WO2006010407A1 - Setting accelerator for sprayed concrete - Google Patents

Setting accelerator for sprayed concrete Download PDF

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Publication number
WO2006010407A1
WO2006010407A1 PCT/EP2005/006442 EP2005006442W WO2006010407A1 WO 2006010407 A1 WO2006010407 A1 WO 2006010407A1 EP 2005006442 W EP2005006442 W EP 2005006442W WO 2006010407 A1 WO2006010407 A1 WO 2006010407A1
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WO
WIPO (PCT)
Prior art keywords
dissolved
liquid mixture
weight
aluminium
accelerating
Prior art date
Application number
PCT/EP2005/006442
Other languages
French (fr)
Inventor
Terje Angelskar
Original Assignee
Construction Research & Technology Gmbh
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 Construction Research & Technology Gmbh filed Critical Construction Research & Technology Gmbh
Priority to EP05750547A priority Critical patent/EP1805115A1/en
Priority to CA2575146A priority patent/CA2575146C/en
Priority to CN2005800253292A priority patent/CN1989082B/en
Priority to JP2007522931A priority patent/JP4928450B2/en
Priority to US11/658,549 priority patent/US8118930B2/en
Publication of WO2006010407A1 publication Critical patent/WO2006010407A1/en
Priority to NO20070623A priority patent/NO20070623L/en

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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
    • 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
    • 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

