CN112408876B - Cement-based porous material based on silicon dioxide and preparation method thereof - Google Patents
Cement-based porous material based on silicon dioxide 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
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- 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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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
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- C—CHEMISTRY; METALLURGY
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- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- 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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- 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
- C04B2201/52—High compression strength concretes, i.e. with a compression strength higher than about 55 N/mm2, e.g. reactive powder concrete [RPC]
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention relates to the technical field of building materials, and discloses a cement-based porous material based on silicon dioxide and a preparation method thereof, wherein the cement-based porous material is mainly obtained by mixing cement, an admixture, water, an additive and a silicon dioxide dispersion liquid and then coagulating and hardening; wherein the silica dispersion is a dispersion system in which silica particles are dispersed in water. According to the invention, because the cement hydration reaction can not completely consume the introduced water, a large amount of capillary space is formed, the cement hydration product and the spherical silicon dioxide surface generate volcanic ash reaction, the cement hydration product grows on the silicon dioxide and is mutually overlapped, the capillary space can be finely divided, a large amount of nano-pore space is constructed in the capillary space, and the nano-pore proportion in the cement composite porous material is increased; meanwhile, the capillary space is constructed through the nano-pore structure, the microstructure of the material is strengthened, the development of the material strength is facilitated, and the mechanical property of the cement-based porous material is improved.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to a cement-based porous material based on silicon dioxide and a preparation method thereof.
Background
The cement-based porous material has great potential in the aspect of being used as a building heat-insulating material due to the advantages of simple process, low cost, safety, fire prevention and the like, and the common cement-based porous material is a cement-based material with rich pore structure prepared by introducing air into the cement-based material through air entraining agents such as aluminum powder, hydrogen peroxide and the like to form pores or carrying a pore structure into the cement-based material through prefabricated foam, lightweight aggregate and the like.
Introducing more pore structures into the cement-based material can realize the ultralight material and further improve the heat insulation performance of the material, but the introduction of pores can also lead to the great weakening of the mechanical property of the cement-based porous material, and particularly, the higher the content of pores with the pore diameter of more than 0.1 mu m is, the more the mechanical property of the porous material can be obviously reduced. Research shows that the air hole nanocrystallization, reasonable nano hole proportion and porosity have great potential in the aspect of realizing the design and preparation of lightweight, high-strength and low-heat-conduction cement-based materials.
Disclosure of Invention
Based on the problems, the invention provides a cement-based porous material based on silicon dioxide and a preparation method thereof, wherein a large amount of capillary space is formed because the hydration reaction of cement cannot completely consume introduced water, the cement hydration product and the surface of spherical silicon dioxide generate volcanic ash reaction, the cement hydration product grows on the silicon dioxide and is mutually overlapped, the capillary space can be finely divided, a large amount of nano-pore space is constructed in the capillary space, and the proportion of nano-pores in the cement composite porous material is increased; meanwhile, the capillary space is constructed through the nano-pore structure, the microstructure of the material is strengthened, the development of the material strength is facilitated, and the mechanical property of the cement-based porous material is improved.
In order to realize the technical effect, the invention adopts the following technical scheme:
a cement-based porous material based on silicon dioxide is mainly a porous material obtained by uniformly mixing cement, admixture, water, admixture and silicon dioxide dispersion liquid and then coagulating and hardening; wherein, the water cement ratio is 0.2-2, and the dosage of the admixture is 0-30% of the mass of the cement and the admixture; the silica dispersion is a dispersion system in which silica particles are dispersed in water.
Further, the admixture is 0-99% of the total mass of the cement and the admixture, and the admixture is mainly any one or more of slag, fly ash, silica fume, an expanding agent or fiber.
Further, the admixture comprises any one or more of a water reducing agent, a shrinkage reducing agent, a retarder or an early strength agent.
Further, the dry density of the cement-based porous material is 50-1800kg/m3The porosity is 20-98%, the average pore diameter is 2-100nm, and the cumulative pore volume is 0.13-19.50 cc/g.
Further, the dry density of the cement-based porous material is 700-1250kg/m3Porosity of 50-75%, average pore diameter of 25-35nm, cumulative pore volume of 0.45-1.45 cc/g; wherein the average pore diameter of the nano pores is 7-15nm, and the volume of the nano pores is 0.16-0.90 cc/g.
