EP1713744A1 - Accelerateur de solidification et de rigidification a base d'eau destine a des liants hydrauliques et procede de fabrication - Google Patents
Accelerateur de solidification et de rigidification a base d'eau destine a des liants hydrauliques et procede de fabricationInfo
- Publication number
- EP1713744A1 EP1713744A1 EP05707950A EP05707950A EP1713744A1 EP 1713744 A1 EP1713744 A1 EP 1713744A1 EP 05707950 A EP05707950 A EP 05707950A EP 05707950 A EP05707950 A EP 05707950A EP 1713744 A1 EP1713744 A1 EP 1713744A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hardening accelerator
- water
- aluminum
- accelerator according
- solidification
- 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.)
- Withdrawn
Links
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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/10—Accelerators; Activators
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00146—Sprayable or pumpable mixtures
- C04B2111/00155—Sprayable, i.e. concrete-like, materials able to be shaped by spraying instead of by casting, e.g. gunite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
- C04B2111/1025—Alkali-free or very low alkali-content materials
Definitions
- the invention is based on a setting and hardening accelerator for hydraulic binders according to the preamble of the first claim.
- the invention is also based on a method for producing a setting and hardening accelerator for hydraulic binders according to the preamble of the independent method claim.
- the mixture containing the binder mentioned is added from 0.5 to 10% by weight, based on the weight of this binder , an alkali-free setting and hardening accelerator, which accelerator contains aluminum hydroxide.
- an alkali-free setting and hardening accelerator which accelerator contains aluminum hydroxide.
- Solidification and hardening accelerators in dissolved form for hydraulic binders are known from EP 0 946451 B1, which can be more easily admixed to the concrete when the concrete is sprayed.
- Such a solidification and hardening accelerator consists among other things of aluminum hydroxide, aluminum salts and organic carboxylic acids.
- Such known accelerators contain a relatively large amount of aluminum salts and amorphous aluminum hydroxide is required for the production, which is very expensive. To enable the production of such accelerators, the water must be heated to approx. 60 - 70 ° C for the reaction. Further disadvantages of such solidification and hardening accelerators are also a relatively low early strength in the first hours and days and the insufficient stability of the solution.
- the invention is based on the object in the case of a water-based setting and hardening accelerator for hydraulic binders to achieve the highest possible strength with the longest possible stability of the accelerator.
- the advantages of the invention can be seen, inter alia, in the fact that the accelerators according to the invention provide high stability, i.e. Stabilization of the accelerator solution is achieved and that high strengths are achieved in the first hours and days.
- Water-based setting and hardening accelerators for hydraulic binders according to the invention can be produced in various ways, a molar ratio of aluminum to organic acid being less than 0.65.
- Water-based accelerator refers to an accelerator that can appear as a solution, with partially finely dispersed particles or as a dispersion.
- Such a water-based setting and hardening accelerator according to the invention advantageously comprises (in% by weight): 14.4 to 24.9% sulfate,
- Al 2 O 3 is preferably chosen to be less than 14%, particularly preferably less than 13% and in particular less than 12% Al 2 O 3 .
- the aforementioned substances can advantageously be found as ions in solution, but can also occur in complex form or undissolved in the accelerator. This is particularly the case if the accelerator occurs as a solution with partially finely dispersed particles or as a dispersion.
- a water-based solidification and hardening accelerator for hydraulic binders according to the invention can be produced, for example, from Al 2 (SO 4 ) 3 aluminum sulfate, Al (OH) 3 aluminum hydroxide and organic acid in aqueous solution, a molar ratio of aluminum to organic acid being less than 0.65.
- An aluminum sulfate with approximately 17% Al 2 O 3 is preferably used, but other contents can also be used, in which case the amounts to be added must then be adjusted accordingly.
- the aluminum sulfate can also be produced by a reaction of aluminum hydroxide with sulfuric acid in the production of the accelerator, with sulfate ions correspondingly forming in the aqueous solution.
- aluminum sulfate can be produced by reacting a basic aluminum compound with sulfuric acid.
