CN107434365B - Organic setting accelerator for hydraulic cement binder for spray construction - Google Patents
Organic setting accelerator for hydraulic cement binder for spray construction Download PDFInfo
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- CN107434365B CN107434365B CN201710635203.1A CN201710635203A CN107434365B CN 107434365 B CN107434365 B CN 107434365B CN 201710635203 A CN201710635203 A CN 201710635203A CN 107434365 B CN107434365 B CN 107434365B
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- 239000011230 binding agent Substances 0.000 title claims abstract description 34
- 239000011396 hydraulic cement Substances 0.000 title claims abstract description 33
- 238000010276 construction Methods 0.000 title claims description 39
- 239000007921 spray Substances 0.000 title claims description 14
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims description 32
- 239000000017 hydrogel Substances 0.000 claims description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 229920002873 Polyethylenimine Polymers 0.000 claims description 19
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 18
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 18
- 229920002678 cellulose Polymers 0.000 claims description 18
- 239000001913 cellulose Substances 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910021389 graphene Inorganic materials 0.000 claims description 16
- CMWINYFJZCARON-UHFFFAOYSA-N 6-chloro-2-(4-iodophenyl)imidazo[1,2-b]pyridazine Chemical group C=1N2N=C(Cl)C=CC2=NC=1C1=CC=C(I)C=C1 CMWINYFJZCARON-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000011378 shotcrete Substances 0.000 claims description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 7
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000003623 enhancer Substances 0.000 claims 3
- 238000005507 spraying Methods 0.000 abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 6
- 150000005846 sugar alcohols Polymers 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 description 21
- 238000003756 stirring Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 16
- 239000004568 cement Substances 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 8
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 8
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 8
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 8
- -1 aluminum compound Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- ZUGAOYSWHHGDJY-UHFFFAOYSA-K 5-hydroxy-2,8,9-trioxa-1-aluminabicyclo[3.3.2]decane-3,7,10-trione Chemical compound [Al+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O ZUGAOYSWHHGDJY-UHFFFAOYSA-K 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000012744 reinforcing agent Substances 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000011083 cement mortar Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 229910052920 inorganic sulfate Inorganic materials 0.000 description 3
- 229920000609 methyl cellulose Polymers 0.000 description 3
- 239000001923 methylcellulose Substances 0.000 description 3
- 235000010981 methylcellulose Nutrition 0.000 description 3
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229940024545 aluminum hydroxide Drugs 0.000 description 1
- 229940024546 aluminum hydroxide gel Drugs 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/04—Carboxylic acids; Salts, anhydrides or esters thereof
- C04B24/06—Carboxylic acids; Salts, anhydrides or esters thereof containing hydroxy groups
-
- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
-
- 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
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)
Abstract
The invention provides an organic accelerator for spraying hydraulic cement binder, comprising at least one organic aluminum salt, the aluminum salt has good accelerating effect with mixed water solution of high content polyhydric alcohol, and the invention also provides a method for preparing the accelerator.
Description
Technical Field
The invention relates to an organic accelerator for spraying and constructing hydraulic cement cementing materials and a preparation method thereof.
Background
The accelerator is an additive which can quickly set and harden cementing material containing cement and produce a certain strength, can be widely applied to tunnel mortar injection or concrete construction and rush-repair construction, and mainly aims to accelerate the setting time of the cementing material, accelerate the construction speed, reduce the rebound, improve the early strength without reducing the later strength, and meet the construction requirements of special engineering.
