WO2012052294A1 - Ciment et activateur liquide d'accélérateur de prise rapide pour bétons projetés - Google Patents

Ciment et activateur liquide d'accélérateur de prise rapide pour bétons projetés Download PDF

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Publication number
WO2012052294A1
WO2012052294A1 PCT/EP2011/067394 EP2011067394W WO2012052294A1 WO 2012052294 A1 WO2012052294 A1 WO 2012052294A1 EP 2011067394 W EP2011067394 W EP 2011067394W WO 2012052294 A1 WO2012052294 A1 WO 2012052294A1
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WO
WIPO (PCT)
Prior art keywords
cement
composition
mixture
aluminium
calcium
Prior art date
Application number
PCT/EP2011/067394
Other languages
English (en)
Inventor
Cristiano Maltese
Carlo Pistolesi
Massimo Stefanoni
Enrico Dal Negro
Vito Reinstadler
Marco Squinzi
Original Assignee
Mapei S.P.A.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mapei S.P.A. filed Critical Mapei S.P.A.
Publication of WO2012052294A1 publication Critical patent/WO2012052294A1/fr

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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
    • C04B28/04—Portland cements
    • 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
    • C04B40/0042—Powdery mixtures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00146—Sprayable or pumpable mixtures
    • C04B2111/00155—Sprayable, i.e. concrete-like, materials able to be shaped by spraying instead of by casting, e.g. gunite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the present invention relates to the preparation and use of powder admixtures to be used in combination with a flash setting accelerator able to reduce the quantity of cement and flash setting accelerator thus allowing to produce sprayed concretes more economical and at lower emission of carbon dioxide.
  • Concrete in combination with these setting accelerators should guarantee an excellent adhesion of the sprayed material to the rock wall and a rapid compressive strength development.
  • the first condition can be evaluated by measuring the capability of the accelerator to reduce the setting time of a cement paste.
  • the second requirement is determined by measuring the mechanical strength development during the first hours of hydration of a cementitious mortar or concrete.
  • alkaline accelerators such as: soda, potash, silicate or alkali metal aluminates. Nevertheless, such accelerators are known to negatively affect the long term mechanical strengths. Moreover, due to their alkaline nature, they are irritating to the skin and particular protective devices are requested for the workers' s safety. Furthermore, alkali metal substances reacting with aggregates, could favour alkali silica reaction (ASR) which impairing the concrete properties. Finally, they release alkaline substances that, by increasing the pH of ground waters, could be dangerous polluting agents.
  • alkali-free accelerators According to European rules (Oscher Fisher Betonà, Sprayed Concrete Guideline, Wien, March 1999 and EN 934-5 "Admixtures for Sprayed Concrete-Definitions, Requirements, Conformity, Marking and Labelling"), an accelerating admixture is classified as “alkali- free” when the concentration of sodium and potassium, expressed as equivalents of Na 2 O, is lower than 1%. Lithium is also an alkali metal, however the scientific literature shows that it does not negatively affect the concrete and therefore it is not considered in the calculation of equivalents of Na 2 O.
  • New "alkali-free" admixtures consisting of fluoro aluminates and aluminium sulfate are also known in the art (EP 1 1673 17 B l).
  • These accelerators can be in the form of water solutions (with good long term stability) which cause a quick concrete setting, thereby allowing good adhesion to the rock walls. Nevertheless, they inhibit, in particular during the first hours of hydration, an effective mechanical strength development of the sprayed cementitious material.
