CN109970412B - High-density cement-based material and preparation method thereof - Google Patents
High-density cement-based material and preparation method thereof Download PDFInfo
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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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
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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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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Abstract
The invention belongs to the field of building materials, and particularly relates to a high-density cement-based material and a preparation method thereof. The cement-based material comprises a solid component and a liquid component in parts by weight, and the solid component and the liquid component are stored separately; wherein the solid component comprises: 100-120 parts of cement, 20-40 parts of calcium sulfosilicate, 10-25 parts of sericite powder, 5-10 parts of a water reducing agent, 5-15 parts of an anionic surfactant, 1-5 parts of sodium acetate and 10-18 parts of aluminum hydroxide; the liquid component is 15-38 parts water. The cement-based material provided by the invention can overcome and make up the defect of micro shrinkage of hydrated volume of the portland cement, and obviously improve the structural density of the portland cement.
Description
Technical Field
The invention belongs to the field of building materials, and particularly relates to a high-density cement-based material and a preparation method thereof.
Background
This information disclosed in this background of the invention is only for the purpose of increasing an understanding of the general background of the invention and is not necessarily to be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
The silicate cement is a hydraulic cementing material prepared by grinding silicate cement clinker which mainly comprises tricalcium silicate, dicalcium silicate, tricalcium aluminate and tetracalcium aluminoferrite, and a proper amount of gypsum, fly ash, granulated blast furnace slag and other mixed materials, and is the cementing material with the largest worldwide dosage. For example, patent document 200610025969.X discloses a high-density calcium silicate board, which is made from cement, fly ash, quartz sand, cellulose fiber, wollastonite, kaolin, alumina and mica through the steps of pulping, storing, discharging, taking, forming, pressurizing, steaming at normal pressure, demolding, pressure steaming and sanding, and has the characteristics of high density, high nail holding power, high strength and the like.
Patent document 201710760339.5 discloses a high-density calcium silicate board and a preparation method thereof, wherein the high-density calcium silicate board is prepared from the following raw materials in parts by weight: 10-15 parts of bentonite, 0.1-0.5 part of modifier, 200 parts of cement, 200 parts of fly ash, 10-20 parts of silica fume and 1.5-4 parts of fiber. The calcium silicate board has low porosity and high density, reduces the using amount of paint by 40-50 percent, and obviously reduces the cost.
In fact, the hydration of portland cement is a complex physical and chemical process, and not only a large amount of hydration products, such as C-S-H, calcium hydroxide and the like, are generated in the process, but also the volume is slightly shrunk, so that the finally obtained concrete is a gas-liquid-solid three-phase coexisting body, and the coexisting body has poor structural density and the existence of easily soluble mineral calcium hydroxide, thereby causing poor erosion resistance and freezing resistance of portland cement hardened slurry; therefore, new methods are needed to further improve the structural density of portland cement.
Disclosure of Invention
Aiming at the problems, the invention provides a high-density cement-based material and a preparation method thereof. The cement-based material provided by the invention can overcome and make up the defect of micro shrinkage of hydrated volume of the portland cement, and obviously improve the structural density of the portland cement.
In order to realize the purpose, the invention discloses the following technical scheme:
the first object of the present invention: providing a high-density cement-based material which comprises a solid component and a liquid component in parts by weight, wherein the solid component and the liquid component are stored separately; wherein the solid component comprises: 100-120 parts of cement, 20-40 parts of calcium sulfosilicate, 10-25 parts of sericite powder, 5-10 parts of sodium gluconate, 5-15 parts of anionic surfactant, 1-5 parts of sodium acetate and 10-18 parts of aluminum hydroxide; the liquid component is 15-38 parts water.
Further, the solid component is present in a form comprising: each solid component is present alone, or any two or more of the solid components thereof are mixed.
The anionic surfactant is sodium dodecyl benzene sulfonate. The calcium sulfosilicate prepared by the invention is microcrystalline fine powder which is easy to agglomerate in water, but can generate a crosslinking effect with hydroxyl on a molecular chain of sodium gluconate and sodium dodecyl benzene sulfonate with high surface activity, so that the dispersibility of the calcium sulfosilicate is improved.
Preferably, the high-density cement-based material consists of the following components in parts by weight: 110 parts of cement, 30 parts of calcium sulfosilicate, 20 parts of superfine sericite powder, 8 parts of sodium gluconate, 10 parts of sodium dodecyl benzene sulfonate, 3 parts of sodium acetate, 15 parts of aluminum hydroxide and 25 parts of water. The test shows that: when the content of each component is in the specific value, the compressive strength and the compactness of the cement-based material are improved more obviously.