In the construction process of spraying the cementing material containing cement through a nozzle, the cementing material must be solidified within a specified time to accelerate the spraying construction speed of the tunnel, and for the requirement, the traditional method of using sodium aluminate and alkali metal hydroxide achieves the strong accelerating effect of setting time; however, due to the high alkalinity of the accelerator, the accelerator has very bad influence on the working environment, has non-adverse effect on the long-term strength of the cement cementing material after hardening and has non-negligible potential alkali-aggregate reaction, and is not the preferred accelerator for the reason. In order to fully utilize the advantages of the quick-setting admixture in the spray construction, researchers have carried out many research works, and alkali-free quick-setting admixtures containing aluminum compounds, such as aluminum compounds and/or polymers containing inorganic sulfates, have been proposed, which bring about improvement of construction site environment, are friendly to human body, and most advantageously maintain the long-term strength, greatly expanding the application range of the quick-setting admixtures; however, such an accelerator has the following problems: for most accelerator admixtures of inorganic sulfate-containing aluminum compounds and/or polymers, the sulfur trioxide content introduced in the cement binder exceeds the upper limit of durability, compromising its long-term durability; another problem is that the control of the sedimentation tendency of the accelerator is a problem commonly faced by the industry due to the relatively high content of the aluminum compound and/or polymer of the inorganic sulfate, the relatively high density and the inherently metastable state of the accelerator solution, and the sedimentation problem is mentioned in almost all patents or documents relating to alkali-free accelerators which have been published and is the most difficult problem to be circumvented by the current technological progress.
Disclosure of Invention
The object of the present invention is to improve the disadvantages of the prior art and to provide an organic accelerator for a shotcrete hydraulic cement binder which has a greatly improved long-term storage stability for the hardened cement binder in addition to no loss of late strength, a low spray resilience and a moderate mixing amount, or which has little sedimentation problems due to the absence of inorganic substances in the formulation. Another object of the present invention is to provide a method for preparing the above organic setting accelerator containing a hydraulic cement binder for shotcrete construction. It is a further object of the present invention to provide the use of the above organic accelerator for a hydraulic cement binder for spray construction in spray construction and additive manufacturing of buildings, structures or components thereof.
The inventor researches and discovers that from a traditional alkaline accelerator to a current alkali-free accelerator, the main component or most of the main accelerating action of the traditional alkaline accelerator is a series of compounds of aluminum element, most commonly alkali metal salts of aluminate under the alkaline environment, hydrated trivalent aluminum ion salts under the acidic environment and other valence complex ion salts of aluminum; due to the fact that solubility of the trivalent aluminum ion salt is limited, the effect is poor, technicians increase the use effect by increasing the solubility or adding aluminum hydroxide to be dissolved in the solution or separating out aluminum hydroxide gel from the solution to perform polymerization reaction to generate a polymerized aluminum salt, the essence of the two measures is that a part of trivalent aluminum ions are reacted to generate a series of other complex ion salts of aluminum, namely the total solubility of aluminum in the solution is increased by different ion existence modes, but the effect is often limited.
The inventors have found that a mixed aqueous solution thereof with a high content of polyhydric alcohol has a good quick-setting effect in the presence of a small amount of an organic aluminum salt, and the organic quick-setting agent for hydraulic cement binder for spray construction of the present invention comprises at least one fluorine-containing organic aluminum salt.
Specifically, the content of the fluorine-containing organic aluminum salt selected by the invention is not more than 20 wt%.
Specifically, the fluorine-containing organic aluminum salt selected by the invention is aluminum trifluoromethanesulfonate.
Furthermore, the organic accelerator for spraying construction hydraulic cement binder of the invention preferably comprises at least one hydroxycarboxylic acid, specifically, the hydroxycarboxylic acid selected by the invention is glycolic acid or hydroxypropionic acid or citric acid, the content of which is not more than 10 wt% at most, and the preferred content is between 1 and 8 wt%.
As a preferred alternative to the organic accelerator of the present invention for use in a shotcrete construction hydraulic cement binder, one or more hydroxycarboxylic acids and at least one organic aluminum salt are included. Specifically, the content of the organic aluminum salt selected by the invention is not more than 20 wt%.
Specifically, the organic aluminum salt selected by the invention is one or more of aluminum trifluoromethanesulfonate, aluminum citrate and aluminum dihydroxyformate.
