CN111253108A - Sulfur-free alkali-free accelerator beneficial to durability of sprayed concrete and preparation method thereof - Google Patents
Sulfur-free alkali-free accelerator beneficial to durability of sprayed concrete and preparation method thereof Download PDFInfo
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- CN111253108A CN111253108A CN202010019161.0A CN202010019161A CN111253108A CN 111253108 A CN111253108 A CN 111253108A CN 202010019161 A CN202010019161 A CN 202010019161A CN 111253108 A CN111253108 A CN 111253108A
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- free
- sulfur
- alkali
- durability
- stirring
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- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/61—Corrosion inhibitors
Abstract
The invention relates to the technical field of accelerator production, in particular to a sulfur-free alkali-free accelerator beneficial to the durability of sprayed concrete and a preparation method thereof. The method comprises the following steps: after dissolving the required amount of aluminum nitrate nonahydrate with the required amount of water, adding the required amount of acidic silica sol, magnesium fluosilicate and cellulose ether, and stirring to obtain the sulfur-free alkali-free accelerator beneficial to the durability of sprayed concrete. The sulfur-free alkali-free accelerator beneficial to the durability of sprayed concrete can improve the impermeability and compressive strength of the concrete, and meanwhile, the main component contains nitrate radicals, so that the sulfur-free alkali-free accelerator has an anti-corrosion effect on the concrete, and the service life of the concrete is prolonged.
Description
Technical Field
The invention relates to the technical field of accelerator production, in particular to a sulfur-free alkali-free accelerator beneficial to the durability of sprayed concrete and a preparation method thereof.
Background
Because the traditional accelerator has high alkali content, the later-stage alkali aggregate reaction of the concrete is caused, and the service life of the concrete is shortened. In recent years, a great amount of alkali-free accelerators have been applied to sprayed concrete abroad, the alkali-free accelerators are applied to the sprayed concrete field at home, the starting time is short, but the development is rapid, the existing alkali-free accelerators use aluminum sulfate as a main component, the use of alkali metal salt is avoided, so that the alkali aggregate reaction of the concrete is avoided, but sulfate radicals in the aluminum sulfate have an erosion effect on the concrete, the sulfate radicals react with free calcium ions in the concrete to generate calcium sulfate gypsum crystals, the expansion is generated to destroy the structure of the concrete, and the service life of the concrete is also influenced.
Disclosure of Invention
The invention provides a sulfur-free alkali-free accelerator beneficial to the durability of sprayed concrete, overcomes the defects of the prior art, and can effectively solve the problem of corrosion of the existing alkali-free accelerator aluminum sulfate to the concrete.
One of the technical schemes of the invention is realized by the following measures: a sulfur-free alkali-free accelerator beneficial to the durability of sprayed concrete comprises 40 to 60 parts of aluminum nitrate nonahydrate, 5 to 10 parts of acidic silica sol, 1 to 3 parts of magnesium fluosilicate, 0.1 to 1 part of cellulose ether and 30 to 55 parts of water in parts by weight.
The following is a further optimization or/and improvement of one of the above-mentioned technical solutions of the invention:
the sulfur-free alkali-free accelerator beneficial to the durability of sprayed concrete is obtained by the following method: after dissolving the required amount of aluminum nitrate nonahydrate with the required amount of water, adding the required amount of acidic silica sol, magnesium fluosilicate and cellulose ether, and stirring to obtain the sulfur-free alkali-free accelerator beneficial to the durability of sprayed concrete.
The cellulose ether is hydroxypropyl methylcellulose.
The stirring time is 0.8h to 1.2 h.
The raw material of aluminum nitrate nonahydrate is obtained by the following method: mixing and stirring aluminum hydroxide and water uniformly, continuously dropwise adding nitric acid with the concentration of 66-70%, controlling the dropwise adding time to be 0.8-1.2 h, controlling the temperature to be 88-92 ℃, stirring for 1.8-2.2 h until the nitric acid is completely dissolved, controlling the end-point pH value to be 4-6, and cooling to 28-32 ℃ to obtain aluminum nitrate nonahydrate, wherein the mass ratio of the aluminum hydroxide to the nitric acid is 1: 3-4.