Definitions

  • This invention relates to an accelerating admixture for concrete, to the use of the accelerating admixture and to a layer of hardened concrete.
  • Sprayed concrete or "shotcrete" which is applied to substrates such as rock surfaces and tun ⁇ nels by spraying must set very rapidly.
  • the traditional concrete accelerators such as calciumchloride are not effective and more powerful accelerators must be used, including sodiumaluminate and alkaline metal hydroxide. These are highly alkaline, which gives rive both to handling difficulties and unpleasant conditions when spraying in confined spaces such as tunnels.
  • aluminium hydroxide may be partially reacted with an acid, preferably an organic acid - see, for example EP-A-O 798 300.
  • Aluminium sulfate is also known as a component of accelerating systems, and is described in, for example, EP-B-O 946451.
  • An ⁇ other aluminium compound which has been used in concrete accelerators is basic aluminium sulfate (also known as aluminium hydroxysulfate) - see, for example US-B-5,997,630.
  • admixtures In order to provide a sufficient storage stability accelerating admixtures normally contain in ⁇ gredients which prevent the precipitation of aluminium salts. Such ingredients are for exam ⁇ ple carboxylic acids, which are typically used in sufficient amounts to stabilise the corre ⁇ sponding accelerator composition - see, for example EP-B-I 114 004.
  • the object of the present invention is to provide an accelerating admixture for concrete which fulfils all of the said characteristics.
  • the solution of this object is an accelerating admixture for concrete, containing a liquid mix ⁇ ture being an aqueous solution or an aqueous dispersion, wherein
  • the liquid mixture contains 13 to 43 weight % dissolved aluminium sulfate
  • the liquid mixture contains less than 1 weight % dissolved carboxylic acid
  • the liquid mixture contains at least 31 weight % water
  • the molar ratio of dissolved aluminium to dissolved sulfate in the liquid mixture is from 0.5 to 10.0.
  • Dissolved aluminium sulfate should mean the amount of aluminium sulfate which is in aqueous solution. If the liquid mixture does not contain an equimolar ratio of the both compo ⁇ nents dissolved aluminium and dissolved sulfate (this might be the case, if other aluminium and sulfate providing soluble salts than aluminium sulfate (salt) itself are used) the basis for the dissolved amount of aluminium sulfate should be the component (aluminium or sulfate) which has the lowest concentration in solution (example: if the concentration of dissolved alumimum is X mol and the concentration of dissolved sulfate is X+l mol, the concentration of dissolved aluminium sulfate should be X mol).
  • carboxylic acid is intended to include also carboxylic acids containing more than one carboxylic function and other functional groups like amino groups (amino acids) or hy- droxyl groups (hydroxycarboxylic acids). As carboxylic acids are - depending on the pH- value - often contained in the deprotonated form, the term “carboxylic acid” should also mean carboxylate or a corresponding mixture of carboxylate and carboxylic acid.
  • carboxylic acids are often strong carboxylic acids like formic acid or acetic acid but also amino acids like glycin or asparaginic acid may provide good results.
  • the water of the liquid mixture may have its origin partly in the crystal water of dissolved salts.
  • the liquid mixture is an aqueous dispersion
  • the dispersion should not contain more than 15 weight %, preferably not more than 5 weight % not dissolved material (which might be contained at least partly as a bottom layer).
  • Not dissolved parts of the dispersion may be aluminium and sulfate salts (which are in surplus), polymers, impurities and other ingredients. But it is preferred that all aluminium and sulfate salts are dissolved.
  • an aqueous solution is preferred, because it is easier to handle.
  • the accelerating admixture according to the present invention fulfils all the three important criteria which are normally appreciated by the customers which are using the accelerators:
  • the accelerator is economical, provides fast setting times and shows a sufficient stability.
  • a relatively low price of the said accelerating admixture is achieved because it contains only a low amount of the carboxylic acid, which is normally the most expensive component of such an accelerating admixture.
  • such an accelerating admixture provides very often shorter setting times than corresponding admixtures which have a much higher content of carboxylic acid.
  • the accelerating admixture according to the present invention shows a sufficient stability, so that the precipitation of dissolved ingredi ⁇ ents is hindered or retarded.
  • the liquid mixture contains 15 to 35, preferably 18 to 32 weight % dissolved alu ⁇ minium sulfate.
  • the basis for the dissolved aluminium sulfate (solution/ dispersion) might be aluminium sulfate (salt) and/ or aluminium hydroxysulfate (salt) which both might contain crystal water or for example aluminium hydroxide and sulfuric acid.
  • the higher the weight % amount of aluminium the higher is normally the performance of the accelerator (short setting time). But if the weight % amount of aluminium is too high it is more likely that the stability of the accelerating admixture deteriorates.