The organic accelerator for spraying construction hydraulic cement binder further comprises polyhydroxy dispersion reinforcing agent, specifically, the polyhydroxy dispersion reinforcing agent selected by the invention is one or more of ethylene glycol, polyethylene glycol, propylene glycol and glycerol, the polyethylene glycol is preferably oligomer, preferably polyethylene glycol 400 or polyethylene glycol 600, and specifically, the content of the polyhydroxy dispersion reinforcing agent is not more than 40 wt%.
Further, the organic accelerator for a hydraulic cement binder for spray construction according to the present invention preferably comprises nano graphene oxide. The oxygen-containing groups are introduced into the graphene single sheets of each layer of the nano graphene oxide, so that the nano graphene oxide has a strong hydrophilic dispersion effect, and the organic accelerator for spraying and constructing the hydraulic cement binding material can be quickly condensed and can enhance the compressive strength of the cement binding material; specifically, the content is 4-12 wt%.
Further, the organic accelerator for a hydraulic cement binder for spray construction according to the present invention preferably comprises a stabilizer, and particularly, the stabilizer is a polyethyleneimine-dispersed cellulose composite hydrogel.
Specifically, the content of the cellulose is 0.5-2 wt%, and the cellulose can be one or more selected from methyl cellulose or hydroxypropyl methyl cellulose; the mass ratio of the polyethyleneimine to the cellulose is 1-3.5: specifically, the polyethyleneimine is preferably a low molecular weight product which can certainly obtain a stable dispersion effect, and the preferred low molecular weight products include polyethyleneimine 800, polyethyleneimine 1300 and polyethyleneimine 2000; more specifically, in addition to satisfying the above content requirement, the minimum content of polyethyleneimine should be not less than 1wt% of the total amount of dissolved substances in the solution.
The invention also provides a preparation method of the organic accelerator for the hydraulic cement binder for spray construction, which comprises the following specific steps:
(1) preparing 5-10 wt% of polyethyleneimine into an aqueous solution, adding cellulose, stirring and mixing to obtain polyethyleneimine-dispersed cellulose composite hydrogel;
(2) dispersing nano graphene oxide into the composite hydrogel;
(3) adding a polyhydroxy dispersion reinforcing agent into hydroxycarboxylic acid, adding the rest water to prepare an aqueous solution, and then adding a fluorine-containing organic aluminum salt or an organic aluminum salt to dissolve completely;
(4) and (3) adding the solution prepared in the step (3) into the composite hydrogel prepared in the step (2), and uniformly stirring to obtain the organic accelerator for spraying the hydraulic cement binder in construction.
The invention also provides the application of the organic accelerator for the hydraulic cement binder for spray construction in spray construction and additive manufacturing of buildings, structures or components thereof; the mixing amount of the organic accelerator for spraying the hydraulic cement binder in construction is 3-4% of the mass of the cementing material in the cement binder in the preferred application.
The alkali content of the invention is less than 0.6%.
The invention has the following beneficial effects:
(1) the whole organic solution system has no risk of demixing and sedimentation during storage;
(2) according to experimental conditions of JC477-2005 accelerator for sprayed concrete, the organic accelerator for spraying construction hydraulic cement binder of the invention can cause the initial setting of cement within 5min and the final setting within 8min under a lower doping amount (3-4%);
(3) according to experimental conditions of JC477-2005 & ltquick setting agent for sprayed concrete & gt & lt/EN & gt, the organic quick setting agent for spraying construction hydraulic cement binder prepared by the invention can ensure that the 1d strength of cement mortar is more than 12MPa and the 28d strength is not lost;
(4) the organic accelerator for the hydraulic cement binder for spray construction provided by the invention does not contain sulfate ions, alkali metal ions, chloride ions and other corrosive substances, and plays a positive role in the durability of concrete; in addition, alkali-free is safe for the constructors.
