WO2006043265A2 - Retardation of hydration of cementitous slurry - Google Patents

Retardation of hydration of cementitous slurry Download PDF

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Publication number
WO2006043265A2
WO2006043265A2 PCT/IL2005/001071 IL2005001071W WO2006043265A2 WO 2006043265 A2 WO2006043265 A2 WO 2006043265A2 IL 2005001071 W IL2005001071 W IL 2005001071W WO 2006043265 A2 WO2006043265 A2 WO 2006043265A2
Authority
WO
WIPO (PCT)
Prior art keywords
slurry
acrylic polymer
base material
aquous
polymer base
Prior art date
Application number
PCT/IL2005/001071
Other languages
French (fr)
Other versions
WO2006043265A3 (en
Inventor
Doron Peles
Reuven Irland
Original Assignee
Irland-Peles Ltd.
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 Irland-Peles Ltd. filed Critical Irland-Peles Ltd.
Publication of WO2006043265A2 publication Critical patent/WO2006043265A2/en
Publication of WO2006043265A3 publication Critical patent/WO2006043265A3/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
    • 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
    • C04B28/14—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 calcium sulfate cements
    • C04B28/145—Calcium sulfate hemi-hydrate with a specific crystal form
    • 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
    • C04B40/06—Inhibiting the setting, e.g. mortars of the deferred action type containing water in breakable containers ; Inhibiting the action of active ingredients
    • C04B40/0658—Retarder inhibited mortars activated by the addition of accelerators or retarder-neutralising agents
    • 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
    • C04B2103/20—Retarders
    • C04B2103/22—Set retarders