The second technical scheme of the invention is realized by the following measures: a method for preparing a sulfur-free alkali-free accelerator beneficial to the durability of sprayed concrete comprises the following steps: after dissolving the required amount of aluminum nitrate nonahydrate with the required amount of water, adding the required amount of acidic silica sol, magnesium fluosilicate and cellulose ether, and stirring to obtain the sulfur-free alkali-free accelerator beneficial to the durability of sprayed concrete.
The following is further optimization or/and improvement of the second technical scheme of the invention:
the cellulose ether is hydroxypropyl methylcellulose.
The stirring time is 0.8h to 1.2 h.
The raw material of aluminum nitrate nonahydrate is obtained by the following method: mixing and stirring aluminum hydroxide and water uniformly, continuously dropwise adding nitric acid with the concentration of 66-70%, controlling the dropwise adding time to be 0.8-1.2 h, controlling the temperature to be 88-92 ℃, stirring for 1.8-2.2 h until the nitric acid is completely dissolved, controlling the end-point pH value to be 4-6, and cooling to 28-32 ℃ to obtain aluminum nitrate nonahydrate, wherein the mass ratio of the aluminum hydroxide to the nitric acid is 1: 3-4.
The invention solves the application defect of the alkali-free accelerator taking aluminum sulfate as the main component, provides the sulfur-free alkali-free accelerator which has no sulfate ions and no alkali metal ions and is beneficial to the durability of sprayed concrete, not only avoids alkali aggregate reaction caused by alkali metal ions, but also avoids the corrosion of the sulfate ions to the concrete, and the components which do not damage the durability of the concrete in the product are provided.
The other components of the invention are mutually matched and act, which is also beneficial to the durability of concrete, wherein, the acid silica sol is a nano material and can fill micro cracks generated when the concrete is solidified, thereby improving the impermeability and compressive strength of the concrete; the magnesium fluosilicate is hydrolyzed when meeting free alkali in the concrete, can generate hydrated silica gel with a three-dimensional structure, can accelerate the solidification of the concrete and form concrete with higher strength; cellulose ether improves the stability of concrete by increasing the viscosity of the concrete.
Therefore, the sulfur-free alkali-free accelerator beneficial to the durability of sprayed concrete can improve the impermeability and compressive strength of the concrete, and meanwhile, the main component contains nitrate, so that the sulfur-free alkali-free accelerator has an anti-corrosion effect on the concrete and prolongs the service life of the concrete.
Detailed Description
The present invention is not limited by the following examples, and specific embodiments may be determined according to the technical solutions and practical situations of the present invention. The various chemical reagents and chemical articles mentioned in the invention are all the chemical reagents and chemical articles which are well known and commonly used in the prior art, unless otherwise specified; the percentages in the invention are mass percentages unless otherwise specified; the solution in the present invention is an aqueous solution in which the solvent is water, for example, a hydrochloric acid solution is an aqueous hydrochloric acid solution, unless otherwise specified; the normal temperature and room temperature in the present invention generally mean a temperature of 15 ℃ to 25 ℃, and are generally defined as 25 ℃.
The invention is further described below with reference to the following examples:
example 1: the sulfur-free alkali-free accelerator beneficial to the durability of sprayed concrete comprises, by weight, 40-60 parts of aluminum nitrate nonahydrate, 5-10 parts of acidic silica sol, 1-3 parts of magnesium fluosilicate, 0.1-1 part of cellulose ether and 30-55 parts of water.
Example 2: the sulfur-free alkali-free accelerator beneficial to the durability of sprayed concrete is obtained by the following method: after dissolving the required amount of aluminum nitrate nonahydrate with the required amount of water, adding the required amount of acidic silica sol, magnesium fluosilicate and cellulose ether, and stirring to obtain the sulfur-free alkali-free accelerator beneficial to the durability of sprayed concrete.
Example 3: as the optimization of the above embodiment, hydroxypropyl methylcellulose is used as the cellulose ether.
Example 4: as an optimization of the above examples, the stirring time is from 0.8h to 1.2 h.