Optionally, the cement comprises portland cement or the like.
Furthermore, the calcium sulfosilicate exists in a microcrystalline form, and the preparation method comprises the following steps:
(a) CaO is SiO2:CaSO4Uniformly mixing according to the mass mol ratio of 4-6:2:1, then calcining at the temperature of 1100-1150 ℃ for 30-80 minutes, taking out and water quenching for 10-30 seconds;
(b) grinding the water-quenched product until the sieve residue of a 200-mesh sieve is less than 2%, directly placing the powder into a high-temperature hearth at 1200-1250 ℃ for calcining for 30-80 minutes, taking out the powder, and then performing water quenching again for cooling for 10-30 seconds;
(c) and grinding the product after water quenching again until the sieve residue of a 200-mesh sieve is less than 2 percent, thus obtaining the calcium sulfosilicate existing in a microcrystalline form.
The second purpose of the invention is to provide a preparation method of the high-density cement-based material, which comprises the following steps:
(1) dissolving sodium acetate in water, adding aluminum hydroxide, and stirring while adding to obtain a material A;
(2) mixing calcium sulfosilicate, sodium gluconate and an anionic surfactant, adding the material A after stirring, uniformly stirring, and standing to obtain a material B;
(3) adding superfine sericite powder into water, and stirring to obtain a material C; and then adding the material B and the cement into the material C in sequence, and stirring to obtain the high-density cement-based material.
Further, in the step (1), the adding proportion of the water is 5-18 parts, and the rest water is completely used for preparing the material C in the step (3).
Further, in the steps (1) and (2), the stirring time is 30-90 seconds; in the step (2), the standing time is 3-6 minutes.
The third purpose of the invention is to provide the high-density cement-based material and the application of the preparation method thereof in the field of buildings. The cement-based material provided by the invention has excellent structure density, can remarkably relieve the problems of poor corrosion resistance and poor freezing resistance of portland cement hardened slurry caused by poor structure density and the existence of easily soluble mineral calcium hydroxide, and is very suitable for preparing various building materials in the field of buildings.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts the synergistic effect between calcium sulfosilicate and aluminum hydroxide to ensure that the calcium sulfosilicate is hydrolyzed to generate the ettringite containing 32 crystal water under the excitation of alumina gel (namely hydrated alumina, generally microcrystalline aluminum hydroxide), and the hydration is a process of volume micro-expansion, so that the defect of micro-shrinkage of hydrated volume of the silicate cement can be improved and compensated, and the structural density of the silicate cement is further improved.
(2) The invention regulates the particle size and the hydration activity of calcium sulfosilicate by changing the existing form of the calcium sulfosilicate, thereby controlling the reaction rate of the calcium sulfosilicate and the alumina gel, preventing the hydration product of the calcium sulfosilicate from wrapping tricalcium silicate due to too fast reaction, reducing the reaction amount and the reaction rate of the tricalcium silicate, finally reducing the early strength of concrete, and preventing the generated ettringite from generating expansion stress to a hardened body structure due to too slow reaction and forming microcracks inside.
(3) The invention utilizes the layered structure of the superfine sericite to absorb part of the mixing water, reduces the pores formed by the existence of free water in a cement hardened body, and interlayer water can provide necessary reaction water for the hydration of calcium sulfosilicate and the generation of ettringite, thereby effectively regulating and controlling the hydration reaction rate of calcium sulfosilicate and improving the structural density of silicate cement.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As mentioned above, the hydration of portland cement is a complex physical and chemical process, in the process, not only a large amount of hydration products are generated, but also the volume is slightly shrunk, and the like, so that the finally obtained concrete is a gas-liquid-solid three-phase coexisting body, and the coexisting body not only has poor structural density, but also has the existence of the easily soluble mineral calcium hydroxide, thereby causing poor erosion resistance and freezing resistance of portland cement hardened slurry. Therefore, the invention provides a high-density cement-based material and a preparation method thereof; the invention will now be further described with reference to specific embodiments.
In the following examples, the portland cement was available from innovated cement of the south-JI century, Inc. at a strength rating of 42.5.
