DE102005054190B3 - Hardening and hardening accelerator suspension used in a gunned concrete mixture comprises aluminum sulfate, amorphous aluminum hydroxide, carboxylic acid and/or their salts and sepiolite as stabilizer - Google Patents

Hardening and hardening accelerator suspension used in a gunned concrete mixture comprises aluminum sulfate, amorphous aluminum hydroxide, carboxylic acid and/or their salts and sepiolite as stabilizer Download PDF

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DE102005054190B3
DE102005054190B3 DE200510054190 DE102005054190A DE102005054190B3 DE 102005054190 B3 DE102005054190 B3 DE 102005054190B3 DE 200510054190 DE200510054190 DE 200510054190 DE 102005054190 A DE102005054190 A DE 102005054190A DE 102005054190 B3 DE102005054190 B3 DE 102005054190B3
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hardening
carboxylic acid
sepiolite
stabilizer
salts
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Burkhard Dr. Müller
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Rombold & Gfroehrer & Co GmbH
Rombold & Gfrohrer & Co KG GmbH
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Rombold & Gfroehrer & Co GmbH
Rombold & Gfrohrer & Co KG GmbH
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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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/10—Accelerators; Activators
    • C04B2103/12—Set accelerators
    • 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
    • C04B2103/14—Hardening accelerators
    • 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
    • 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
    • C04B2111/00215—Mortar or concrete mixtures defined by their oxide composition

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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

Hardening and hardening accelerator suspension comprises aluminum sulfate, amorphous aluminum hydroxide, carboxylic acid and/or their salts and sepiolite as stabilizer. The suspension contains (in wt.%) 12-25 aluminum oxide, 15-31 sulfate, 2-30 carboxylic acid and/or their salts and 0.4-1.5 sepiolite.

Description

Die vorliegende Erfindung betrifft einen Erhärtungs- und Erstarrungsbeschleuniger für zementhaltige Bindemittel, insbesondere Spritzbeton.The The present invention relates to a hardening and solidifying accelerator for cementitious binders, in particular shotcrete.

Es ist seit langem bekannt, Abbindebeschleuniger für zementhaltige Bindemittel einzusetzen, wobei früher Wasserglas verwendet wurde. Aufgrund seiner Alkalihaltigkeit führte dies zu sehr hohen pH-Werten, was in der Handhabung zu vielen Unfällen durch Verätzungen bei der Vortriebsmannschaft und Auswaschung von Alkalien führte, was wiederum zu Verstopfungen in Drainageleitungen führte. Mit derartigen Beschleunigern abgebundene Zemente können überdies beträchtliche Festigkeitsverluste aufweisen.It has long been known, setting accelerator for cementitious binders use earlier Water glass was used. Due to its alkalinity this led at very high pH levels, resulting in too many accidents due to acid burns in the tunneling team and leaching of alkalies led what again led to blockages in drainage pipes. With such accelerators hardened cements can also considerable Have strength losses.

Die spätere Verwendung von Alkalialuminaten haben den Nachteil des Festigkeitsverlustes weitgehend behoben, die anderen Nachteile der Verbindung von Wasserglas bleiben jedoch auch bei diesen Beschleunigern bestehen.The latter Use of alkali aluminates have the disadvantage of loss of strength largely resolved, the other disadvantages of the connection of water glass However, they also persist in these accelerators.

Die ersten alkalifreien Beschleuniger z.B. in der Form von Aluminiumsulfatlösungen hatten bei einem pH-Wert von 2,4 eine hohe Arbeitshygiene, jedoch Probleme eine gewünschte Frühfestigkeit des Spritzbetons zu realisieren, da der Aluminiumgehalt bei etwa 8% (Alle %-Angaben in dieser Anmeldung in Gew.-% zu niedrig war. Es folgten Beschleuniger als Aluminiumsulfat, amorphen Aluminiumhydroxid und organischer Säure, die in einer Lösung angeboten wurden, wie es z.B. in dem EP 946 451 B1 beschrieben ist. Dieser Beschleuniger enthält zwar einen hohen Anteil Al2O3, ist jedoch thermodynamisch nicht stabil. Lediglich die begrenzte Kinetik der Stoffe verhindert, dass sofort ein Feststoff auskristallisiert. Über die Zeit beginnt jedoch das Material auszukristallisieren. Dies führt in Vorratsbehältern auf der Baustelle zu dickeren Belägen, die mit großem Aufwand entfernt werden müssen. Die Neigung, dass sich Kristalle bilden, nimmt dabei mit steigendem Sulfatgehalt zu. So ist es z.B. nicht möglich, stabile Lösungen mit einem Gehalt von mehr als 19 Gew.-% SO4 –2 herzustellen.The first alkali-free accelerators, for example in the form of aluminum sulphate solutions, had a high working hygiene at a pH of 2.4 but problems to achieve a desired early strength of the shotcrete since the aluminum content was about 8% (all% data in this application in US Pat It was followed by accelerators as aluminum sulfate, amorphous aluminum hydroxide and organic acid, which were offered in a solution, such as in the EP 946 451 B1 is described. Although this accelerator contains a high proportion of Al 2 O 3 , it is not thermodynamically stable. Only the limited kinetics of the substances prevents a solid from immediately crystallizing out. Over time, however, the material begins to crystallize out. This leads in storage containers on the site to thicker coverings, which must be removed with great effort. The tendency for crystals to form increases with increasing sulfate content. For example, it is not possible to prepare stable solutions containing more than 19% by weight of SO 4 -2 .