Detailed Description
The present invention will be further described with reference to the following examples, which are intended to illustrate and explain the present invention and are not intended to limit the present invention.
The percentages are mass percentages unless otherwise specified.
Example 1
(1) Preparing 1.75g of polyethyleneimine 800 into a 10% aqueous solution, adding 0.5g of hydroxypropyl methyl cellulose, stirring and mixing to obtain polyethyleneimine-dispersed cellulose composite hydrogel;
(2) dispersing 4g of nano graphene oxide into the composite hydrogel;
(3) adding 22g of ethylene glycol into 8g of hydroxypropionic acid, adding the rest water to prepare an aqueous solution, and then adding 15g of aluminum citrate to dissolve completely;
(4) and (3) adding the solution prepared in the step (3) into the composite hydrogel prepared in the step (2), and uniformly stirring to obtain the organic accelerator for spraying the hydraulic cement binder in construction.
Example 2
(1) Preparing 2g of polyethyleneimine 1300 into a 10% aqueous solution, adding 2g of hydroxypropyl methyl cellulose, stirring and mixing to obtain polyethyleneimine-dispersed cellulose composite hydrogel;
(2) dispersing 5g of nano graphene oxide into the composite hydrogel;
(3) adding 40g of ethylene glycol into 1g of glycolic acid, adding the rest water to prepare an aqueous solution, and then adding 5g of aluminum dihydroxyformate to completely dissolve the aluminum dihydroxyformate;
(4) and (3) adding the solution prepared in the step (3) into the composite hydrogel prepared in the step (2), and uniformly stirring to obtain the organic accelerator for spraying the hydraulic cement binder in construction.
Example 3
(1) Preparing 3g of polyethyleneimine 2000 into a 10% aqueous solution, adding 2g of methylcellulose, stirring and mixing to obtain polyethyleneimine-dispersed cellulose composite hydrogel;
(2) dispersing 6g of nano graphene oxide into the composite hydrogel;
(3) adding 10g of ethylene glycol and 2g of polyethylene glycol 400 into 6g of glycolic acid, adding the rest water to prepare an aqueous solution, and then adding 20g of aluminum trifluoromethanesulfonate to completely dissolve the aluminum trifluoromethanesulfonate;
(4) and (3) adding the solution prepared in the step (3) into the composite hydrogel prepared in the step (2), and uniformly stirring to obtain the organic accelerator for spraying the hydraulic cement binder in construction.
Example 4
(1) Preparing 1.1g of polyethyleneimine 800 into a 5% aqueous solution, adding 1.0g of methylcellulose, stirring and mixing to obtain polyethyleneimine-dispersed cellulose composite hydrogel;
(2) dispersing 7g of nano graphene oxide into the composite hydrogel;
(3) adding 7g of propylene glycol and 1g of polyethylene glycol 400 into 5g of glycolic acid, adding the rest water to prepare an aqueous solution, and then adding 18g of aluminum trifluoromethanesulfonate to completely dissolve the mixture;
(4) and (3) adding the solution prepared in the step (3) into the composite hydrogel prepared in the step (2), and uniformly stirring to obtain the organic accelerator for spraying the hydraulic cement binder in construction.
Example 5
(1) Preparing 2.2g of polyethyleneimine 800 into 9% aqueous solution, adding 1.1g of hydroxypropyl methyl cellulose, stirring and mixing to obtain polyethyleneimine dispersed cellulose composite hydrogel;
(2) dispersing 8g of nano graphene oxide into the composite hydrogel;
(3) adding 27g of propylene glycol and 1g of glycerol into 4g of glycolic acid, adding the rest water to prepare an aqueous solution, and then adding 16g of aluminum trifluoromethanesulfonate to completely dissolve the materials;
(4) and (3) adding the solution prepared in the step (3) into the composite hydrogel prepared in the step (2), and uniformly stirring to obtain the organic accelerator for spraying the hydraulic cement binder in construction.