In order to realize the technical effects, the invention also provides a preparation method of the cement-based porous material based on the silicon dioxide, which comprises the following steps:
s1, adding the silicon dioxide powder into water, and dispersing the silicon dioxide in the water by adopting any one or more modes of mechanical stirring, ultrasonic dispersion, water reducing agent addition or surfactant addition to form a silicon dioxide dispersion liquid;
s2, weighing cement, admixture, water and admixture according to the proportion, and uniformly stirring to obtain a base material;
s3, mixing and stirring the prepared silicon dioxide dispersion liquid and a base material uniformly according to any ratio to prepare intermediate slurry;
and S4, forming and maintaining the intermediate slurry, and drying to obtain the cement-based porous material.
Further, the ratio of the silica dispersion to the matrix material in step S3 is calculated by a volume substitution method, wherein the volume substitution range of the silica dispersion is 0-95% of the total volume of the cement-based porous material.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, because the cement hydration reaction can not completely consume the introduced water, a large amount of capillary space is formed, the cement hydration product and the spherical silicon dioxide surface generate volcanic ash reaction, the cement hydration product grows on the silicon dioxide and is mutually overlapped, the capillary space can be finely divided, a large amount of nano-pore space is constructed in the capillary space, and the nano-pore proportion in the cement composite porous material is increased; meanwhile, the capillary space is constructed through the nano-pore structure, the microstructure of the material is strengthened, the development of the material strength is facilitated, and the mechanical property of the cement-based porous material is improved.
Drawings
FIG. 1 is a graph of the compressive strength curves of a silica-based cement-based porous material and aerated concrete at different dry densities in example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples and accompanying drawings, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not meant to limit the present invention.
Example 1:
a cement-based porous material based on silicon dioxide is mainly a porous material obtained by uniformly mixing cement, admixture, water, admixture and silicon dioxide dispersion liquid and then coagulating and hardening; wherein, the water cement ratio is 0.2-2, and the dosage of the admixture is 0-30% of the mass of the cement and the admixture; the silica dispersion is a dispersion system in which silica particles are dispersed in water.
The preparation method of the silica-based cement-based porous material in the embodiment specifically comprises the following operation steps:
s1, adding the silicon dioxide powder into water, and dispersing the silicon dioxide in the water by adopting any one or more modes of mechanical stirring, ultrasonic dispersion, water reducing agent addition or surfactant addition to form a silicon dioxide dispersion liquid;
s2, weighing cement, admixture, water and admixture according to the proportion, and uniformly stirring to obtain a base material; the additives in the embodiment can be water reducing agent, shrinkage reducing agent, retarder, early strength agent and other additives for improving the performance of cement and concrete.
S3, mixing and stirring the prepared silicon dioxide dispersion liquid and a base material uniformly according to any ratio to prepare intermediate slurry;
and S4, forming and maintaining the intermediate slurry, and drying to obtain the cement-based porous material.
In this example, the silica dispersion carried a large amount of water, which resulted in the formation of a large amount of capillary space due to incomplete consumption of the introduced water by the cement hydration reaction; spherical silicon dioxide particles exist in a capillary pore space of cement slurry, after a certain period of maintenance, cement hydration products grow on the silicon dioxide, the hydration products and the spherical silicon dioxide surface generate volcanic ash reaction, and the hydration products are mutually lapped to generate interaction; drying to remove water in the capillary pore space, thinning and dividing a large amount of water into capillary pore spaces formed by introducing a large amount of water due to mutual lapping and generated interaction of hydration products on the silicon dioxide, and largely constructing a nano pore space, thereby realizing construction of a nano pore structure of the silicon dioxide-cement composite porous material and increasing the proportion of nano pores; moreover, due to the interaction between the pore-forming agent and the cement hydration product, the nano-pore structure builds a capillary space, so that the microstructure of the material is strengthened, the development of the material strength is facilitated, and the mechanical property of the cement-based porous material is improved.
The cement, admixture, water and admixture in this embodiment may be mixed in any ratio with the silica dispersion to form a slurry. Wherein the proportion of the silicon dioxide dispersion liquid and the matrix material is calculated by a volume substitution method, the volume substitution range of the silicon dioxide dispersion liquid is 0-95 percent of the total volume of the cement-based porous material, and the dry density of the prepared cement-based porous material is 50-1800kg/m3The porosity is 20-98%, the average pore diameter is 2-100nm, and the cumulative pore volume is 0.13-19.50 cc/g.