Definitions

  • the invention relates to a process and composition for retardation of hydration reaction of cementitous slurry comprising calcium sulphate hemihydrate or cement.
  • cementitous materials namely cement, gypsum and the like, are widely used in the construction industry. Typically these materials are available in solid powder form, and are mixed with water and additives to form slurry, which is then cast and allowed to harden.
  • CSH calcium sulphate hemihydrate
  • cement slurry typically hardens over a period of minutes to hours (with the use of retardant additives, su ch as tartaric acid, lignosulphonate, citric acid, sodium gluconate and other retarding agents.
  • retardation of the hydration reaction of CSH may be prolonged to a number of hours, maybe up to several days
  • a method for retarding hydration reaction in a cementitous aquous slurry, in which hydration reaction has not commenced yet comprising: mixing into the aquous slurry acrylic polymer base material, thereby substantially retarding commen cement of hydration reaction in the solution.
  • the cementitious aquous slurry comprises calcium sulphate hemihydrate (CSH). Furthermore, in accordance with some preferred embodiments of the present invention, the acrylic polymer base material is at least 0.1% in weight of the CSH.
  • a condenser is added to the aquous solution.
  • the condenser is selected from the group of condensers containing polysaccharide, starch ether.
  • the cementitious aquous slurry comprises ce ment.
  • acrylic polymer base material is in powder state Furthermore, in accordance with some preferred embodiments of the present invention, the acrylic polymer base material is in liquid state.
  • the acrylic polymer base material is a dispersant.
  • the acrylic polymer is copolymer.
  • the acrylic polymer base material is selected from the group containing: REOTAN L obtainable from Lamberti spa ), Ciba Dispex R50/A40/N40 (obtainable from Ciba), Dispex Nl OO (Allied Colloids), BEVALOID 66770 (PPMC).
  • the acrylic polymer is homopolymer.
  • the method further comprises adding accelrator into the aquous solution, thereby causing beginning of hydration reacti on.
  • the accelerator is selected from the group of accelerators containing: KAI(SO 4 )2*12(H 2 O), gypsum (CaSO 4 . 2 H 2 O), K 2 CO 3 , NaHSO 4 , KHSO 4 , cement, calcium formate, sodium carbonate, lithiumcarbonate, calcium nitrate, calcium nitrite.
  • a cementitious aquous slu rry in which hydration reaction is retarded, comprising acrylic polymer base material mixed homogeneously in the slurry.
  • An aspect of the present invention is the provision of a process and composition for retardation of hydration of CSH and other cemeniteous slurry, using acrylic polymer base material in the slurry.
  • the present invention is aimed at any cemeniteous material, such as cement, all kinds of "gypsum" Csuch as CSH including ⁇ -CSH or ⁇ -CSH) and the like.
  • the inventors of the present invention have unexpectedly discovered that it is possible to retard hydration of cemeniteous materials in the form of aquous solution for substantially long time - in the order of months and even years, much longer than currently possible, rendering it effectively "dormant".
  • the inventors of the present invention have discovered that the retarded aquous solution can be caused to harden in a very short time (typically in a matter of minutes), after a long period of storage in its "dormant" stage.
  • ca lcium sulphate hemihydrate (CSH) base material in a liquid slurry form is a main raw material in the composition.
  • the CSH aquous slurry also includes a conventional retardant (for preventing immediate hardening of the slurry), into which acrylic po lymer base material is mixed.
  • a conventional retardant for preventing immediate hardening of the slurry
  • acrylic po lymer base material is mixed.
  • Other additives may be included in the composition of the present invention, without limiting the scope of the invention.
  • the process includes the following main steps:
  • CSH in a powder form is mixed with a common retard ant (preventing instantaneous commen cement of the hydration reaction, typically retarding it for a matter of a few minutes), such as Tartaric acid (typically using some 0.01 - 0.05% % by weight of the CSH, or mo re).
  • a condenser agent may be used, such as starch ether, polysaccharide (typically using some 0.05 - 0.5% by weight of the CSH , or more).
  • acrylic polymer base material in aqueous solution or in a solid state is added homogeneously mixed in the slurry, typically some 0.1 % by weight of the CSH, or more (the amount varies depending on the period of time it should be retarded and on the purity of the slurry). It is recommended to add a preservative, such as formalin, phenol or other preservative, to prevent cultivation of microorganisms in the slurry.
  • a preservative such as formalin, phenol or other preservative
  • the acrylic polymer base material may be for example selected from the following: REOTAN L obtainable from Lamberti spa ), Ciba Dispex R5O/A40/N40 (obtainable from Ciba), Dispex NlOO (Allied Colloi ds), BEVALOID 66770 (PPMC). These are all examples and do not constitute a closed group, as other acrylic polymer base materials may also be used.
  • the acrylic polymer may be copolymer or homopolymer.
  • the acrylic polymer base material is selected preferably also to be a dispersant.
  • gypsum CaSO 4 • 2 H 2 O
  • gypsum CaSO 4 • 2 H 2 O
  • the aquous mixture is prepared it is stored in a closed container, preferably in a cool place, preferably making sure no air is in direct contact with the surface of the aquous mixture.
  • Thi s may be achieved by covering the mixture by a nylon sheet or a similar protective impervious layer.
  • an accelerator such as KAI(SO 4 ) 2 l2(H 2 O), gypsum (CaSO 4 • 2 H 2 O), K 2 CO 3 , INIaHSO 4 , KHSO 4 , cement, calcium formate, sodium carbonate, l ithiumcarbonate, calcium nitrate, calcium nitrite, or other accelerators is added and mixed into the aquous mixture, causing the hydration reaction to commence and thus in effect puling out the mixture from its "hibernation" state.
  • the use of accelerators is recommended when the slurry is in a long hibernation state (more than a few days). In most cases, for short term hibernation (up to 2-3 days) accelerators are not necessary.
  • This last stage is typically performed on site, where the cemeniteous material needs to be used (at a construction site or si milar locale).
  • the advantage in the present invention is enourmous. It allows a factory regulated quality control rather than relaying on on-site mixing and preparation that is hard to standardize. Furthermore it facilitates a wide range of end-user products, aimed at simplifying construction and building, which means that the preparation stage, that was previously conducted solely on-site is much simpler and faster.
  • the present invention allows manufacturing of ready-for-use materials also reduces health hazards, as the end user is less likely to be exposed to fine powder particles.
  • the present invention also effectively reduces costs, as constructors will not have to bring mixing machines to the construction site (saving water, electricity and machinery). It should be clear that the description of the embodiments set forth in this specification serves only for a better understanding of the invention, without limiting its scope as covered by the following Claims.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

A method for retarding hydration reaction in a cementitous aquous slurry, in which hydration reaction has not commenced yet, the method comprising: mixing into the aquous slurry acrylic polymer base material, thereby substantially retarding commencement of hydration reaction in the solution.