  • EP 1 114004 B l and EP 946451 B l disclose accelerators based on aluminium carboxylates and aluminium sulfate. These accelerators are in the form of water solution and, compared to those based on fluoro aluminates, are characterised by a faster development of early mechanical strength with a lower capability to reduce the setting time and, therefore, they can negatively affect the adhesion of the fresh sprayed material on the rock walls, determining a large rebound.
  • EP2080741A1 describes a complex spraying method which comprises mixing water and a powder quick setting admixture comprising an alkaline earth metal carbonate, water soluble acidic substance, calcium aluminate and an alkali metal sulphate to form a slurry quick setting admixture; mixing this slurry with concrete which is immediately projected on the substrate.
  • EP 1657226 Al discloses an accelerating system for cement composed of a liquid quick setting admixture containing an aluminium source, a sulphur source and a fluorine source which is combined with one or more quick- setting aids selected from the group consisting of calcium aluminate, calcium sulfoaluminate, calcium alumino silicate, an alkali metal containing substance, calcium hydroxide and aluminium hydroxide. Nevertheless, the addition to hydrating cement of these quick setting aids strongly reduce concrete workability thus hindering the possibility to use practically this technique.
  • cement is a raw material with high environmental impact.
  • the construction of a short tunnel (7 m of diameter and 1 km of length) coated with 0.3 m of sprayed concrete requires at least 1630 ton of cement which causes the emission of about 1076 ton of CO 2 .
  • the object of the present invention is to provide admixtures for concretes or mortars which are sprayed in combination with liquid flash setting accelerators. These admixtures should allow to reduce cement and liquid flash setting accelerator content in the sprayed mixture without reducing its workability and mechanical performance.
  • an admixture comprising a powdery mixture of at least an aluminium, calcium, magnesium, sodium, potassium or lithium silicate, aluminate, sulphate, nitrate, halide, carboxylate, hydroxide or oxide, or mixture thereof in combination with one or more alkali earth metal carbonates added to a concrete which is sprayed in combination with a liquid flash setting accelerator aluminium sulphate based, strongly improves liquid flash setting accelerator performance without affecting concrete workability and allowing the production of sprayed concrete with lower amount of cement and liquid flash setting accelerator. In this way, a reduction of the total cost of the infrastructure is possible also limiting the environmental impact.
  • the performances of the powdery mixture are further improved by the addition of pozzolanic material, hydraulic lime, nonhydraulic lime or latent hydraulic binders.
  • Silica fume is an amorphous silicon oxide powder, obtained after filtering the dusts extracted from the ferrosilicon production in an electric arc furnace.
  • the characteristics of silica fume are preferably the following:
  • Fly ash is a by-product of the combustion of coal from coal fired power plant and they are composed of fine particle in the flue gas which are separated by electrostatic or mechanical filters. Depending upon the source and makeup of the coal being burned, the components of fly ash vary considerably, but all fly ash includes substantial amounts of silicon dioxide (SiO 2 ) (both amorphous and crystalline) and calcium oxide (CaO), both being endemic ingredients in many coal-bearing rock strata.
  • the chemical physical characteristics are preferably the following:
  • Latent hydraulic binders are for example blast furnace slags which are co-products from the making of Iron. After being tapped from the furnace and separated from the Iron, the slag is instantaneously cooled by quenching in large volumes of cold water. This process produces a glassy homogeneous, non crystalline material that has cementitious properties.