- Amorphous aluminum hydroxide is advantageously used as the aluminum hydroxide.
- the aluminum hydroxide can also be used in the form of aluminum hydroxide carbonate, aluminum hydroxysulfate or the like.
- a carboxylic acid particularly preferably a formic acid, is preferably used as the organic acid, but other organic acids having the same effect, such as, for example, acetic acid, can also be used. In general, however, all mono- or polyprotonic carboxylic acids can be used.
- magnesium hydroxide Mg (OH) 2 is preferably used as the alkaline earth hydroxide.
- Diethanolamine DEA is advantageously used as the alkanolamine.
- Polycarboxylates and particularly advantageously Sika ViscoCrete® are advantageously used as flow agents.
- Silicasol is advantageously used as a stabilizer.
- the following are essentially used (in% by weight): - 30 - 50% Al 2 (S ⁇ 4) 3 aluminum sulfate, preferably 35 - 45%, in particular 35 - 38%, and / or
- Al (OH) 3 aluminum hydroxide in particular 7 - 15%, and / or
- a molar ratio of aluminum to organic acid being less than 0.65, preferably less than 0.60, particularly preferably less than 0.55 and in particular less than 0.50.
- the molar ratio of aluminum to organic acid is preferably in a range from 0.38 to 0.65, particularly preferably in a range from 0.38 to 0.60, in particular between 0.50 and 0.60. Below a value of 0.38, the pH value becomes relatively low and a very high proportion of acid must be used, and in some cases stability is no longer guaranteed.
- both the amount of aluminum sulfate used in the production and, in particular, the aluminum hydroxide is reduced by up to 10% and 38%, respectively.
- Up to 10% magnesium hydroxide and / or a corresponding amount of magnesium oxide are preferably used in the production of the accelerator.
- the pure amount of Mg, based on the total amount of accelerator, is 0 to 4.2%, preferably 0.8 to 2.9%, particularly preferably 1.3 to 2.1%.
- the ratio of aluminum to organic acid is adjusted to a value of less than 0.65, preferably less than 0.60, by the increased organic acid content compared to known accelerators, and the pH is adjusted to pH 3-4 by up to 5% alkanolamine.
- the sulfate resistance is promoted by the amount of aluminum used in the production, which is reduced by up to 25%. This is an advantage over conventional accelerators, in which the accelerator drastically deteriorates the sulfate resistance.
- the reduction in the sulfate resistance due to aluminum input is caused in particular by the fact that the aluminate phases have a special affinity for sulfate.
- the additional aluminum increases the proportion of aluminate phases in the concrete, which then cause a not insignificant crystallization pressure by ettringite formation on the hardened concrete when exposed to external sulfate and thus lead to damage.
- the aluminum content stated as Al 2 O 3 is therefore preferably less than 14%, more preferably less than 13% and in particular less than 12% Al 2 O 3 .
- magnesium hydroxide and / or oxide is used in the production of the accelerator, the strong reaction of the magnesium hydroxide and / or oxide with the organic acid increases the temperature of the mixture so much that the water does not have to be heated for these batches. The other components are then added to this heated mixture. The components can also be added in any other order. This simplifies the process and less energy is required.
- An additional advantage of using magnesium is the significantly higher storage stability of the accelerators caused by the magnesium ions. Good storage stability is achieved even with a content of 1% by weight of magnesium hydroxide during manufacture. At higher levels, the shelf life is at least four months. By using magnesium hydride and / or oxide, the accelerator can also be manufactured significantly cheaper, since expensive aluminum hydroxide can be replaced.
- the stability of the accelerators is positively influenced by the reduced amount of aluminum.
- the reduced amount of aluminum also increases the sulfate resistance.
- the development of the compressive strength of the shotcrete in the first hours and days is also influenced very positively and is better than with conventionally used accelerators.
- Table 2 shows the molar ratios of aluminum to sulfate and from aluminum to organic acid, here formic acid, of the samples measured.