Example 6
(1) Preparing 1.0g of polyethyleneimine 1300 into an 8% aqueous solution, adding 0.8g of hydroxypropyl methyl cellulose, stirring and mixing to obtain polyethyleneimine-dispersed cellulose composite hydrogel;
(2) dispersing 9g of nano graphene oxide into the composite hydrogel;
(3) adding 30g of ethylene glycol, 1g of polyethylene glycol 600 and 1g of propylene glycol into 3g of glycolic acid, adding the rest water to prepare an aqueous solution, and then adding 6g of aluminum trifluoromethanesulfonate, 2g of aluminum citrate and 1g of aluminum dihydroxyformate to completely dissolve;
(4) and (3) adding the solution prepared in the step (3) into the composite hydrogel prepared in the step (2), and uniformly stirring to obtain the organic accelerator for spraying the hydraulic cement binder in construction.
Example 7
(1) Preparing 0.8g of polyethyleneimine 2000 into a 7% aqueous solution, adding 0.7g of hydroxypropyl methyl cellulose, stirring and mixing to obtain polyethyleneimine-dispersed cellulose composite hydrogel;
(2) dispersing 12g of nano graphene oxide into the composite hydrogel;
(3) adding 28g of ethylene glycol and 2g of propylene glycol into 7g of hydroxypropionic acid, adding the rest water to prepare an aqueous solution, and then adding 10g of aluminum trifluoromethanesulfonate and 4g of aluminum dihydroxyformate to completely dissolve;
(4) and (3) adding the solution prepared in the step (3) into the composite hydrogel prepared in the step (2), and uniformly stirring to obtain the organic accelerator for spraying the hydraulic cement binder in construction.
Example 8
(1) Preparing 1.0g of polyethyleneimine 1300 into a 10% aqueous solution, adding 0.7g of hydroxypropyl methyl cellulose, stirring and mixing to obtain polyethyleneimine-dispersed cellulose composite hydrogel;
(2) dispersing 10g of nano graphene oxide into the composite hydrogel;
(3) adding 27g of ethylene glycol into 2g of glycolic acid, adding the rest water to prepare an aqueous solution, and then adding 10g of aluminum trifluoromethanesulfonate and 2g of aluminum citrate to dissolve completely;
(4) and (3) adding the solution prepared in the step (3) into the composite hydrogel prepared in the step (2), and uniformly stirring to obtain the organic accelerator for spraying the hydraulic cement binder in construction.
Example 9
(1) Preparing 1.6g of polyethyleneimine 800 into a 10% aqueous solution, adding 0.8g of hydroxypropyl methyl cellulose, stirring and mixing to obtain polyethyleneimine-dispersed cellulose composite hydrogel;
(2) dispersing 10g of nano graphene oxide into the composite hydrogel;
(3) adding 22g of ethylene glycol into 3g of glycolic acid, adding the rest water to prepare an aqueous solution, and then adding 8g of aluminum trifluoromethanesulfonate to completely dissolve the aluminum trifluoromethanesulfonate;
(4) and (3) adding the solution prepared in the step (3) into the composite hydrogel prepared in the step (2), and uniformly stirring to obtain the organic accelerator for spraying the hydraulic cement binder in construction.
Application example 1
Each accelerator of preparation examples 1 to 9 was added to a cement paste or a cement mortar sample in an amount of 3 to 4% by weight of the cement, and the setting time and compressive strength were measured according to the standard of JC477-2005 accelerator for shotcrete. The alkali content is tested according to GB/T8077-2012 'concrete admixture homogeneity test method', and a blank is made without adding any accelerator.
The test mixture ratio of the cement paste setting time is as follows: the reference cement is water 400: 160.
The test proportion of the compressive strength of the cement mortar is as follows: the standard cement is standard sand and water is 900:1350: 450.