  • the chemical physical characteristics of blast furnace slags suitable for the invention are preferably the following:
  • SiO 2 content 25-50%
  • Hydraulic lime is produced by heating calcining limestone containing clay and other impurities. Calcium reacts in the kiln with the clay minerals to produce hydrated silicates and calcium aluminates with hydraulic properties.
  • the chemical physical characteristics of hydraulic lime suitable for the invention are preferably the following:
  • the powdery admixture containing at least an aluminium, calcium, magnesium, sodium, potassium or lithium silicate, aluminate, sulphate, nitrate, halide, carboxylate, hydroxide or oxide, or mixture thereof (defined as component A) in combination with one or more alkali earth metal carbonates (defined as component B) should be composed as follows:
  • the addition to powdery admixture of pozzolanic materials, hydraulic lime, nonhydraulic lime or latent hydraulic binder can be made up to 40% by weight.
  • Water reducers can also be added to the powdery admixture in a range between 0.1 and 10% by mass.
  • the powdery admixture of the present invention can be easily prepared by adding the components and mixing them in order to obtain a homogeneous mixture.
  • An admixture of the invention (Formula 1) was prepared according to the following procedure: 70 g of calcium carbonate (particle size distribution reported in Tab. 2) and 30 g of calcium hydroxide were added to a 350 ml plastic container; the mixture was shaken by hand for about 1 minute in order to obtain a homogeneous system.
  • An admixture of the invention (Formula 2; Tab. 4) was prepared according to the following procedure: 90 g of calcium carbonate (particle size distribution reported in Tab. 2) and 10 g of calcium oxide were added to a 350 ml plastic container; the mixture was shaken by hand for about 1 minute in order to obtain a homogeneous system.
  • the mortars were prepared according to EN 196/1.
  • the powdery admixture of the present invention was added to cement whereas alkali free flash setting accelerator was added at the end of the mixing cycle and further mixed for 10 sec.
  • the mechanical strength was measured by a digital force gauge (O faux Fischer Betonà, Sprayed Concrete Guideline, Wien, March 1999) and it was expressed in N.
  • the mechanical strength was measured according to the EN 196/1 and the values were expressed in MPa. The results are shown in Table 8.
  • Mixture 6 (containing a powdery admixture of the present invention and a lower dosage of cement and alkali free accelerator) is significantly more performing than Mixture 5 in terms of mechanical strength development.
  • An admixture of the invention (Formula 4; Tab. 9) was prepared according to the following procedure: 90 g of calcium carbonate 2 (particle size distribution reported in Tab. 10), 5 g of calcium hydroxide and 5 g of fly ash were added to a 350 ml plastic container; the mixture was shaken by hand for about 1 minute in order to obtain a homogeneous system.
  • Mapequick AF 2000 was added at the end of the standard mixing cycle (3% by cement mass). The mixtures were then stirred for other 30 sec and transferred into a 10x10x10 cm mould.
  • An admixture of the invention (Formula 7; Tab. 16) was prepared according to the following procedure: 90 g of dolomite (0- 100 ⁇ ) and 10 g of aluminium sulphate were added to a 350 ml plastic container; the mixture was shaken by hand for about 1 minute in order to obtain a homogeneous system.
  • An admixture of the invention (Formula 8; Tab. 18) was prepared according to the following procedure: 90 g of calcium carbonate 1 and 10 g of aluminium sulphate were added to a 350 ml plastic container; the mixture was shaken by hand for about 1 minute in order to obtain a homogeneous system.