  • the liquid mixture contains 0 to 0.9 weight % carboxylic acid, for some applications preferably no dissolved carboxylic acid. If the accelerator contains no carboxylic acid the price is normally optimised but it may be an advantage to take also the stability of the ad ⁇ mixture into consideration (some applicants might appreciate a long life stability). Then the liquid mixture should normally contain 0.1 to 0.9 weight % dissolved carboxylic acid. But it is generally typical that the molar ratio of dissolved aluminium to dissolved carboxylic acid is at least 7 to 1, more preferably 13 to 1.
  • the liquid mixture contains 43 to 76, preferably 51 to 65 weight % water. If too much water is used, the corresponding accelerator admixture provides not sufficient performance (setting times will be too long) but if the content of water is not high enough, the accelerating admixture might not be stable enough.
  • the molar ratio of dissolved aluminium to dissolved sufate in the liquid mixture is from 1.1 to 7.0, preferably from 1.1 to 4.3.
  • Admixtures which have a molar ratio of dissolved aluminium to dissolved sulfate which is greater than 1.1 show very often a better performance than corresponding admixtures which have a lower ratio.
  • an admixture which has a corresponding ratio which is smaller than 7.0 is often more stable than a corre ⁇ sponding admixture which has a higher ratio.
  • the liquid mixture contains dissolved aluminium hydroxide, wherein it is advantageous that the liquid mixture contains 3 to 35, more preferably 6 to 19 weight % dis ⁇ solved aluminium hydroxide.
  • the aluminium hydroxide may react with other dissolved ingre ⁇ ders in solution (for example with carboxylic acid) so that it is sometimes impossible to find aluminium hydroxide in solution.
  • the basis for the dissolved aluminium hydroxide can be aluminium hydroxide (salt) itself (preferably amorphous aluminium hydroxide) and basic aluminium sulfate like aluminium hydroxysulfate. All these salts may contain crystal water.
  • the liquid mixture may additionally contain further components which are for example alka- nolamines like diethanloamine or triethanolamine or mixtures thereof, polymers, which are preferably not completely dissolved, phosphoric acid, phosphorous acid and corrosion inhibitors which are typically used in sprayed concrete.
  • further components which are for example alka- nolamines like diethanloamine or triethanolamine or mixtures thereof, polymers, which are preferably not completely dissolved, phosphoric acid, phosphorous acid and corrosion inhibitors which are typically used in sprayed concrete.
  • the liquid mixture contains except alkanolamines and carboxylic acids no further organic compounds. If alkanolamines are not taken into consideration the liquid mixture contains preferably less than 1 weight % dissolved organic compounds. This provides an improved environmental compatibility, a reduced price of the product and very often a better performance of the accelerator.
  • the accelerating admixture of the present invention consists of the said liquid mixture.
  • the admixture (the liquid mixture) according to the invention may be manufactured by any convenient means.
  • the order of addition of components is normally not critical.
  • it is possible and permissible first to react the carboxylic acid (only if carboxylic acid is used) and the aluminium hydroxide (only if aluminium hydroxide is used) to form corresponding aluminium carboxylates and then to add the other components thereto.
  • the mixing/ reaction could be carried out at elevated temperature, no higher than 90 to 95 °C.
  • the aluminium hydroxide (if used) may be added last, to a heated mixture of the other components. This is a preferred method.
  • the admixture of the present invention may be used in an art-recognised manner with sprayed concrete or "shotcrete".
  • the invention therefore provides the use of an accelerating admixture as described above for spraying concrete in a tunnel or in a mine. This means that in a corre ⁇ sponding process a substrate is coated with concrete by preparing a sprayable concrete mix and spraying this mix on the substrate through a nozzle, there being supplied to the mix at the nozzle an accelerating admixture as hereinabove described.
  • the admixture is provided to the nozzle as an aqueous solution or suspension at typically 50 to 60 % solids by weight of the suspension, and so that the concrete receives from 0.5 to 25 % by weight of admixture (solids on cement).
  • the actual figure used will vary, depending on the type of cement and the mix design, but the provision of a suitable quantity is well within the skill of the art.
  • the pre- nozzle, hardening having been accelerated by the edition at the nozzle of an accelerating amount of an accelerator admixture as hereinabove described.
  • compositions which are accelerating admixtures according to the present invention compositions number Ib, Ic, 2b and 2c
  • compositions number Ia and 2a compositions which are accelerating admixtures according to the present invention
  • Al(OH) 3 amorphous aluminium hydroxide
  • the used mortar was prepared according to SOP 3.3-410032 (based on EN 480).
  • the setting time was determined according to SOP 3.3-410032 (based on EN 480): the pene ⁇ tration of a cylindrical needle with a diameter of 1.13 mm and a load weight of 30Og in the mortar is measured periodically. Initial setting is said to have taken place when the mortar stiffens sufficiently for the needle to penetrate no deeper than to a point of 4 ⁇ lmm from the bottom. Final setting is determined by means of measuring the time from completing of mix ⁇ ing until the needle, gently lowered to the surface of the mortar, no longer penetrates it.