- the molar ratio of aluminum to organic acid is below 0.67, preferably below 0.60.
- the aluminum content of the various examples is also given.
- Molar ratios Hydraulic binders can be added 0.1 to 10 wt .-% of the accelerator according to the invention.
- 6% of the accelerator based on the content of the hydraulic binder, was added to a conventional concrete mixture for use as shotcrete.
- Portland cement was used as the hydraulic binder.
- the admixture took place in the area of the spray nozzle when processing the shotcrete.
- the strength of the sprayed concrete was determined. For this purpose, cores measuring 5x5 cm are removed. The compressive strength of the drill cores is then determined using a hydraulic press.
- Example A5 also shows a relatively high strength after one day, but with significantly higher aluminum contents than the examples A6 to A8. Versions according to Examples A4 and A6 to A7 are therefore particularly preferred, since the lower Al content also improves the sulfate resistance.
- the accelerators according to the invention can also be used for hydraulic binders other than cement such as mixed cements, lime, hydraulic lime and gypsum and mortar and concrete made therefrom.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
L'invention concerne un accélérateur de solidification et de rigidification à base d'eau destiné à des liants hydrauliques, contenant du sulfate, de l'aluminium et un acide organique, le rapport molaire de l'aluminium sur l'acide organique étant inférieur à 0,65. Le rapport molaire de l'aluminium sur l'acide carboxylique est de préférence inférieur à 0,60 et supérieur 0,38.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP05707950A EP1713744A1 (fr) | 2004-02-06 | 2005-02-04 | Accelerateur de solidification et de rigidification a base d'eau destine a des liants hydrauliques et procede de fabrication |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04002676 | 2004-02-06 | ||
EP05707950A EP1713744A1 (fr) | 2004-02-06 | 2005-02-04 | Accelerateur de solidification et de rigidification a base d'eau destine a des liants hydrauliques et procede de fabrication |
PCT/EP2005/050497 WO2005075381A1 (fr) | 2004-02-06 | 2005-02-04 | Accelerateur de solidification et de rigidification a base d'eau destine a des liants hydrauliques et procede de fabrication |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1713744A1 true EP1713744A1 (fr) | 2006-10-25 |
Family
ID=34673682
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP05707950A Withdrawn EP1713744A1 (fr) | 2004-02-06 | 2005-02-04 | Accelerateur de solidification et de rigidification a base d'eau destine a des liants hydrauliques et procede de fabrication |
Country Status (5)
Country | Link |
---|---|
US (2) | US20100071595A1 (fr) |
EP (1) | EP1713744A1 (fr) |
JP (2) | JP2007520413A (fr) |
NO (1) | NO20063950L (fr) |
WO (1) | WO2005075381A1 (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2248780A1 (fr) | 2009-05-06 | 2010-11-10 | BK Giulini GmbH | Accélérateur de prise et de durcissement |
CN112110703A (zh) * | 2020-08-17 | 2020-12-22 | 济南大学 | 一种防水抗渗修补砂浆及施工方法与应用 |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2006224732B2 (en) * | 2005-03-16 | 2011-10-27 | Sika Technology Ag | Hardening and setting accelerator additive, use of the latter and method for producing said additive |
DE102005054190B3 (de) * | 2005-11-14 | 2007-10-04 | Rombold & Gfröhrer GmbH & Co. KG | Erhärtungs- und Erstarrungsbeschleuniger und dessen Verwendung |