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

Abstract

Cette invention concerne la préparation et l'utilisation d'adjuvants en poudre qui s'utilisent en combinaison avec un accélérateur de prise rapide et permettent de réduire la quantité nécessaire de ciment et d'accélérateur de prise, et donc de produire des bétons projetés de manière plus économique pour de moindres émissions de dioxyde de carbone.
PCT/EP2011/067394 2010-10-22 2011-10-05 Ciment et activateur liquide d'accélérateur de prise rapide pour bétons projetés WO2012052294A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT001950A ITMI20101950A1 (it) 2010-10-22 2010-10-22 Additivo attivatore di cemento e accelerante per calcestruzzi proiettati
ITMI2010A001950 2010-10-22

Publications (1)

Publication Number Publication Date
WO2012052294A1 true WO2012052294A1 (fr) 2012-04-26

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Family Applications (1)

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PCT/EP2011/067394 WO2012052294A1 (fr) 2010-10-22 2011-10-05 Ciment et activateur liquide d'accélérateur de prise rapide pour bétons projetés

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Country Link
IT (1) ITMI20101950A1 (fr)
WO (1) WO2012052294A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITMI20121255A1 (it) * 2012-07-18 2014-01-19 Mapei Spa Additivi acceleranti di presa e indurimento
JP2018087101A (ja) * 2016-11-29 2018-06-07 太平洋マテリアル株式会社 吹付け材料及び湿式吹付け工法
CN108285286A (zh) * 2018-02-28 2018-07-17 湖北工业大学 一种适用于砂浆的聚羧酸减水剂的制备方法
CN114735961A (zh) * 2022-02-23 2022-07-12 武汉源锦建材科技有限公司 一种固液两用无碱速凝剂及其制备方法和应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995035266A1 (fr) * 1994-06-17 1995-12-28 Blue Oak Materials Limited Partnership Procede et dispositif de melange, de pulverisation et de mise en place de materiau a base de ciment
US5660625A (en) 1993-07-24 1997-08-26 Giulini Chemie Gmbh Use of basic aluminium sulphates as low-alkali set accelerators for cement
EP0946451B1 (fr) 1996-10-25 2000-09-20 BK Giulini Chemie GmbH & Co. OHG Accelerateur de solidification et de prise pour liants hydrauliques
EP1114004A1 (fr) 1999-06-18 2001-07-11 Mbt Holding Ag Accelerateur de prise destine au beton
EP1167317B1 (fr) 2000-06-21 2003-11-26 Sika Schweiz AG Accelerateur de prise et de durcissement exempt de métaux alcalins
EP1657226A1 (fr) 2003-08-20 2006-05-17 Denki Kagaku Kogyo Kabushiki Kaisha Matiere de pulverisation et technique de pulverisation faisant appel a cette matiere
EP2080741A1 (fr) 2006-11-09 2009-07-22 Denki Kagaku Kogyo Kabushiki Kaisha Accélérateur de prise et technique de pulvérisation avec ledit accélérateur de prise

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5660625A (en) 1993-07-24 1997-08-26 Giulini Chemie Gmbh Use of basic aluminium sulphates as low-alkali set accelerators for cement
WO1995035266A1 (fr) * 1994-06-17 1995-12-28 Blue Oak Materials Limited Partnership Procede et dispositif de melange, de pulverisation et de mise en place de materiau a base de ciment
EP0946451B1 (fr) 1996-10-25 2000-09-20 BK Giulini Chemie GmbH & Co. OHG Accelerateur de solidification et de prise pour liants hydrauliques
EP1114004A1 (fr) 1999-06-18 2001-07-11 Mbt Holding Ag Accelerateur de prise destine au beton
EP1167317B1 (fr) 2000-06-21 2003-11-26 Sika Schweiz AG Accelerateur de prise et de durcissement exempt de métaux alcalins
EP1657226A1 (fr) 2003-08-20 2006-05-17 Denki Kagaku Kogyo Kabushiki Kaisha Matiere de pulverisation et technique de pulverisation faisant appel a cette matiere
EP2080741A1 (fr) 2006-11-09 2009-07-22 Denki Kagaku Kogyo Kabushiki Kaisha Accélérateur de prise et technique de pulvérisation avec ledit accélérateur de prise

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Osterreichischer Betonverein, Sprayed Concrete Guideline", March 1999, article "Admixtures for Sprayed Concrete-Definitions, Requirements, Conformity, Marking and Labelling"

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITMI20121255A1 (it) * 2012-07-18 2014-01-19 Mapei Spa Additivi acceleranti di presa e indurimento
WO2014012844A1 (fr) * 2012-07-18 2014-01-23 Mapei S.P.A. Accélérateurs de prise et de durcissement en poudre pour béton pulvérisé
JP2018087101A (ja) * 2016-11-29 2018-06-07 太平洋マテリアル株式会社 吹付け材料及び湿式吹付け工法
CN108285286A (zh) * 2018-02-28 2018-07-17 湖北工业大学 一种适用于砂浆的聚羧酸减水剂的制备方法
CN114735961A (zh) * 2022-02-23 2022-07-12 武汉源锦建材科技有限公司 一种固液两用无碱速凝剂及其制备方法和应用
CN114735961B (zh) * 2022-02-23 2023-03-10 武汉源锦建材科技有限公司 一种固液两用无碱速凝剂及其制备方法和应用

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