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  • 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)
  • Lining And Supports For Tunnels (AREA)

Abstract

An accelerating admixture for concrete, containing a liquid mixture being an aqueous solution or an aqueous dispersion, wherein a) the liquid mixture contains 13 to 43 weight % dissolved aluminium sulfate, b) the liquid mixture contains less than 1 weight % dissolved carboxylic acid, c) the liquid mixture contains at least 31 weight % water, d) the molar ratio of dissolved aluminium to dissolved sulfate in the liquid mixture is from 0.5 to 10.0.

Description

Setting accelerator for sprayed concrete
Description
This invention relates to an accelerating admixture for concrete, to the use of the accelerating admixture and to a layer of hardened concrete.
Sprayed concrete or "shotcrete" which is applied to substrates such as rock surfaces and tun¬ nels by spraying must set very rapidly. In such a use, the traditional concrete accelerators such as calciumchloride are not effective and more powerful accelerators must be used, including sodiumaluminate and alkaline metal hydroxide. These are highly alkaline, which gives rive both to handling difficulties and unpleasant conditions when spraying in confined spaces such as tunnels.
An alternative accelerating technology based on aluminium compounds has been known for some time. The use of aluminium hydroxide either alone or combined with other materials is described in EP-B-O 076 927.
In a variation on this, aluminium hydroxide may be partially reacted with an acid, preferably an organic acid - see, for example EP-A-O 798 300. Aluminium sulfate is also known as a component of accelerating systems, and is described in, for example, EP-B-O 946451. An¬ other aluminium compound which has been used in concrete accelerators is basic aluminium sulfate (also known as aluminium hydroxysulfate) - see, for example US-B-5,997,630.
In order to provide a sufficient storage stability accelerating admixtures normally contain in¬ gredients which prevent the precipitation of aluminium salts. Such ingredients are for exam¬ ple carboxylic acids, which are typically used in sufficient amounts to stabilise the corre¬ sponding accelerator composition - see, for example EP-B-I 114 004.
The disadvantage of known accelerating admixtures is that they generally do not fulfil all of the following characteristics which are in combination appreciated by the users of accelerat¬ ing admixtures: providing a short setting time,
- having a sufficient storage stability and
- being economical.
Thus, the object of the present invention is to provide an accelerating admixture for concrete which fulfils all of the said characteristics.
The solution of this object is an accelerating admixture for concrete, containing a liquid mix¬ ture being an aqueous solution or an aqueous dispersion, wherein
a) the liquid mixture contains 13 to 43 weight % dissolved aluminium sulfate,
b) the liquid mixture contains less than 1 weight % dissolved carboxylic acid,
c) the liquid mixture contains at least 31 weight % water,
d) the molar ratio of dissolved aluminium to dissolved sulfate in the liquid mixture is from 0.5 to 10.0.
"Dissolved aluminium sulfate" should mean the amount of aluminium sulfate which is in aqueous solution. If the liquid mixture does not contain an equimolar ratio of the both compo¬ nents dissolved aluminium and dissolved sulfate (this might be the case, if other aluminium and sulfate providing soluble salts than aluminium sulfate (salt) itself are used) the basis for the dissolved amount of aluminium sulfate should be the component (aluminium or sulfate) which has the lowest concentration in solution (example: if the concentration of dissolved alumimum is X mol and the concentration of dissolved sulfate is X+l mol, the concentration of dissolved aluminium sulfate should be X mol).
The term "carboxylic acid" is intended to include also carboxylic acids containing more than one carboxylic function and other functional groups like amino groups (amino acids) or hy- droxyl groups (hydroxycarboxylic acids). As carboxylic acids are - depending on the pH- value - often contained in the deprotonated form, the term "carboxylic acid" should also mean carboxylate or a corresponding mixture of carboxylate and carboxylic acid.
Appropriate carboxylic acids are often strong carboxylic acids like formic acid or acetic acid but also amino acids like glycin or asparaginic acid may provide good results.
The water of the liquid mixture may have its origin partly in the crystal water of dissolved salts.
If the liquid mixture is an aqueous dispersion the basis of this mixture is water. The dispersion should not contain more than 15 weight %, preferably not more than 5 weight % not dissolved material (which might be contained at least partly as a bottom layer). Not dissolved parts of the dispersion may be aluminium and sulfate salts (which are in surplus), polymers, impurities and other ingredients. But it is preferred that all aluminium and sulfate salts are dissolved. Generally, an aqueous solution is preferred, because it is easier to handle.
The accelerating admixture according to the present invention fulfils all the three important criteria which are normally appreciated by the customers which are using the accelerators:
The accelerator is economical, provides fast setting times and shows a sufficient stability. A relatively low price of the said accelerating admixture is achieved because it contains only a low amount of the carboxylic acid, which is normally the most expensive component of such an accelerating admixture. Surprisingly such an accelerating admixture provides very often shorter setting times than corresponding admixtures which have a much higher content of carboxylic acid. It should be also emphasised that the accelerating admixture according to the present invention shows a sufficient stability, so that the precipitation of dissolved ingredi¬ ents is hindered or retarded.
It is possible that after several months or a few years a corresponding aqueous solution devel¬ ops into a dispersion because dissolved ingredients may precipitate, but also such a dispersion has the advantages of the present invention, because it still contains sufficient dissolved amounts of the corresponding ingredients (especially aluminium sulfate). Normally the liquid mixture contains 15 to 35, preferably 18 to 32 weight % dissolved alu¬ minium sulfate. The basis for the dissolved aluminium sulfate (solution/ dispersion) might be aluminium sulfate (salt) and/ or aluminium hydroxysulfate (salt) which both might contain crystal water or for example aluminium hydroxide and sulfuric acid. The higher the weight % amount of aluminium the higher is normally the performance of the accelerator (short setting time). But if the weight % amount of aluminium is too high it is more likely that the stability of the accelerating admixture deteriorates.
Normally the liquid mixture contains 0 to 0.9 weight % carboxylic acid, for some applications preferably no dissolved carboxylic acid. If the accelerator contains no carboxylic acid the price is normally optimised but it may be an advantage to take also the stability of the ad¬ mixture into consideration (some applicants might appreciate a long life stability). Then the liquid mixture should normally contain 0.1 to 0.9 weight % dissolved carboxylic acid. But it is generally typical that the molar ratio of dissolved aluminium to dissolved carboxylic acid is at least 7 to 1, more preferably 13 to 1.