The water comprises water in the accelerator, and the water amount is obtained by deducting the using amount of the water in the accelerator according to the measured solid content of the accelerator during preparation.
The results of the correlation property measurements are shown in table 1:
TABLE 1 test results of the properties of the accelerator of the invention
The test results are shown in Table 1, the alkali content of each example is less than 0.1%, and according to the standard analysis of JC477-2005, the alkali-free accelerator prepared by the invention can meet the requirements when the mixing amount is 3-4%. In addition, the accelerator prepared by the invention has the characteristics of high strength, such as 1d strength of the mortar is as high as 16.5MPa in example 8, and 28d strength ratio is as high as 120 percent in example 7.
Application example 2
The stability of the liquid accelerator of the invention is tested.
The test method was carried out in accordance with the method mentioned in the patent (201310450025.7) published by the institute of science and engineering of building materials of China, in which the conditions of standing were natural environments.
The test results are shown in table 2.
The stability of the liquid accelerator exceeds 18 months in the storage period.
TABLE 2 stability test results of the accelerating agent of the present invention in storage period
The present invention has been described in detail with reference to the attached tables, and it is obvious that the present invention is not limited to the above embodiments, and various insubstantial modifications can be made by using the method concept and technical scheme of the present invention; the present invention is not limited to the above embodiments, and can be modified in various ways.
Claims (3)
1. An organic accelerator for use in spray construction of hydraulic cement binders, characterized in that,
the composition consists of the following components: at least one fluorine-containing organic aluminum salt, at least one hydroxycarboxylic acid, a polyhydroxy dispersion enhancer, nano graphene oxide and a stabilizer;
the fluorine-containing organic aluminum salt is aluminum trifluoromethanesulfonate; the content of the fluorine-containing organic aluminum salt is not more than 20 wt%;
the hydroxycarboxylic acid content is not more than 10 wt%;
the polyhydroxy dispersion enhancer content is not more than 40 wt%;
the content of the nano graphene oxide is 4-12 wt%;
the stabilizer is a polyethyleneimine-dispersed cellulose composite hydrogel, wherein the cellulose content is 0.5-2 wt%, and the mass ratio of polyethyleneimine to cellulose is 1-3.5: 1 and the minimum content of polyethyleneimine is not less than 1wt% of the total amount of dissolved substances in the solution.
2. The organic accelerator for a shotcrete construction hydraulic cement binder of claim 1, wherein the hydroxy carboxylic acid is glycolic acid or hydroxypropionic acid.
3. The organic accelerator for a shotcrete construction hydraulic cement binder of claim 1, wherein the polyhydroxy dispersion enhancer is one or more of ethylene glycol, polyethylene glycol, propylene glycol, and glycerol.
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| US20020035952A1 (en) * | 2000-06-21 | 2002-03-28 | Marcel Sommer | Alkali-free setting and hardening accelerator |
| JP4286434B2 (en) * | 2000-06-12 | 2009-07-01 | 電気化学工業株式会社 | Powder setting agent and spray material |
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| CN106746846A (en) * | 2016-11-29 | 2017-05-31 | 江苏中铁奥莱特新材料股份有限公司 | A kind of enhanced alkali-free liquid accelerator of low resilience and preparation method thereof |
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| JP4286434B2 (en) * | 2000-06-12 | 2009-07-01 | 電気化学工業株式会社 | Powder setting agent and spray material |
| US20020035952A1 (en) * | 2000-06-21 | 2002-03-28 | Marcel Sommer | Alkali-free setting and hardening accelerator |
| CN102173630A (en) * | 2011-01-04 | 2011-09-07 | 昆明合起工贸有限公司 | High-performance chlorine-free alkali-free liquid accelerating agent |
| CN103396027A (en) * | 2013-07-25 | 2013-11-20 | 北京市建筑工程研究院有限责任公司 | Preparation method of novel alkali-free liquid accelerator |
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