Description

RETARDATION OF HYDRATION OF CEMENTITOUS SLURRY
FIELD OF THE INVENTION
The invention relates to a process and composition for retardation of hydration reaction of cementitous slurry comprising calcium sulphate hemihydrate or cement.
BACKGROUND OF THE INVENTION
Cementitous materials, namely cement, gypsum and the like, are widely used in the construction industry. Typically these materials are available in solid powder form, and are mixed with water and additives to form slurry, which is then cast and allowed to harden.
CSH (calcium sulphate hemihydrate) slurry or cement slurry typically hardens over a period of minutes to hours (with the use of retardant additives, su ch as tartaric acid, lignosulphonate, citric acid, sodium gluconate and other retarding agents.
Conventionally, retardation of the hydration reaction of CSH may be prolonged to a number of hours, maybe up to several days
It is an object of the present invention to provide a process and compositi on for substantial retardation (in the order of months, and even years) of hydration of CSH and other cementitous aquous slurry. Yet another object of the present invention is to provide a process and composition for retardation of hydration of CSH and other cemeniteous aquous slurry, which after a long "dormant" peri od may be rapidly hydrated (in the order of minutes or a few hours) and allowed to harden.
Other advantages and aspects of the present invention will become apparent after reading the present specification.
SUMMARY OF THE INVENTION
There is thus provided, in accordance with some preferred embodiments of the present invention, a method for retarding hydration reaction in a cementitous aquous slurry, in which hydration reaction has not commenced yet, the method comprising: mixing into the aquous slurry acrylic polymer base material, thereby substantially retarding commen cement of hydration reaction in the solution.
Furthermore, in accordance with some preferred embodiments of the present invention, the cementitious aquous slurry comprises calcium sulphate hemihydrate (CSH). Furthermore, in accordance with some preferred embodiments of the present invention, the acrylic polymer base material is at least 0.1% in weight of the CSH.
Furthermore, in accordance with some preferred embodiments of the present invention, a condenser is added to the aquous solution. Furthermore, in accordance with some preferred embodiments of the present invention, the condenser is selected from the group of condensers containing polysaccharide, starch ether. Furthermore, in accordance with some preferred embodiments of the present invention, the cementitious aquous slurry comprises ce ment.
Furthermore, in accordance with some preferred embodiments of the present invention, acrylic polymer base material is in powder state Furthermore, in accordance with some preferred embodiments of the present invention, the acrylic polymer base material is in liquid state.
Furthermore, in accordance with some preferred embodiments of the present invention, the acrylic polymer base material is a dispersant.
Furthermore, in accordance with some preferred embodiments of the present invention, the acrylic polymer is copolymer.
Furthermore, in accordance with some preferred embodiments of the present invention, the acrylic polymer base material is selected from the group containing: REOTAN L obtainable from Lamberti spa), Ciba Dispex R50/A40/N40 (obtainable from Ciba), Dispex Nl OO (Allied Colloids), BEVALOID 66770 (PPMC).
Furthermore, in accordance with some preferred embodiments of the present invention, the acrylic polymer is homopolymer.
Furthermore, in accordance with some preferred embodiments of the present invention, the method further comprises adding accelrator into the aquous solution, thereby causing beginning of hydration reacti on.
Furthermore, in accordance with some preferred embodiments of the present invention, the accelerator is selected from the group of accelerators containing: KAI(SO4)2*12(H2O), gypsum (CaSO4. 2 H2O), K2CO3, NaHSO4, KHSO4 , cement, calcium formate, sodium carbonate, lithiumcarbonate, calcium nitrate, calcium nitrite.
Furthermore, in accordance with some preferred embodiments of the present invention, there is provided a cementitious aquous slu rry, in which hydration reaction is retarded, comprising acrylic polymer base material mixed homogeneously in the slurry.
DESCRIPTION OF PREFERRED EMBODIMENTS
An aspect of the present invention is the provision of a process and composition for retardation of hydration of CSH and other cemeniteous slurry, using acrylic polymer base material in the slurry. The present invention is aimed at any cemeniteous material, such as cement, all kinds of "gypsum" Csuch as CSH including α-CSH or β-CSH) and the like.
The inventors of the present invention have unexpectedly discovered that it is possible to retard hydration of cemeniteous materials in the form of aquous solution for substantially long time - in the order of months and even years, much longer than currently possible, rendering it effectively "dormant".
Furthermore, the inventors of the present invention have discovered that the retarded aquous solution can be caused to harden in a very short time (typically in a matter of minutes), after a long period of storage in its "dormant" stage.
According to a preferred embodiment of the present invention ca lcium sulphate hemihydrate (CSH) base material in a liquid slurry form is a main raw material in the composition.