Example 5: as optimization of the above example, the raw material, aluminum nitrate nonahydrate, was obtained as follows: mixing and stirring aluminum hydroxide and water uniformly, continuously dropwise adding nitric acid with the concentration of 66-70%, controlling the dropwise adding time to be 0.8-1.2 h, controlling the temperature to be 88-92 ℃, stirring for 1.8-2.2 h until the nitric acid is completely dissolved, controlling the end-point pH value to be 4-6, and cooling to 28-32 ℃ to obtain aluminum nitrate nonahydrate; the mass ratio of the aluminum hydroxide to the nitric acid is 1:3 to 4.
Example 6: after 40 to 60 parts of aluminum nitrate nonahydrate is dissolved by 30 to 55 parts of water, 5 to 10 parts of acidic silica sol, 1 to 3 parts of magnesium fluosilicate and 0.1 to 1 part of cellulose ether are added, and the mixture is stirred for 0.8 to 1.2 hours to obtain the sulfur-free alkali-free accelerator beneficial to the durability of sprayed concrete.
Example 7: mixing and uniformly stirring 10 parts of aluminum hydroxide and 22 parts of water, continuously dropwise adding 37 parts of nitric acid with the concentration of 66-70%, controlling the dropwise adding time to be 0.8-1.2 h, controlling the temperature to be 88-92 ℃, stirring for 1.8-2.2 h until the nitric acid is completely dissolved, controlling the end point pH value to be 4-6, adding 31 parts of water, cooling to 28-32 ℃ to obtain aluminum nitrate nonahydrate, then adding 5-10 parts of acidic silica sol, 1-3 parts of magnesium fluosilicate and 0.1-1 part of hydroxypropyl methyl cellulose, and stirring for 0.8-1.2 h to obtain the sulfur-free alkali-free accelerator beneficial to the durability of sprayed concrete.
Example 8: mixing and uniformly stirring 10 parts of aluminum hydroxide and 22 parts of water, continuously dropwise adding 37 parts of nitric acid with the concentration of 70%, controlling the dropwise adding time to be 1.2h, controlling the temperature to be 92 ℃, stirring for 2.2h until the nitric acid is completely dissolved, controlling the end point pH value to be 4-6, adding 31 parts of water, cooling to 32 ℃ to obtain aluminum nitrate nonahydrate, adding 10 parts of acidic silica sol, 3 parts of magnesium fluosilicate and 1 part of hydroxypropyl methyl cellulose, and stirring for 1.2h to obtain the sulfur-free and alkali-free accelerator beneficial to the durability of sprayed concrete.
Example 9: mixing and uniformly stirring 10 parts of aluminum hydroxide and 22 parts of water, continuously dropwise adding 37 parts of nitric acid with the concentration of 66%, controlling the dropwise adding time to be 0.8h, controlling the temperature to be 88 ℃, stirring for 1.8h until the nitric acid is completely dissolved, controlling the end point pH value to be 4-6, adding 31 parts of water, cooling to 28 ℃ to obtain aluminum nitrate nonahydrate, adding 5 parts of acidic silica sol, 1 part of magnesium fluosilicate and 0.1 part of hydroxypropyl methyl cellulose, and stirring for 0.8h to obtain the sulfur-free alkali-free accelerator beneficial to the durability of sprayed concrete.
Example 10: mixing and uniformly stirring 10 parts of aluminum hydroxide and 22 parts of water, continuously dropwise adding 37 parts of nitric acid with the concentration of 68%, controlling the dropwise adding time to be 1.0h, controlling the temperature to be 90 ℃, stirring for 2.0h until the nitric acid is completely dissolved, controlling the end point pH value to be 4-6, adding 31 parts of water, cooling to 30 ℃ to obtain aluminum nitrate nonahydrate, adding 5 parts of acidic silica sol, 2 parts of magnesium fluosilicate and 1 part of hydroxypropyl methyl cellulose, and stirring for 1.0h to obtain the sulfur-free and alkali-free accelerator beneficial to the durability of sprayed concrete.
The water is softened water for removing calcium and magnesium ions.
The chemical indexes and performance indexes of the sulfur-free and alkali-free accelerator useful for durability of shotcrete prepared in examples 8 to 10 and the commercially available alkali-free accelerator containing aluminum sulfate as a main component are examined below.