In an preferred embodiment of the invention the liquid mixture contains 43 to 76, preferably 51 to 65 weight % water. If too much water is used, the corresponding accelerator admixture provides not sufficient performance (setting times will be too long) but if the content of water is not high enough, the accelerating admixture might not be stable enough.
Mostly the molar ratio of dissolved aluminium to dissolved sufate in the liquid mixture is from 1.1 to 7.0, preferably from 1.1 to 4.3. Admixtures which have a molar ratio of dissolved aluminium to dissolved sulfate which is greater than 1.1 show very often a better performance than corresponding admixtures which have a lower ratio. But on the other hand an admixture which has a corresponding ratio which is smaller than 7.0 is often more stable than a corre¬ sponding admixture which has a higher ratio.
It is preferred that the liquid mixture contains dissolved aluminium hydroxide, wherein it is advantageous that the liquid mixture contains 3 to 35, more preferably 6 to 19 weight % dis¬ solved aluminium hydroxide. The aluminium hydroxide may react with other dissolved ingre¬ dients in solution (for example with carboxylic acid) so that it is sometimes impossible to find aluminium hydroxide in solution. The basis for the dissolved aluminium hydroxide can be aluminium hydroxide (salt) itself (preferably amorphous aluminium hydroxide) and basic aluminium sulfate like aluminium hydroxysulfate. All these salts may contain crystal water.
The liquid mixture may additionally contain further components which are for example alka- nolamines like diethanloamine or triethanolamine or mixtures thereof, polymers, which are preferably not completely dissolved, phosphoric acid, phosphorous acid and corrosion inhibitors which are typically used in sprayed concrete.
In a preferred embodiment the liquid mixture contains except alkanolamines and carboxylic acids no further organic compounds. If alkanolamines are not taken into consideration the liquid mixture contains preferably less than 1 weight % dissolved organic compounds. This provides an improved environmental compatibility, a reduced price of the product and very often a better performance of the accelerator.
In a preferred embodiment the accelerating admixture of the present invention consists of the said liquid mixture. The admixture (the liquid mixture) according to the invention may be manufactured by any convenient means. The order of addition of components is normally not critical. Thus, for example, it is possible and permissible first to react the carboxylic acid (only if carboxylic acid is used) and the aluminium hydroxide (only if aluminium hydroxide is used) to form corresponding aluminium carboxylates and then to add the other components thereto. The mixing/ reaction could be carried out at elevated temperature, no higher than 90 to 95 °C. Alternatively, the aluminium hydroxide (if used) may be added last, to a heated mixture of the other components. This is a preferred method.
The admixture of the present invention may be used in an art-recognised manner with sprayed concrete or "shotcrete". The invention therefore provides the use of an accelerating admixture as described above for spraying concrete in a tunnel or in a mine. This means that in a corre¬ sponding process a substrate is coated with concrete by preparing a sprayable concrete mix and spraying this mix on the substrate through a nozzle, there being supplied to the mix at the nozzle an accelerating admixture as hereinabove described. The admixture is provided to the nozzle as an aqueous solution or suspension at typically 50 to 60 % solids by weight of the suspension, and so that the concrete receives from 0.5 to 25 % by weight of admixture (solids on cement). The actual figure used will vary, depending on the type of cement and the mix design, but the provision of a suitable quantity is well within the skill of the art. Thus the pre- nozzle, hardening having been accelerated by the edition at the nozzle of an accelerating amount of an accelerator admixture as hereinabove described.
The invention is further described with reference to the following non-limiting examples:
The following table shows compositions which are accelerating admixtures according to the present invention (compositions number Ib, Ic, 2b and 2c) and comparative accelerating ad¬ mixtures which are not according to the present invention (compositions number Ia and 2a).
Figure imgf000007_0001
DEA = diethylamine
Al(OH)3 = amorphous aluminium hydroxide
The values in the table are given in weight %
All these accelerating admixtures (Ia, Ib, Ic, 2a, 2b and 2c) are clear to opaque solutions which are stable at about 20°C for at least 8 weeks.
Testing of the admixture compositions according to the above mentioned table:
1. Preparing of mortar mix for laboratory testing
The used mortar was prepared according to SOP 3.3-410032 (based on EN 480).
2. Determination of setting time
The setting time was determined according to SOP 3.3-410032 (based on EN 480): the pene¬ tration of a cylindrical needle with a diameter of 1.13 mm and a load weight of 30Og in the mortar is measured periodically. Initial setting is said to have taken place when the mortar stiffens sufficiently for the needle to penetrate no deeper than to a point of 4 ± lmm from the bottom. Final setting is determined by means of measuring the time from completing of mix¬ ing until the needle, gently lowered to the surface of the mortar, no longer penetrates it.
3. Determination of compressive strength
Compressive strength tests on mortar specimens have been done according to EN 196-1 : the mortar specimens, derived from 40 x 40 x 160 mm prisms, were placed on a hydraulic press and the load necessary for rupture measured.
4. Results
Following results were obtained, if the accelerating admixtures according to the table above were used:
Figure imgf000009_0001
(1) The W/C ratio (water/cement ratio) has been adjusted to obtain a consistence of 19±1 cm Evaluation of the results:
The above mentioned results show that all of the accelerating admixtures (Ia, Ib, Ic, 2a, 2b, and 2c) provide short initial setting times, short final setting times and high compressive strenghts. Also the stability of all tested accelerating admixtures is positive, because all these admixtures (Ia, Ib, Ic, 2a, 2b and 3c) are stable at about 20°C for at least 8 weeks. This means that the use of high amounts of carboxylic acid (more than 1 weight % of the corre¬ sponding admixture) does not provide any technical advantage but only the disadvantages that these admixtures which contain a high amount of carboxylic acid (like composition Ia and 2a) are more expensive than the compositions according to the present invention (for example composition Ib, Ic, 2b and 2c). Thus the accelerating admixtures according to the present invention fulfil all of the three criteria: providing a short setting time, having a sufficient stor¬ age stability and being economical.