The CSH aquous slurry also includes a conventional retardant (for preventing immediate hardening of the slurry), into which acrylic po lymer base material is mixed. Other additives may be included in the composition of the present invention, without limiting the scope of the invention. In accordance with some preferred embodiments of the present invention, the process includes the following main steps:
First, CSH in a powder form is mixed with a common retard ant (preventing instantaneous commen cement of the hydration reaction, typically retarding it for a matter of a few minutes), such as Tartaric acid (typically using some 0.01 - 0.05% % by weight of the CSH, or mo re). Optionally a condenser agent may be used, such as starch ether, polysaccharide (typically using some 0.05 - 0.5% by weight of the CSH , or more). After mixing the solids into a homogeneous powder, water is added in mixing (the a mount of water varies, depending on the intended use of the specific product) to attain a homogeneous slurry.
After homogeneous slurry is achieved, and preferably after mixin g it for a few more minutes, acrylic polymer base material in aqueous solution or in a solid state, is added homogeneously mixed in the slurry, typically some 0.1 % by weight of the CSH, or more (the amount varies depending on the period of time it should be retarded and on the purity of the slurry). It is recommended to add a preservative, such as formalin, phenol or other preservative, to prevent cultivation of microorganisms in the slurry. The acrylic polymer base material may be for example selected from the following: REOTAN L obtainable from Lamberti spa), Ciba Dispex R5O/A40/N40 (obtainable from Ciba), Dispex NlOO (Allied Colloi ds), BEVALOID 66770 (PPMC). These are all examples and do not constitute a closed group, as other acrylic polymer base materials may also be used. The acrylic polymer may be copolymer or homopolymer.
The acrylic polymer base material is selected preferably also to be a dispersant.
During the preparation stages it is highly recommended to avoid any contamination by any impurities, such as gypsum (CaSO4 • 2 H2O) that acts as an accelerator, and therefore hinders the retardation of the hydration reaction, or other such contaminants. It is therefore recommended to use clean mixing tools and take care not to conta minate the solution. After the aquous mixture is prepared it is stored in a closed container, preferably in a cool place, preferably making sure no air is in direct contact with the surface of the aquous mixture. Thi s may be achieved by covering the mixture by a nylon sheet or a similar protective impervious layer.
Tests carried out on a stored mixture, in accordance with the present i nvention, clearly show that the hydration reaction can be retarded for a substantially long time (the tested mixture was retarded over a year at the time of writing of this specification and still effectively hydration reaction has not commenced).
Once it is desired to use the aquous mixture — and as mentioned hereinabove this may well be many months after the mixture had been prepared - an accelerator, such as KAI(SO4)2 l2(H2O), gypsum (CaSO4 • 2 H2O), K2CO3, INIaHSO4, KHSO4, cement, calcium formate, sodium carbonate, l ithiumcarbonate, calcium nitrate, calcium nitrite, or other accelerators is added and mixed into the aquous mixture, causing the hydration reaction to commence and thus in effect puling out the mixture from its "hibernation" state. The use of accelerators is recommended when the slurry is in a long hibernation state (more than a few days). In most cases, for short term hibernation (up to 2-3 days) accelerators are not necessary.
This last stage is typically performed on site, where the cemeniteous material needs to be used (at a construction site or si milar locale).
The example given hereinabove was aimed at demonstrating retaring hydration reaction in CSH aquous solution, but the method of the present invention is not limited to this material only, and can be used to retard hydration in any aquous solution of cemeniteous material. Quantities and specific materials of which family groups are mentioed herein may have to be changed accordingly.
The advantage in the present invention is enourmous. It allows a factory regulated quality control rather than relaying on on-site mixing and preparation that is hard to standardize. Furthermore it facilitates a wide range of end-user products, aimed at simplifying construction and building, which means that the preparation stage, that was previously conducted solely on-site is much simpler and faster.
The fact that the present invention allows manufacturing of ready-for-use materials also reduces health hazards, as the end user is less likely to be exposed to fine powder particles.
The present invention also effectively reduces costs, as constructors will not have to bring mixing machines to the construction site (saving water, electricity and machinery). It should be clear that the description of the embodiments set forth in this specification serves only for a better understanding of the invention, without limiting its scope as covered by the following Claims.
It should also be clear that a person skilled in the art, after reading the present specification could make adjustments or amendments to the above described embodiments that would still be covered by the following Claims.