Chemical index
Test samples: comparative example: a commercially available alkali-free accelerator (available from Baiqiang construction materials works) containing aluminum sulfate as a main component was used.
The test method comprises the following steps: the chemical indexes of the sulfur-free and alkali-free accelerator beneficial to the durability of the sprayed concrete prepared in the comparative example and the examples 8 to 10 are detected according to the detection method in GB/T35159-2017 accelerating agent for sprayed concrete, and the chemical indexes comprise alkali content and sulfate radical content.
And (3) test results: the alkali content and the sulfate radical content of the sulfur-free and alkali-free setting accelerators beneficial to the durability of sprayed concrete prepared in the comparative example and the examples 8 to 10 are shown in the table 1, and the sulfate radical content of the sulfur-free and alkali-free setting accelerators beneficial to the durability of sprayed concrete prepared in the examples 8 to 10 is not detected, and the alkali content is less than or equal to 1.0, which all meet the national standard requirements.
(II) index of Performance
Test samples: the sulfur-free and alkali-free accelerators useful for shotcrete durability prepared in comparative example and examples 8 to 10 above were blended in 5% in the neat paste and mortar respectively and mixed well.
The test method comprises the following steps: and detecting the performance indexes of the test samples according to GB/T35159-2017 accelerator for sprayed concrete, wherein the performance indexes comprise the setting time of the doped neat slurry and the mortar strength.
And (3) test results: as shown in Table 2, the set time and the set time after the sulfur-free and alkali-free accelerators for shotcrete durability prepared in examples 8 to 10 were added to the neat paste were shorter and the setting rate was faster than the set time and the set time after the sulfur-free and alkali-free accelerators for shotcrete durability were added to the neat paste in a comparative manner; the sulfur-free and alkali-free setting accelerators useful for shotcrete durability prepared in examples 8 to 10 above were better in 1d compressive strength, 28d compressive strength ratio and 90d compressive strength retention rate after being blended into mortar than those of comparative examples. Therefore, the performance indexes of the sulfur-free and alkali-free accelerator beneficial to the durability of sprayed concrete prepared in examples 8 to 10 of the present invention meet the national standards and are better than those of the commercially available alkali-free accelerator containing aluminum sulfate as a main component.
In conclusion, the invention solves the application defect of the alkali-free accelerator taking aluminum sulfate as the main component, provides the sulfur-free alkali-free accelerator which has no sulfate ions and no alkali metal ions and is beneficial to the durability of sprayed concrete, not only avoids alkali aggregate reaction caused by alkali metal ions, but also avoids the corrosion of the sulfate ions to the concrete, and has no damage to the durability of the concrete in the product.
The other components of the invention are mutually matched and act, which is also beneficial to the durability of concrete, wherein, the acid silica sol is a nano material and can fill micro cracks generated when the concrete is solidified, thereby improving the impermeability and compressive strength of the concrete; the magnesium fluosilicate is hydrolyzed when meeting free alkali in the concrete, can generate hydrated silica gel with a three-dimensional structure, can accelerate the solidification of the concrete and form concrete with higher strength; cellulose ether improves the stability of concrete by increasing the viscosity of the concrete.
Therefore, the sulfur-free alkali-free accelerator beneficial to the durability of sprayed concrete can improve the impermeability and compressive strength of the concrete, and meanwhile, the main component contains nitrate, so that the sulfur-free alkali-free accelerator has an anti-corrosion effect on the concrete and prolongs the service life of the concrete.
The technical characteristics form an embodiment of the invention, which has strong adaptability and implementation effect, and unnecessary technical characteristics can be increased or decreased according to actual needs to meet the requirements of different situations.
Claims (9)
1. The sulfur-free alkali-free setting accelerator beneficial to the durability of sprayed concrete is characterized by comprising 40 to 60 parts by weight of aluminum nitrate nonahydrate, 5 to 10 parts by weight of acidic silica sol, 1 to 3 parts by weight of magnesium fluosilicate, 0.1 to 1 part by weight of cellulose ether and 30 to 55 parts by weight of water.
2. The sulfur-free and alkali-free accelerator useful for shotcrete durability according to claim 1, which is obtained by the following method: after dissolving the required amount of aluminum nitrate nonahydrate with the required amount of water, adding the required amount of acidic silica sol, magnesium fluosilicate and cellulose ether, and stirring to obtain the sulfur-free alkali-free accelerator beneficial to the durability of sprayed concrete.