Claims

Claims
1. An accelerating admixture for concrete, containing a liquid mixture being an aqueous so¬ lution or an aqueous dispersion, wherein
a) the liquid mixture contains 13 to 43 weight % dissolved aluminium sulfate,
b) the liquid mixture contains less than 1 weight % dissolved carboxylic acid,
c) the liquid mixture contains at least 31 weight % water,
d) the molar ratio of dissolved aluminium to dissolved sulfate in the liquid mixture is from 0.5 to 10.0.
2. An accelerating admixture according to claim 1, wherein the liquid mixture contains 15 to 35, preferably 18 to 32 weight % dissolved aluminium sulfate.
3. An accelerating admixture according to claims 1 or 2, wherein the liquid mixture contains 0 to 0.9 weight %, preferably no dissolved carboxylic acid.
4. An accelerating admixture according to claim 1 or 2, wherein the liquid mixture contains 0.1 to 0.9 weight % dissolved carboxylic acid.
5. An accelerating admixture according to one of the claims 1 to 4, wherein the liquid mix¬ ture contains 43 to 76, preferably 51 to 65 weight % water.
6. An accelerating admixture according to one of the claims 1 to 5, wherein the molar ratio of dissolved aluminium to dissolved sulfate in the liquid mixture is from 1.1 to 7.0, pref¬ erably from 1.1 to 4.3.
7. An accelerating admixture according to one of the claims 1 to 6, wherein the liquid mix¬ ture contains dissolved aluminium hydroxide.
8. An accelerating admixture according to claim 7, wherein the liquid mixture contains 3 to 35, preferably 6-19 weight % dissolved aluminium hydroxide.
9. Use of an accelerating admixture according to one of the claims 1 to 8 for spraying con¬ crete in a tunnel or in a mine.
10. A layer of hardened concrete applied by spraying to a substrate via a nozzle, hardening having been accelerated by the addition at the nozzle of an accelerating amount of an ac¬ celerator admixture according to any of the claims 1 to 8.
PCT/EP2005/006442 2004-07-28 2005-06-16 Setting accelerator for sprayed concrete WO2006010407A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP05750547A EP1805115A1 (en) 2004-07-28 2005-06-16 Setting accelerator for sprayed concrete
CA2575146A CA2575146C (en) 2004-07-28 2005-06-16 Setting accelerator for sprayed concrete
CN2005800253292A CN1989082B (en) 2004-07-28 2005-06-16 Setting accelerator for sprayed concrete
JP2007522931A JP4928450B2 (en) 2004-07-28 2005-06-16 Curing accelerator for shotcrete
US11/658,549 US8118930B2 (en) 2004-07-28 2005-06-16 Setting accelerator for sprayed concrete
NO20070623A NO20070623L (en) 2004-07-28 2007-02-02 Hardening accelerator for spray concrete

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB0416791.2A GB0416791D0 (en) 2004-07-28 2004-07-28 Setting accelerator for sprayed concrete
GB0416791.2 2004-07-28

Publications (1)

Publication Number Publication Date
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US (1) US8118930B2 (en)
EP (1) EP1805115A1 (en)
JP (1) JP4928450B2 (en)
CN (1) CN1989082B (en)
AU (1) AU2005266646A1 (en)
CA (1) CA2575146C (en)
GB (1) GB0416791D0 (en)
NO (1) NO20070623L (en)
TW (1) TWI413628B (en)
WO (1) WO2006010407A1 (en)

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EP2248780A1 (en) 2009-05-06 2010-11-10 BK Giulini GmbH Set- and hardening accelerator
US8075688B2 (en) 2008-01-11 2011-12-13 Construction Research & Technology Gmbh Aqueous accelerator mixture
WO2015173213A1 (en) * 2014-05-14 2015-11-19 Sika Technology Ag Stabilized solidification and setting accelerator for hydraulic binders
CN107586054A (en) * 2017-09-06 2018-01-16 江苏尼高科技有限公司 Gunite concrete alkali-free liquid accelerator and preparation method thereof
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JP2014019623A (en) * 2012-07-20 2014-02-03 Denki Kagaku Kogyo Kk Suspension type cement quick-setting agent, and quick-setting cement concrete using the same
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CN111377654B (en) * 2018-12-29 2021-11-09 江苏苏博特新材料股份有限公司 Hybrid alkali-free accelerator and preparation method thereof
CN111377638A (en) * 2018-12-29 2020-07-07 江苏苏博特新材料股份有限公司 Liquid alkali-free accelerator for improving cohesiveness of sprayed concrete and preparation method thereof
CN114057422B (en) * 2021-12-22 2022-12-02 云南云天化股份有限公司 Alkali-free fluorine-free chlorine-free liquid concrete accelerator and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000078688A1 (en) * 1999-06-18 2000-12-28 Mbt Holding Ag Concrete admixture
WO2001042165A2 (en) * 1999-12-08 2001-06-14 Mbt Holding Ag Preparation of concrete accelerator
WO2003029163A2 (en) * 2001-09-28 2003-04-10 Construction Research & Technology Gmbh Accelerator composition
WO2003045872A1 (en) * 2001-11-28 2003-06-05 Construction Research & Technology Gmbh Cement accelerator and method