Claims

1. A method for retarding hydration reaction in a cementitous aquous slurry, in which hydration reaction has not commenced yet, the method comprising :
Mixing into the aquous slurry acrylic polymer base material, thereby substantially retarding commencement of hydration reaction in the solution.
2. The method of claim 1, wherein the cementitious aquous slurry comprises calcium sulphate hemihydrate (CSH).
3. The method of claim 2, wherein the acrylic polymer base material is at least 0.1% in weig ht of the CSH.
4. The method of claim 1, wherein a condenser is added to the aquous solution.
5. The method of claim 4, wherein the condenser is selected from the group of condensers containing polysaccharide, starch ether.
6. The method of claim 1, wherein the cementitious aquous slurry comprises cement.
7. The method of claim 1, wherein the acrylic polymer base material is in powder state
8. The method of claim 1, wherein the acrylic polymer base material is in liquid state.
9. The method of claim 8, wherein the acrylic polymer base material is a dispersant.
10. The method of claim 1, wherein the acrylic polymer base material is selected from the group containing : REOTAN L obtainable from Lamberti spa), Ciba Dispex R50/A40/N40 (obtainable from Ciba), Dispex NlOO (Allied Colloids), BEVALOID 66770 (PPMC).
11. The method of claim 1, wherein the acrylic polymer is copolymer.
12. The method of claim 1, wherein the acrylic polymer is homopolymer.
13. The method of claim 1, further comprising adding accelrator into the aquous solution, thereby causing beginning of hydration reaction.
14. The method of claim 13, wherein the accelerator is selected from the group of accelerators containing: KAI(S04)2*12(H2O), gypsum (CaSO4. 2 H2O), K2CO3, NaHSO4, KHSO4 , cement, calcium formate, sodium carbonate, lithiumcarbonate, calcium nitrate, calcium nitrite.
15. A cementitious aquous slurry in which hydration reaction is retarded, comprising acrylic polymer base material mixed homogeneously in the slurry.
16. The slurry of claim 15, wherein the cem entitious aquous slurry comprises calcium sulphate hemihydrate (CSH).
17. The slurry of claim 16, wherein the acrylic polymer base material is at least 0.1% in weight of the CSH.
18. The slurry of claim 15, further comprising a condenser.
19. The slurry of claim 18, wherein the condenser is selected from the group of condensers containing polysaccharide, starch ether.
20. The slurry of claim 15, wherein the cementitious aquous slurry comprises cement.
21. The slurry of claim 15, wherein the acrylic polymer base material is a dispersant.
22. The slurry of claim 15, wherein the acrylic polymer base material is selected from the group containing: REOTAN L obtai nable from Lamberti spa),
Ciba Dispex R50/A40/N40 (obtainable from Ciba), Dispex NlOO (Allied Colloids), BEVALOID 66770 (PPMC).
23. The slury of claim 15, wherein the acrylic polymer is copolymer.
24. The slury of claim 15, wherein the acrylic polymer is homopolymer.
25. The slurry of claim 15, further comprising an accelerator.
26. The slurry of claim 25, wherein the accelerator is selected from the group of accelerators containing : KAI(SO4)2*12(H20), gypsum (CaSO4. 2 H2O), K2Cθ3, NaHSO4, KHSO4 , cement, calcium formate, sodium carbonate, lithiumcarbonate, calcium nitrate, calcium nitrite.
PCT/IL2005/001071 2004-10-21 2005-10-10 Retardation of hydration of cementitous slurry WO2006043265A2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IL164748 2004-10-21
IL16474804A IL164748A0 (en) 2004-10-21 2004-10-21 Retardation of hydration of cmentitous slurry

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WO2006043265A2 true WO2006043265A2 (en) 2006-04-27
WO2006043265A3 WO2006043265A3 (en) 2006-05-26

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2070673A3 (en) * 2007-12-12 2010-11-10 Deutsche Amphibolin-Werke von Robert Murjahn Stiftung & Co KG Apparatus for mixing building materials
IT201700107064A1 (en) * 2017-09-25 2019-03-25 Mapei Spa ACCELERATING ADDITIVE FOR HYDRAULIC COMPOSITIONS

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4157264A (en) * 1976-09-15 1979-06-05 Imperial Chemical Industries Limited Calcium sulphate hemihydrate plaster
US5421879A (en) * 1993-01-14 1995-06-06 Halliburton Company Cement set retarding additives, compositions and methods
US5421881A (en) * 1993-07-02 1995-06-06 Halliburton Company Cement set retarding additives, compositions and methods

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4157264A (en) * 1976-09-15 1979-06-05 Imperial Chemical Industries Limited Calcium sulphate hemihydrate plaster
US5421879A (en) * 1993-01-14 1995-06-06 Halliburton Company Cement set retarding additives, compositions and methods
US5421881A (en) * 1993-07-02 1995-06-06 Halliburton Company Cement set retarding additives, compositions and methods

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2070673A3 (en) * 2007-12-12 2010-11-10 Deutsche Amphibolin-Werke von Robert Murjahn Stiftung & Co KG Apparatus for mixing building materials
IT201700107064A1 (en) * 2017-09-25 2019-03-25 Mapei Spa ACCELERATING ADDITIVE FOR HYDRAULIC COMPOSITIONS
WO2019058313A1 (en) * 2017-09-25 2019-03-28 Mapei Spa Accelerating admixture for hydraulic compositions
US11365151B2 (en) 2017-09-25 2022-06-21 Mapei Spa Accelerating admixture for hydraulic compositions

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IL164748A0 (en) 2005-12-18

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