Example 1
1. A preparation method of a high-density portland cement-based material comprises the following steps:
(1) dissolving 1 part of sodium acetate in 5 parts of water, adding 10 parts of aluminum hydroxide, and stirring for 30 seconds while adding to obtain a material A;
(2) mixing 20 parts of calcium sulfosilicate, 5 parts of sodium gluconate and 15 parts of sodium dodecyl benzene sulfonate, stirring for 30 seconds, adding the material A, uniformly stirring, and standing for 3 minutes; obtaining a material B;
(3) mixing 25 parts of superfine sericite powder and 10 parts of water, and uniformly stirring to obtain a material C; and then sequentially adding the material B and 100 parts of Portland cement into the material C, and uniformly stirring to obtain the high-density Portland cement-based material.
The calcium sulfosilicate exists in a microcrystalline form, and the preparation method comprises the following steps:
(a) CaO is SiO2:CaSO4Uniformly mixing the raw materials according to the mass molar ratio of 4:2:1, directly putting the raw materials into a high-temperature hearth at 1100 ℃ for calcining for 80 minutes, taking out the raw materials, and then performing water quenching and cooling for 10 seconds;
(b) grinding the water-quenched product until the sieve residue of a 200-mesh sieve is less than 2%, directly putting the powder into a high-temperature hearth at 1200 ℃ for calcining for 80 minutes, taking out the powder, and then performing water quenching again for cooling for 10 seconds;
(c) and grinding the product after water quenching again until the sieve residue of a 200-mesh sieve is less than 2 percent to obtain the calcium sulfosilicate existing in microcrystalline.
Example 2
1. A preparation method of a high-density portland cement-based material comprises the following steps:
(1) dissolving 5 parts of sodium acetate in 18 parts of water, adding 18 parts of aluminum hydroxide, and stirring for 90 seconds while adding to obtain a material A;
(2) mixing 40 parts of calcium sulfosilicate, 10 parts of sodium gluconate and 5 parts of sodium dodecyl benzene sulfonate, stirring for 90 seconds, adding the material A, uniformly stirring, and standing for 6 minutes; obtaining a material B;
(3) mixing 10 parts of superfine sericite powder and 20 parts of water, and uniformly stirring to obtain a material C; and then sequentially adding the material B and 120 parts of Portland cement into the material C, and uniformly stirring to obtain the high-density Portland cement-based material.
The calcium sulfosilicate exists in a microcrystalline form, and the preparation method comprises the following steps:
(a) CaO is SiO2:CaSO4Uniformly mixing the raw materials according to the mass molar ratio of 6:2:1, directly putting the raw materials into a high-temperature hearth at 1150 ℃ for calcining for 30 minutes, taking out the raw materials, and then quenching and cooling the raw materials for 30 seconds;
(b) grinding the water-quenched product to a powder size of less than 2% of the sieve residue of a 200-mesh sieve, directly putting the powder into a high-temperature hearth at 1250 ℃ for calcining for 30 minutes, taking out the powder, and then performing water quenching again for cooling for 30 seconds;
(c) and grinding the product after water quenching again until the sieve residue of a 200-mesh sieve is less than 2 percent to obtain the calcium sulfosilicate existing in microcrystalline.
Example 3
1. A preparation method of a high-density portland cement-based material comprises the following steps:
(1) dissolving 3 parts of sodium acetate in 10 parts of water, adding 15 parts of aluminum hydroxide, and stirring for 60 seconds while adding to obtain a material A;
(2) mixing 30 parts of calcium sulfosilicate, 8 parts of sodium gluconate and 10 parts of sodium dodecyl benzene sulfonate, stirring for 45 seconds, adding the material A, uniformly stirring, and standing for 5 minutes; obtaining a material B;
(3) mixing 20 parts of superfine sericite powder and 15 parts of water, and uniformly stirring to obtain a material C; and then, sequentially adding the material B and 110 parts of Portland cement into the material C, and uniformly stirring to obtain the high-density Portland cement-based material.
The calcium sulfosilicate exists in a microcrystalline form, and the preparation method comprises the following steps:
(a) CaO is SiO2:CaSO4Uniformly mixing the raw materials according to the mass molar ratio of 5:2:1, directly putting the raw materials into a 1120 ℃ high-temperature hearth for calcining for 50 minutes, taking out the raw materials, and then performing water quenching and cooling for 20 seconds;
(b) grinding the water-quenched product until the sieve residue of a 200-mesh sieve is less than 2%, directly putting the powder into a high-temperature hearth at 1230 ℃ for calcining for 40 minutes, taking out the powder, and then performing water quenching again for cooling for 25 seconds;
(c) and grinding the product after water quenching again until the sieve residue of a 200-mesh sieve is less than 2 percent to obtain the calcium sulfosilicate existing in microcrystalline.