EP1964824A1 (fr) * | 2007-02-13 | 2008-09-03 | Sika Technology AG | Accélérateur de prise et de durcissement pour liant hydraulique et son procédé de fabrication |
EP2072479A1 (fr) * | 2007-12-20 | 2009-06-24 | Sika Technology AG | Réactivation de systèmes cimenteux retardés |
SG178023A1 (en) | 2009-09-02 | 2012-03-29 | Constr Res & Tech Gmbh | Sprayable hydraulic binder composition and method of use |
EP2623477A4 (fr) * | 2010-09-27 | 2016-10-05 | Sika Technology Ag | Agent de prise rapide pour liant hydraulique, et procédé pour prise rapide d'un liant hydraulique |
JP5800487B2 (ja) * | 2010-10-08 | 2015-10-28 | 太平洋セメント株式会社 | グラウトの製造方法 |
US20140199488A1 (en) | 2010-11-30 | 2014-07-17 | Construction Research & Technology Gmbh | Cement Hydrate Products For Sprayed Concrete |
EP3819279A1 (fr) | 2019-11-07 | 2021-05-12 | Sika Technology Ag | Suspensions de sulfate d'aluminium à viscosité réduite |
EP4082995B1 (fr) | 2021-04-30 | 2024-01-31 | Sika Technology AG | Réduction de la viscosité des suspensions de sulfate d'aluminium avec des composés de métal alcalin |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH648272A5 (de) | 1981-10-12 | 1985-03-15 | Sika Ag | Alkalifreier abbinde- und erhaertungsbeschleuniger sowie verfahren zur beschleunigung des abbindens und erhaertens eines hydraulischen bindemittels. |
GB9513116D0 (en) * | 1995-06-28 | 1995-08-30 | Sandoz Ltd | Improvements in or relating to organic compounds |
CA2271629C (fr) | 1996-10-25 | 2003-03-25 | Bk Giulini Chemie Gmbh & Co. Ohg | Accelerateur de solidification et de prise pour liants hydrauliques |
PT1114004E (pt) * | 1999-06-18 | 2003-11-28 | Mbt Holding Ag | Misturas de betao |
GB9928977D0 (en) * | 1999-12-08 | 2000-02-02 | Mbt Holding Ag | Process |
JP3328258B2 (ja) * | 2000-01-27 | 2002-09-24 | ニチハ株式会社 | セメント硬化促進方法 |
ES2228354T3 (es) * | 2000-06-21 | 2005-04-16 | Sika Schweiz Ag | Gente acelerador del fraguado y del endurecimiento, exento de sulfatos y alcalis. |
GB0123364D0 (en) | 2001-09-28 | 2001-11-21 | Mbt Holding Ag | Composition |
GB0128438D0 (en) * | 2001-11-28 | 2002-01-16 | Mbt Holding Ag | Method |
JP3967279B2 (ja) | 2002-06-17 | 2007-08-29 | コンストラクション リサーチ アンド テクノロジー ゲーエムベーハー | 混和剤 |
-
2005
- 2005-02-04 WO PCT/EP2005/050497 patent/WO2005075381A1/fr not_active Application Discontinuation
- 2005-02-04 EP EP05707950A patent/EP1713744A1/fr not_active Withdrawn
- 2005-02-04 JP JP2006551860A patent/JP2007520413A/ja not_active Withdrawn
-
2006
- 2006-09-05 NO NO20063950A patent/NO20063950L/no not_active Application Discontinuation
-
2009
- 2009-02-24 US US12/391,775 patent/US20100071595A1/en not_active Abandoned
-
2010
- 2010-10-04 US US12/897,373 patent/US20110017100A1/en not_active Abandoned
- 2010-10-06 JP JP2010226465A patent/JP2011001266A/ja active Pending
Non-Patent Citations (2)
Title |
---|
None * |
See also references of WO2005075381A1 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2248780A1 (fr) | 2009-05-06 | 2010-11-10 | BK Giulini GmbH | Accélérateur de prise et de durcissement |
CN112110703A (zh) * | 2020-08-17 | 2020-12-22 | 济南大学 | 一种防水抗渗修补砂浆及施工方法与应用 |
Also Published As
Publication number | Publication date |
---|---|
NO20063950L (no) | 2006-09-05 |
WO2005075381A1 (fr) | 2005-08-18 |
JP2007520413A (ja) | 2007-07-26 |
US20110017100A1 (en) | 2011-01-27 |
US20100071595A1 (en) | 2010-03-25 |
JP2011001266A (ja) | 2011-01-06 |
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Legal Events
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