 wt.%, then it is possible to produce a particularly stable product .
- ingredients may be added during the preparation of the pre-mixture.
- sodium gluconate may be added when preparing the pre-mixture, or before adding the rest of the plasticiser to the final product.
- the dispersing agents, defoamers can be added between steps i) and ii) .
- the processes according to the present invention may be carried out at ambient temperature.
- the processes may be carried out using a conventional high speed, high shear mixer such as IKA stirrer, type ST DV S2 on a laboratory scale basis; or any other mixers appropriate to industrial full-scale, such as a Silverson GX10 or GX20 mixer.
- a conventional high speed, high shear mixer such as IKA stirrer, type ST DV S2 on a laboratory scale basis
- any other mixers appropriate to industrial full-scale such as a Silverson GX10 or GX20 mixer.
- mixing may be facilitated at relatively high solids content in the premix, due to the increased shear of the mixer being more efficient .
- the viscosity modifying agent is added slowly under vigorous stirring (approximately 750 rpm) as to avoid the formation of lumps.
- the speed of the mixer may be increased to approximately 1000 rpm and stirring may be continued so as to allow the product to thicken.
- Corresponding mixing speeds appropriate to larger scales can be routinely determined by one skilled in the art seeking to carry out the present process on a full-scale industrial basis.
- the present invention also provides for the use of the suspensions as herein described as admixtures for cementitious compositions.
- Cementitious compositions comprising the admixtures as herein described are a further aspect of the present invention.
- the present invention more specifically refers to concrete .
- the present invention more specifically refers to Self Compacting Concrete (SCC) .
- monopropylene glycol may be added to the admixture to disperse the viscosity modifying agent.
- the invention provides for the use of monopropylene glycol as a dispersing agent in a polysaccharide suspension.
- polysaccharide suspensions comprising monopropylene glycol are also encompassed by the present invention. The present invention will be further understood with reference to the following experimental examples .
- Sokalan HP80 is the trade name of a PCE available from BASF. It has a solids content of approximately 39%.
- the sodium gluconate acts as a retarder.
- the propylene glycol acts to aid dispersions of the welan gum.
- K1C376 is for Kelco-crete K1C376, which is the trade name of a welan gum available from CP Kelco UK Ltd.
- the biocide acts as a preservative.
- the sodium hydroxide helps break down the flocks of welan formed (see other examples) .
- IKA stirrer type ST DV S2 having a speed range of 50-200 rpm. Dissolver blade.
- IKA stirrer type ST DV S2 having a speed range of 50-200 rpm. Dissolver blade.
- IKA stirrer type ST DV S2 having a speed range of 50-200 rpm.
- Dissolver blade
- IKA stirrer type ST DV S2 having a speed range of 50-200 rpm. Dissolver blade.
- Equipment IKA stirrer type ST DV S2 having a speed range of 50-200 rpm. Dissolver blade.
- IKA stirrer type ST DV S2 having a speed range of 50-200 rpm. Dissolver blade.
- IKA stirrer type ST DV S2 having a speed range of 50-200 rpm.
- Dissolver blade
- IKA stirrer type ST DV S2 having a speed range of 50-200 rpm. Dissolver blade.
- Sokalan CP10 is the trade name of a sodium salt of a modified polyacrylic acid available from BASF. It has a solids content of approximately 45%.
- the biocide acts as a preservative.
- the sodium gluconate acts as a retarder.
- the propylene glycol acts to aid dispersion of the welan gum.
- K1C376 is for Kelco-crete K1C376, which is the trade name of a welan gum available from CP Kelco UK Ltd.
- Narlex LD 36V is the trade name of a sodium salt of a modified polycarboxylate from National Starch. It has a solids content of approximately 39%.
- Mighty ES is the trade name of a sodium salt of a modified polycarboxylate from KAO. It has a solids content of approximately 40%.
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- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2002326017A AU2002326017A1 (en) | 2001-08-24 | 2002-08-27 | Admixture for cementitious compositions and process for preparation thereof |
EP02760398A EP1419121A2 (en) | 2001-08-24 | 2002-08-27 | Admixture for cementitious compositions and process for preparation thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB0120699.4 | 2001-08-24 | ||
GB0120699A GB2378946A (en) | 2001-08-24 | 2001-08-24 | Preparation of an admixture for cementitious compositions |
Publications (2)
Publication Number | Publication Date |
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WO2003018505A2 true WO2003018505A2 (en) | 2003-03-06 |
WO2003018505A3 WO2003018505A3 (en) | 2003-10-16 |
Family
ID=9920991
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB2002/003926 WO2003018505A2 (en) | 2001-08-24 | 2002-08-27 | Admixture for cementitious compositions and process for preparation thereof |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1419121A2 (en) |
AU (1) | AU2002326017A1 (en) |
GB (1) | GB2378946A (en) |
WO (1) | WO2003018505A2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2608830C1 (en) * | 2015-11-02 | 2017-01-25 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Казанский государственный архитектурно-строительный университет" | Method of preparing concrete mixture |
CN112218839A (en) * | 2018-07-17 | 2021-01-12 | Sika技术股份公司 | Improved concrete admixture |
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US6800129B2 (en) | 2003-01-30 | 2004-10-05 | W. R. Grace & Co.-Conn. | High solids pumpable cement additives |
SE524924C2 (en) * | 2003-03-10 | 2004-10-26 | Johnny Johansson | Ways to make construction lightweight ballast concrete |
DE112007003702A5 (en) * | 2007-08-23 | 2010-07-29 | Ecc Ltd. | Additive composition for building materials based on minerals |
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2001
- 2001-08-24 GB GB0120699A patent/GB2378946A/en not_active Withdrawn
-
2002
- 2002-08-27 WO PCT/GB2002/003926 patent/WO2003018505A2/en not_active Application Discontinuation
- 2002-08-27 AU AU2002326017A patent/AU2002326017A1/en not_active Abandoned
- 2002-08-27 EP EP02760398A patent/EP1419121A2/en not_active Withdrawn
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RU2608830C1 (en) * | 2015-11-02 | 2017-01-25 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Казанский государственный архитектурно-строительный университет" | Method of preparing concrete mixture |
CN112218839A (en) * | 2018-07-17 | 2021-01-12 | Sika技术股份公司 | Improved concrete admixture |
JP2021529714A (en) * | 2018-07-17 | 2021-11-04 | シーカ テクノロジー アクチェンゲゼルシャフト | Improved concrete admixture |
JP7489328B2 (en) | 2018-07-17 | 2024-05-23 | シーカ テクノロジー アクチェンゲゼルシャフト | Improved Concrete Admixtures |
Also Published As
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AU2002326017A1 (en) | 2003-03-10 |
EP1419121A2 (en) | 2004-05-19 |
WO2003018505A3 (en) | 2003-10-16 |
GB2378946A (en) | 2003-02-26 |
GB0120699D0 (en) | 2001-10-17 |
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