Experimental example 1
A method for preparing a high-density cement-based material, which is the same as the method in example 1, and is characterized in that: aluminum hydroxide is not added in the step (1) to verify the influence of hydration reaction of calcium sulfosilicate under the excitation of the aluminum hydroxide on the structural compactness of the portland cement.
Experimental example 2
A method for preparing a high-density cement-based material, which is the same as the method in example 1, and is characterized in that: and (3) no calcium sulfosilicate is added in the step (2) to verify the influence of hydration reaction of the calcium sulfosilicate under the excitation of aluminum hydroxide on the structural compactness of the portland cement.
Experimental example 3
A method for preparing a high-density cement-based material, which is the same as the method in example 1, and is characterized in that: the calcium sulfosilicate in the step (2) is a commercially available common calcium sulfosilicate powder, and is not calcium sulfosilicate existing in a microcrystalline form prepared by the method described in example 1, so as to verify the influence of the existing form of the calcium sulfosilicate on the reaction rate of the calcium sulfosilicate and the alumina cement on the early strength of the portland cement concrete.
Experimental example 4
A method for preparing a high-density cement-based material, which is the same as the method in example 1, and is characterized in that: and (3) not adding superfine sericite to verify the influence of the existence form of the laminated structure of the sericite on the structural density of the portland cement.
Experimental example 5
A method for preparing a high-density cement-based material, which is the same as the method in example 1, and is characterized in that: and (3) omitting the step (2) to verify the influence of the sodium gluconate and the sodium dodecyl benzene sulfonate on the prepared calcium sulfosilicate and further on the performance of the obtained Portland cement.
And (3) performance testing:
concrete test blocks made of the highly dense cement-based materials obtained in examples 1 to 3 and experimental examples 1 to 5 were subjected to compression strength (28 days) and porosity tests according to the standard for evaluating concrete strength (GB/T50107-2010) and the method for testing the long-term performance and durability of ordinary concrete (GB/T50082-2009), and the results are shown in table 1.
TABLE 1
| Example 1 | Example 2 | Example 3 | Experimental example 1 | Experimental example 2 | Experimental example 3 | Experimental example 4 | Test example 5 | |
| Compressive strength/MPa | 67.8 | 69.1 | 76.8 | 43.6 | 48.2 | 35.6 | 56.3 | 50.5 |
| Porosity/% | 15.9 | 18.7 | 12.9 | 28.5 | 33.4 | 28.3 | 30.6 | 24.1 |
As can be seen from the test results in table 1, the structural compactness of the portland cement obtained in experimental examples 1 and 2 is greatly reduced compared with that obtained in example 1; this shows that the structural compactness of the portland cement can be improved when calcium sulfosilicate and aluminum hydroxide exist simultaneously. Further analysis shows that: the calcium sulfosilicate is hydrolyzed to generate ettringite containing 32 crystal water under the excitation of aluminum hydroxide, and the hydration is a volume micro-expansion process, so that the defect of micro-shrinkage of the hydrated volume of the portland cement can be effectively improved and compensated, and the structural compactness of the portland cement is further improved.
The early strength of the portland cement obtained in experimental example 3 is greatly reduced, and the structural density is reduced to a certain extent, which shows that the existing form of calcium sulfosilicate can obviously influence the early strength of the portland cement; further research shows that: the calcium sulfosilicate existing in the microcrystalline form can effectively control the reaction rate of the calcium sulfosilicate and the alumina gel, so that the problems that hydration products of the calcium sulfosilicate wrap tricalcium silicate due to too fast reaction, the reaction amount and the reaction rate of the tricalcium silicate are reduced, and the early strength of concrete is finally reduced can be solved, and the problems that the generated ettringite generates expansion stress on a hardened body structure and forms microcracks in the interior due to too slow reaction can be solved.
The structural density of the portland cement obtained in experimental example 4 is also greatly reduced, which shows that the structural density of the portland cement can be effectively improved by adding the ultrafine sericite; further research finds that the pores formed by the existence of free water in a cement hardened body can be reduced due to the fact that the layered structure of the superfine sericite absorbs part of mixing water, and interlayer water can provide necessary reaction water for the hydration of calcium sulfosilicate and the generation of ettringite, so that the hydration reaction rate of calcium sulfosilicate is effectively regulated and controlled, and the structural compactness of silicate cement is improved.