Family Cites Families (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB650745A (en) 1946-10-24 1951-02-28 Kaspar Winkler Improvements in and relating to hydraulic binding agents
CH648272A5 (en) * 1981-10-12 1985-03-15 Sika Ag ALKALIF-FREE SETTING AND HARDENING ACCELERATOR AND METHOD FOR ACCELERATING THE SETTING AND HARDENING OF A HYDRAULIC BINDING AGENT.
DE3140784A1 (en) * 1981-10-14 1983-04-28 Freudenberg, Carl, 6940 Weinheim "SUCTIONABLE SURFACE AND METHOD FOR THE PRODUCTION THEREOF"
US4836855A (en) * 1983-03-01 1989-06-06 Abc Bio-Industries Additive of protein nature for hydraulic cements, mortars & concretes, and use thereof in the field construction
US4473405A (en) * 1983-04-11 1984-09-25 Martin Marietta Corporation Admixture for hydraulic cement
JPS61229807A (en) * 1985-04-05 1986-10-14 G C Dental Ind Corp Dental cement composition
CH680730A5 (en) 1990-07-09 1992-10-30 Sika Ag
CH681720A5 (en) 1991-04-12 1993-05-14 Sika Ag
US5211751A (en) * 1992-02-28 1993-05-18 W.R. Grace & Co.-Conn. Hydraulic cement set-accelerating admixtures incorporating amino acid derivatives
CH686513A5 (en) * 1993-12-06 1996-04-15 Sika Ag Method of accelerating the setting and setting of a binder and setting and setting accelerators.
ES2107258T3 (en) * 1994-03-03 1997-11-16 Sika Ag HARDENING AND SETTING ACCELERATOR WITHOUT CHLORIDE OR NITRITE AND PROCEDURE FOR THE ACCELERATION OF THE SETTING AND HARDENING OF HYDRAULIC BINDING SUBSTANCES AND THE MIXTURES CONTAINING THEM.
GB9416114D0 (en) 1994-08-10 1994-09-28 Sandoz Ltd Improvements in or relating to organic compounds
FR2732260B1 (en) * 1995-04-03 1997-05-09 Rhone Poulenc Chimie CONCRETE OR MORTAR PROJECTION PROCESS
GB9513116D0 (en) * 1995-06-28 1995-08-30 Sandoz Ltd Improvements in or relating to organic compounds
BR9612120A (en) * 1995-12-05 1999-12-28 Periclasse Pty Ltd Consolidable composition, manufactured article and residual product encapsulation method.
DE59605357D1 (en) 1996-03-09 2000-07-06 Bk Giulini Chem Gmbh & Co Ohg Aluminum connections
EP0812812B1 (en) 1996-06-14 2003-01-29 Mbt Holding Ag Concrete spraying additives
AU723970B2 (en) * 1996-06-14 2000-09-07 Construction Research & Technology Gmbh Concrete spraying additives
DK0946451T4 (en) 1996-10-25 2005-12-27 Bk Giulini Gmbh Strengthening and curing accelerator for hydraulic binders
GB9723945D0 (en) * 1997-11-12 1998-01-07 Nat Environmental Research Cou Tissue cement
JP2000185952A (en) 1998-10-13 2000-07-04 Taiheiyo Cement Corp Liquid accelerator for cement
JP2001130935A (en) 1999-10-29 2001-05-15 Katekkusu:Kk Rapidly curing agent for concrete
JP3328258B2 (en) * 2000-01-27 2002-09-24 ニチハ株式会社 Method of promoting cement hardening
JP3600155B2 (en) 2000-05-25 2004-12-08 電気化学工業株式会社 Liquid quick-setting agent, quick-setting cement concrete using the same, and method for producing the same
EP1167315B1 (en) * 2000-06-21 2004-09-15 Sika Schweiz AG Sulphate and alkali-free set and hardening accelerator
ATE255075T1 (en) * 2000-06-21 2003-12-15 Sika Schweiz Ag ALKALINE-FREE SETTING AND HARDENING ACCELERATOR
US6367550B1 (en) * 2000-10-25 2002-04-09 Halliburton Energy Service, Inc. Foamed well cement slurries, additives and methods
JP2002241159A (en) * 2001-02-09 2002-08-28 Mitsubishi Materials Corp Accelerator for spraying and spraying material using the same
JP3960590B2 (en) 2002-02-26 2007-08-15 電気化学工業株式会社 Composition for liquid quick setting agent, liquid quick setting agent, spraying material, and spraying method using the same
AUPS200702A0 (en) * 2002-04-29 2002-06-06 Dolomatrix International Limited Treatment of hazardous waste material
JP3967279B2 (en) * 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 Admixture
GB0304158D0 (en) * 2003-02-25 2003-03-26 Mbt Holding Ag Admixture
EP1628931B1 (en) * 2003-05-30 2008-07-23 Construction Research & Technology GmbH Admixture for sprayable cement compositions
JP4452473B2 (en) 2003-09-19 2010-04-21 Ｂａｓｆポゾリス株式会社 Liquid accelerator
ITMI20031983A1 (en) 2003-10-14 2005-04-15 Mapei Spa ACCELERATING FOR HYDRAULIC BINDERS
JP2006193388A (en) 2005-01-14 2006-07-27 Construction Research & Technology Gmbh Liquid quick-setting agent