3. The sulfur-free and alkali-free accelerator useful for shotcrete durability according to claim 1 or 2, wherein the cellulose ether is hydroxypropyl methylcellulose.
4. The sulfur-free and alkali-free accelerator useful for shotcrete durability according to claim 1 or 2, wherein the stirring time is 0.8 to 1.2 hours.
5. The sulfur-free and alkali-free accelerator useful for durability of shotcrete according to claim 3, wherein the stirring time is 0.8 to 1.2 hours.
6. The sulfur-free and alkali-free accelerator useful for shotcrete durability according to claim 1, 2 or 5, wherein the starting material aluminum nitrate nonahydrate is obtained by the following method: mixing and stirring aluminum hydroxide and water uniformly, continuously dropwise adding nitric acid with the concentration of 66-70%, controlling the dropwise adding time to be 0.8-1.2 h, controlling the temperature to be 88-92 ℃, stirring for 1.8-2.2 h until the nitric acid is completely dissolved, controlling the end-point pH value to be 4-6, and cooling to 28-32 ℃ to obtain aluminum nitrate nonahydrate, wherein the mass ratio of the aluminum hydroxide to the nitric acid is 1: 3-4.
7. The sulfur-free and alkali-free accelerator useful for shotcrete durability according to claim 3, wherein the starting material aluminum nitrate nonahydrate is obtained by the following method: mixing and stirring aluminum hydroxide and water uniformly, continuously dropwise adding nitric acid with the concentration of 66-70%, controlling the dropwise adding time to be 0.8-1.2 h, controlling the temperature to be 88-92 ℃, stirring for 1.8-2.2 h until the nitric acid is completely dissolved, controlling the end-point pH value to be 4-6, and cooling to 28-32 ℃ to obtain aluminum nitrate nonahydrate, wherein the mass ratio of the aluminum hydroxide to the nitric acid is 1: 3-4.
8. The sulfur-free and alkali-free accelerator useful for shotcrete durability according to claim 4, wherein the starting material aluminum nitrate nonahydrate is obtained by the following method: mixing and stirring aluminum hydroxide and water uniformly, continuously dropwise adding nitric acid with the concentration of 66-70%, controlling the dropwise adding time to be 0.8-1.2 h, controlling the temperature to be 88-92 ℃, stirring for 1.8-2.2 h until the nitric acid is completely dissolved, controlling the end-point pH value to be 4-6, and cooling to 28-32 ℃ to obtain aluminum nitrate nonahydrate, wherein the mass ratio of the aluminum hydroxide to the nitric acid is 1: 3-4.
9. A method for preparing a sulfur-free and alkali-free accelerator useful for shotcrete durability according to any one of claims 1 to 8, which is carried out by the following method: after dissolving the required amount of aluminum nitrate nonahydrate with the required amount of water, adding the required amount of acidic silica sol, magnesium fluosilicate and cellulose ether, and stirring to obtain the sulfur-free alkali-free accelerator beneficial to the durability of sprayed concrete.
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| CN202010019161.0A CN111253108A (en) | 2020-01-08 | 2020-01-08 | Sulfur-free alkali-free accelerator beneficial to durability of sprayed concrete and preparation method thereof |
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Cited By (3)
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| CN111992152A (en) * | 2020-08-07 | 2020-11-27 | 贵州石博士科技有限公司 | Preparation method of ultrasonic-assisted concrete self-repairing microcapsule under magnetic field coupling |
| CN114644485A (en) * | 2020-12-18 | 2022-06-21 | 四川苏博特新材料有限公司 | Tunnel shotcrete with high sulfate corrosion resistance and construction method thereof |
| CN115611545A (en) * | 2022-08-22 | 2023-01-17 | 贵州天威建材科技有限责任公司 | Method for preparing dry powder accelerator from fluorine and silicon residues |
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| CN111992152A (en) * | 2020-08-07 | 2020-11-27 | 贵州石博士科技有限公司 | Preparation method of ultrasonic-assisted concrete self-repairing microcapsule under magnetic field coupling |
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