In addition, as can be seen from the test results of test example 5, when sodium gluconate and sodium dodecylbenzenesulfonate are not added, the structural density and strength of the obtained portland cement are lower than those of example 1, and after the study, the following findings are obtained: although the calcium sulfosilicate prepared by the invention can generate good synergistic effect with components such as aluminum hydroxide and the like to improve the performance of the portland cement, on the premise that the calcium sulfosilicate can be uniformly dispersed in the prepared portland cement, because the calcium sulfosilicate prepared by the invention is microcrystalline fine powder which is easy to agglomerate in water, the calcium sulfosilicate can only locally improve the performance of the portland cement, and as a result, the overall performance distribution of the portland cement is not uniform.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A highly densified cement-based material, characterized in that the cement-based material comprises, in parts by weight, a solid component and a liquid component, and the solid component and the liquid component are stored separately; wherein the content of the first and second substances,
the solid component comprises: 100-120 parts of cement, 20-40 parts of calcium sulfosilicate, 10-25 parts of superfine sericite powder, 5-10 parts of sodium gluconate, 5-15 parts of sodium dodecyl benzene sulfonate, 1-5 parts of sodium acetate and 10-18 parts of aluminum hydroxide;
the liquid component is 15-38 parts of water;
the calcium sulfosilicate is microcrystalline fine powder;
the preparation method of the calcium sulfosilicate comprises the following steps:
(a) CaO is SiO2:CaSO4Uniformly mixing according to the mass mol ratio of 4-6:2:1, then calcining at the temperature of 1100-1150 ℃ for 30-80 minutes, taking out and water quenching for 10-30 seconds;
(b) grinding the water-quenched product until the sieve residue of a 200-mesh sieve is less than 2%, directly placing the powder into a high-temperature hearth at 1200-1250 ℃ for calcining for 30-80 minutes, taking out the powder, and then performing water quenching again for cooling for 10-30 seconds;
(c) and grinding the product after water quenching again until the sieve residue of a 200-mesh sieve is less than 2 percent, thus obtaining the calcium sulfosilicate existing in a microcrystalline form.
2. The highly densified cement-based material of claim 1, wherein the solid component is present in a form comprising: each solid component is present alone, or any two or more of the solid components thereof are mixed.
3. The highly densified cement-based material of claim 1, wherein: the high-density cement-based material is composed of the following components in parts by weight: 110 parts of cement, 30 parts of calcium sulfosilicate, 20 parts of superfine sericite powder, 8 parts of sodium gluconate, 10 parts of sodium dodecyl benzene sulfonate, 3 parts of sodium acetate, 15 parts of aluminum hydroxide and 25 parts of water.
4. A method of producing a highly compacted cementitious material as claimed in any one of claims 1 to 3, characterised in that it includes the steps of:
(1) dissolving sodium acetate in water, adding aluminum hydroxide, and stirring while adding to obtain a material A;
(2) mixing calcium sulfosilicate, sodium gluconate and sodium dodecyl benzene sulfonate, adding the material A after stirring, uniformly stirring, and standing to obtain a material B;
(3) adding superfine sericite powder into water, and stirring to obtain a material C; and then adding the material B and the cement into the material C in sequence, and stirring to obtain the high-density cement-based material.
5. The process according to claim 4, wherein in step (1), the water is added in a proportion of 5 to 18 parts, and the remaining water is used entirely for the production of the material C in step (3).
6. The method according to claim 4, wherein the stirring time in each of the steps (1) and (2) is 30 to 90 seconds.
7. The method according to claim 4, wherein the standing time in the step (2) is 3 to 6 minutes.
8. Use of a highly compacted cementitious material according to any of claims 1 to 3 and/or a method of manufacture according to any of claims 4 to 7 in the field of construction.
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| CN103889923A (en) * | 2011-08-18 | 2014-06-25 | 海德堡水泥公司 | Method and additive for increasing starting resistance |
| CN104609434A (en) * | 2015-02-09 | 2015-05-13 | 重庆大学 | Preparation method and application method of calcium sulphosilicate mineral |
| CN108529992A (en) * | 2018-07-03 | 2018-09-14 | 济南大学 | A kind of high-Miller-index surface and preparation method thereof |
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| CN103889923A (en) * | 2011-08-18 | 2014-06-25 | 海德堡水泥公司 | Method and additive for increasing starting resistance |
| CN104609434A (en) * | 2015-02-09 | 2015-05-13 | 重庆大学 | Preparation method and application method of calcium sulphosilicate mineral |
| CN108529992A (en) * | 2018-07-03 | 2018-09-14 | 济南大学 | A kind of high-Miller-index surface and preparation method thereof |
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