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000078688A1 (en) * 1999-06-18 2000-12-28 Mbt Holding Ag Concrete admixture
WO2001042165A2 (en) * 1999-12-08 2001-06-14 Mbt Holding Ag Preparation of concrete accelerator
WO2003029163A2 (en) * 2001-09-28 2003-04-10 Construction Research & Technology Gmbh Accelerator composition
WO2003045872A1 (en) * 2001-11-28 2003-06-05 Construction Research & Technology Gmbh Cement accelerator and method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1805115A1 *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2007272060B2 (en) * 2006-07-14 2010-01-21 Construction Research & Technology Gmbh Stable air-placed concrete accelerator dispersion with a high active substance content
WO2008006410A1 (en) * 2006-07-14 2008-01-17 Construction Research & Technology Gmbh Stable air-placed concrete accelerator dispersion with a high active substance content
EP1878713A1 (en) * 2006-07-14 2008-01-16 Construction Research and Technology GmbH Stable shotcrete accelerator dispersion with high content in active matter
CN101605737B (en) * 2007-02-13 2013-04-17 Sika技术股份公司 Setting and hardening accelerator for hydraulic binders and method for its manufacture
EP1964824A1 (en) * 2007-02-13 2008-09-03 Sika Technology AG Setting and hardening accelerator for hydraulic binders and method for its manufacture
US8221543B2 (en) 2007-02-13 2012-07-17 Sika Technology Ag Solidification and hardening accelerator for hydraulic binders and process for its preparation
WO2008098961A1 (en) * 2007-02-13 2008-08-21 Sika Technology Ag A solidification and hardening accelerator for hydraulic binders and process for its preparation
US8075688B2 (en) 2008-01-11 2011-12-13 Construction Research & Technology Gmbh Aqueous accelerator mixture
EP2248780A1 (en) 2009-05-06 2010-11-10 BK Giulini GmbH Set- and hardening accelerator
WO2015173213A1 (en) * 2014-05-14 2015-11-19 Sika Technology Ag Stabilized solidification and setting accelerator for hydraulic binders
US9834478B2 (en) 2014-05-14 2017-12-05 Sika Technology Ag Stabilized solidification and setting accelerator for hydraulic binders
RU2693214C2 (en) * 2014-05-14 2019-07-01 Сикэ Текнолоджи Аг Stabilized hardening and setting accelerator for hydraulic binders
CN107586054A (en) * 2017-09-06 2018-01-16 江苏尼高科技有限公司 Gunite concrete alkali-free liquid accelerator and preparation method thereof
CN107586054B (en) * 2017-09-06 2020-09-01 江苏尼高科技有限公司 Alkali-free liquid accelerator for sprayed concrete and preparation method thereof
EP3868730A1 (en) 2020-02-18 2021-08-25 Sika Technology Ag Accelerator for mineral binder compositions
WO2021165221A1 (en) 2020-02-18 2021-08-26 Sika Technology Ag Accelerator for mineral binder compositions

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AU2005266646A1 (en) 2006-02-02
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US20080090016A1 (en) 2008-04-17
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TWI413628B (en) 2013-11-01
CN1989082A (en) 2007-06-27

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