Die DE 102 38 789 zeigt einen Abbinde- oder Erhärtungsbeschleuniger, der Aluminiumsulfat in Form einer Lösung enthält, die mehr als 8 Gew.-% Al2O3 und dispergierten Bentonit in Mengen von 1–7 Gew.-% enthält. Nachteilhaft ist hier, dass der Al2O3-Gehalt begrenzt ist, und die Festigkeitsentwicklung, insbesondere die Frühfestigkeit, verbesserungswürdig ist.The DE 102 38 789 shows a setting or hardening accelerator containing aluminum sulfate in the form of a solution containing more than 8 wt .-% Al 2 O 3 and dispersed bentonite in amounts of 1-7 wt .-%. The disadvantage here is that the Al 2 O 3 content is limited, and the strength development, especially the early strength, is in need of improvement.

Die WO 2005/075381 A1 zeigt einen Beschleuniger für hydraulische Bindemittel, der aus Aluminiumsulfat, Aluminiumhydroxid, Ameisensäure oder Essigsäure und einen Stabilisierer besteht, wobei für den Stabilisierer Silicasol angegeben ist.The WO 2005/075381 A1 shows an accelerator for hydraulic binders, from aluminum sulfate, aluminum hydroxide, formic acid or acetic acid and a stabilizer, wherein for the stabilizer silica sol is specified.

Die DE 600 02 918 T2 zeigt einen Beschleuniger, der neben Auluminiumsulfat und Aluminiumhydroxid einen Stabilisator in Form von Hydrocarbon- oder Phosphorsäuren umfasst.The DE 600 02 918 T2 shows an accelerator comprising in addition to aluminum sulfate and aluminum hydroxide, a stabilizer in the form of hydrocarbon or phosphoric acids.

Es ist daher Aufgabe der Erfindung, Abbinde- und Erhärtungsbeschleuniger für zementhaltige Bindemittel zu schaffen, die eine hohe Frühfestigkeit aufweisen, einen geringen Festigkeitsverlust haben, zu einer schnellen Beschleunigung führen und in der Anwendung und Lagerung sehr beständig ist. Diese Aufgabe wird erfindungsgemäß durch die Merkmale des Anspruchs 1 gelöst. Ein mit einem derartigen Abbinde- und Erhärtungsbeschleuniger abgebundener Spritzbeton ist Gegenstand des Anspruchs 4.It is therefore an object of the invention, setting and hardening accelerator for cementitious To provide binders which have a high early strength, a have low strength loss, to a fast acceleration to lead and is very stable in application and storage. This object is achieved by the features of claim 1 solved. A set with such a setting and hardening accelerator Shotcrete is the subject of claim 4.

Die Erfindung macht sich die Entdeckung zunutze, dass entgegen bisheriger Annahme, Suspensionen, die aus amorphem Aluminiumhydroxid, Aluminiumsulfat und Carbonsäure hergestellt werden, Spritzbeton genau so gut beschleunigen wie vergleichbare Lösungen. Dies hat zudem gegenüber Lösungen den Vorteil, dass durch die Suspension der für die Beschleunigung benötigte hohe Sulfatgehalt realisierbar ist, wobei die Suspension über einen geeigneten Stabilisierer aus der Gruppe der Schichtsilikate stabilisiert wird. Ferner sind mühelos Aluminium-Gehalte von über 15% realisierbar. Der Beschleuniger zeigt damit einen guten Festigkeitsverlauf und hohe Endfestigkeiten.The Invention makes use of the discovery that contrary to previous Assumption, suspensions made of amorphous aluminum hydroxide, aluminum sulfate and carboxylic acid made shotcrete accelerate just as well as comparable Solutions. This also has opposite solutions the advantage that due to the suspension required for the acceleration high Sulfate content is feasible, the suspension over a stabilizer stabilized from the group of phyllosilicates becomes. Furthermore, effortless Aluminum contents of over 15% feasible. The accelerator thus shows a good strength course and high final strengths.

Als Carbonsäure wird vorzugsweise eine Monocarbonsäure, wie z.B. eine Essigsäure, Proprionsäure oder Ameisensäure verwendet. Anstelle der Carbonsäure können auch deren Salze, insbesondere Aluminiumsalze verwendet werden, wobei in diesem Fall die Summe von Carbonsäure und deren Salzen in einem Bereich von 2 bis 30% liegen sollte.When carboxylic acid is preferably a monocarboxylic acid, e.g. an acetic acid, propionic acid or formic acid used. Instead of the carboxylic acid can also their salts, in particular aluminum salts are used, in which case the sum of carboxylic acid and its salts is in one range should be from 2 to 30%.

Für den Stabiliserer sollte aufgrund seiner hervorragenden stabiliserenden Eigenschaften Sepiolith in einer Menge von 0,4 bis 1,5% verwendet werden.For the stabilizer should due to its excellent stabilizing properties Sepiolite can be used in an amount of 0.4 to 1.5%.

Nachfolgend wird ein Ausführungsbeispiel in Vergleich mit einem Abbinde- und Erhärtungsbeschleuniger nach dem Stand der Technik beschrieben.following becomes an embodiment in comparison with a setting and hardening accelerator after State of the art described.

Beispiel 1:Example 1:

Ein Beispiel einer erfindungsgemäßen Suspension eines Erstarrungsbeschleunigers zur Verwendung als Spritzbetonbeschleuniger enthält (Alle Angaben in Gew.-%):
46,5% Aluminiumsulfat 14 Hydrat
15,0% Amorphes Aluminiumhydroxid
5,0% Ameisensäure
0,7% Sepiolith als StabilisiererAn example of a suspension according to the invention of a solidification accelerator for use as a shotcrete accelerator contains (all data in% by weight):
46.5% aluminum sulfate 14 hydrate
15.0% amorphous aluminum hydroxide
5.0% formic acid
0.7% Sepiolite as stabilizer

Der Al2O3-Gehalt dieses Beschleunigers beträgt 15,8%, der Sulfatgehalt 22,5%.Of the Al2O3 content of this accelerator is 15.8%, the sulfate content 22.5%.

Vergleichsbeispiel:Comparative Example:

Ein Vergleichsbeispiel eines Beschleunigers aus dem Stand der Technik liegt als Lösung vor und enthält:
39,0% Aluminiumsulfat 14 Hydrat
15,0% Amorphes Aluminiumhydroxid
5,0% AmeisensäureA comparative example of an accelerator of the prior art is available as a solution and contains:
39.0% aluminum sulfate 14 hydrate
15.0% amorphous aluminum hydroxide
5.0% formic acid

Der Aluminiumoxid(=Al2O3)-Gehalt betrug 14,5%, der Sulfatgehalt 18,9%.Of the Alumina (= Al2O3) content was 14.5%, the sulfate content 18.9%.

Für die Beurteilung der Eigenschaften der Beschleuniger gemäß Beispiel 1 und Vergleichsbeispiel wurde ein Transportbeton mit folgenden Eigenschaften verwendet:
400 kg CEM I42,5 R pro Kubikmeter Beton
Sieblinie B8
Wasser/Bindemittelwert 0,52For the evaluation of the properties of the accelerators according to Example 1 and Comparative Example, a ready-mixed concrete having the following properties was used:
400 kg CEM I42.5 R per cubic meter of concrete
Grading curve B8
Water / binder value 0.52

Gespritzt wurde der Beton mit einer Spritzmaschine Suprema von MBT.injected was the concrete with a machine Suprema MBT.

Die Fördermenge betrug 11 Kubikmeter/h.The output was 11 cubic meters / h.

Der Beschleunigergehalt betrug 7% bezogen auf den Zementgehalt im Beton.Of the Accelerator content was 7% based on the cement content in the concrete.

Es wurden folgende Festigkeitswerte erzielt (Angaben in N/mm2)

Figure 00040001
The following strength values were achieved (data in N / mm 2 )
Figure 00040001

Der Festigkeitsverlauf des Betons mit einem Beschleuniger des erfindungsgemäßen Beispiels 1 entspricht einem Festigkeitsverlauf der Klasse J3. Der Festigkeitsverlauf des Vergleichsbeispiels entspricht der Klasse J2 nach der Richtlinie Spritzbeton des Österreichischen Vereinigung für Beton- und Bautechnik.Of the Strength curve of the concrete with an accelerator of the example according to the invention 1 corresponds to a strength progression of class J3. The strength process of the comparative example corresponds to class J2 according to the directive Shotcrete of the Austrian Association for Concrete and construction engineering.

Claims (3)

Erstarrungs- und Erhärtungsbeschleunigersuspension für zementhaltige Bindemittel, umfassend Aluminiumsulfat, amorphes Aluminiumhydroxid, Carbonsäure und/oder deren Salze und Sepiolith als Stabilisierer mit folgenden Bestandteilen: – einem als Al2O3 bestimmten Gehalt von 12 bis 25 Gew.-%, – einem als SO4 bestimmten Gehalt von 15 bis 31 Gew.-%, – einem Gehalt an Carbonsäure und/oder deren Salz(e) von 2 bis 30 Gew.-%, und – einem Gehalt an Sepiolith von 0,4 bis 1,5 Gew.-%.A solidification and hardening accelerator suspension for cementitious binders comprising aluminum sulfate, amorphous aluminum hydroxide, carboxylic acid and / or salts thereof and sepiolite stabilizer having the following components: a content of 12 to 25% by weight determined as Al 2 O 3 , one as SO 2 4 content of 15 to 31 wt .-%, - a content of carboxylic acid and / or its salt (s) of 2 to 30 wt .-%, and - a content of sepiolite of 0.4 to 1.5 wt. -%. Erstarrungs- und Erhärtungsbeschleuniger nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Carbonsäure durch eine Monocarbonsäure, z.B. Ameisensäure, Essigsäure oder Proprionsäure gebildet ist.A solidification and hardening accelerator according to claim 1 or 2, characterized in that the Carboxylic acid is formed by a monocarboxylic acid, for example formic acid, acetic acid or propionic acid. Verwendung der Erstarrungs- und Erhärtungsbeschleunigersuspension nach einem der vorhergehenden Ansprüche in einer Spritzbetonmischung.Use of the solidification and hardening accelerator suspension according to one of the preceding claims in a shotcrete mixture.
DE200510054190 2005-11-14 2005-11-14 Hardening and hardening accelerator suspension used in a gunned concrete mixture comprises aluminum sulfate, amorphous aluminum hydroxide, carboxylic acid and/or their salts and sepiolite as stabilizer Expired - Fee Related DE102005054190B3 (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2075240A1 (en) * 2007-12-20 2009-07-01 Sika Technology AG Catalyst for reactivation of delayed cementitious systems
WO2013023730A3 (en) * 2011-08-18 2013-03-28 Heidelbergcement Ag Method and additive for increasing early strength
EP2617692A1 (en) * 2011-08-18 2013-07-24 HeidelbergCement AG Method and additive for increasing early strength
CN115448630A (en) * 2022-10-08 2022-12-09 湘潭家园建材有限公司 Accelerating agent and preparation method thereof

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Publication number Priority date Publication date Assignee Title
EP1167317B1 (en) * 2000-06-21 2003-11-26 Sika Schweiz AG Alkali-free set and hardening accelerator
DE60002918T2 (en) * 1999-12-08 2003-12-24 Mbt Holding Ag, Zuerich MANUFACTURE OF CONCRETE ACCELERATOR
WO2005075381A1 (en) * 2004-02-06 2005-08-18 Sika Technology Ag Water-based coagulating and hardening accelerator for hydraulic binders and method for the production thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE60002918T2 (en) * 1999-12-08 2003-12-24 Mbt Holding Ag, Zuerich MANUFACTURE OF CONCRETE ACCELERATOR
EP1167317B1 (en) * 2000-06-21 2003-11-26 Sika Schweiz AG Alkali-free set and hardening accelerator
WO2005075381A1 (en) * 2004-02-06 2005-08-18 Sika Technology Ag Water-based coagulating and hardening accelerator for hydraulic binders and method for the production thereof

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2075240A1 (en) * 2007-12-20 2009-07-01 Sika Technology AG Catalyst for reactivation of delayed cementitious systems
WO2013023730A3 (en) * 2011-08-18 2013-03-28 Heidelbergcement Ag Method and additive for increasing early strength
EP2617692A1 (en) * 2011-08-18 2013-07-24 HeidelbergCement AG Method and additive for increasing early strength
US9067825B2 (en) 2011-08-18 2015-06-30 Heidelbergcement Ag Method for producing ternesite-belite calcium sulfoaluminate clinker
US9067826B2 (en) 2011-08-18 2015-06-30 Heidelbergcement Ag Ternesite used as an additive in Portland cement
US9073784B2 (en) 2011-08-18 2015-07-07 Heidelbergcement Ag Calcium sulfoaluminate cement with ternesite
US9212091B2 (en) 2011-08-18 2015-12-15 Heidelbergcement Ag Method and additive for increasing early strength
US9302940B2 (en) 2011-08-18 2016-04-05 Heidelbergcement Ag Ternesite used as an activator for latent-hydraulic and pozzolanic materials
EA027741B1 (en) * 2011-08-18 2017-08-31 Хайдельбергцемент Аг Method and additives for increasing starting resistance
CN115448630A (en) * 2022-10-08 2022-12-09 湘潭家园建材有限公司 Accelerating agent and preparation method thereof

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