Meanwhile, the admixture is 0-99% of the total mass of the cement and the admixture, and the admixture is mainly any one or more of slag, fly ash, silica fume, an expanding agent or fiber. The active admixtures can generate a nano-pore structure through self-hydration reaction in the cement hydration and setting hardening processes, or react with cement hydration products to be mutually overlapped to divide capillary pore space to form the nano-pore structure.
Example 2:
in the embodiment, P.O 42.5.5 cement, water and an additive (with a solid content of 10%) are uniformly stirred to prepare a base material with a water-to-gel ratio of 0.3; dispersing silicon dioxide powder in water by ultrasonic wave for 5-60min to obtain silicon dioxide dispersion liquid with solid content of 30%; then, the volume substitution method is adopted to design and calculate the mixing dosage of the matrix material and the silicon dioxide dispersion liquid under different dry densities, and the preparation ratio is shown in the following table 1:
TABLE 1 silica-based Cement-based cellular Material mix ratio (kg/m)3)
| Numbering | Designed dry density | Cement | Water (W) | Additive agent | Silica dispersion |
| 1 | 1800 | 2000 | 585.6 | 16.00 | 0 |
| 2 | 1500 | 1100 | 322.1 | 8.80 | 295 |
| 3 | 1200 | 840 | 246.0 | 6.72 | 548 |
| 4 | 900 | 600 | 175.7 | 4.80 | 845 |
| 5 | 600 | 280 | 82.0 | 2.24 | 1151 |
| 6 | 400 | 90 | 26.4 | 0.72 | 1372 |
Preparing a cement-based porous material according to the designed mixing proportion in the table, and sequentially adding water, an additive and a silicon dioxide dispersion liquid into cement to be uniformly stirred; then the fresh slurry is filled into a mould with the size of 40mm multiplied by 40mm to be compacted and formed, and a fresh-keeping cover is covered by a film to prevent the water loss; storing indoors for 24h, and then demoulding; after demoulding, maintaining the test block under standard maintenance conditions (20 +/-2 ℃ and 95% of humidity) to obtain a cement-based porous material, and measuring the dry density of the cement-based porous material; placing the cement-based porous material obtained in the steps at 60 ℃ to dry to constant weight, and carrying out a pore structure test:
adopts nitrogen adsorption technology (NA)D) The test is carried out, an isothermal adsorption curve is obtained under the condition of 77K, and the cumulative pore volume of the material is obtained when the relative pressure P/P0 is 0.99; the pore type and structure can be judged from the shape of the isotherm; when parameter CBETWhen the value of (a) is within an effective range (-5-300), calculating the specific surface area of the material by a Brunauer-Emmett-Teller (BET) method at a low-pressure end (P/P0 is 0.05-0.3); and analyzing the pore structure of the cement material by a mercury intrusion method. Porosity is related to mercury intrusion, so an approximate macropore size distribution can be derived from mercury intrusion. And (3) obtaining the pore structure parameters and the pore size distribution of the material by using a mercury intrusion spectrometer (MIP). The test data are shown in table 2:
TABLE 2 Dry Density and pore Structure of silica-based Cement-based porous Material
| Numbering | 1 | 2 | 3 | 4 | 5 | 6 |
| Dry density (kg/m)3) | 1702 | 1539 | 1171 | 933 | 646 | 424 |
| Average pore diameter (nm) | 44.2 | 32.7 | 28.4 | 24.4 | 33.9 | 38.8 |
| Porosity (%) | 23.6 | 31.3 | 49.7 | 61.4 | 72.5 | 80.4 |
| Cumulative pore volume (cc/g) | 0.128 | 0.213 | 0.472 | 0.735 | 1.022 | 1.51 |
| Specific surface area (m)2/g) | 16.1 | 29.0 | 43.3 | 126.9 | 161.8 | 176.6 |
| Average diameter of nanopore (nm) | 36.3 | 15.4 | 7.6 | 8.1 | 13.7 | 16.8 |
| Nanopore volume (cc/g) | 0.044 | 0.117 | 0.169 | 0.546 | 0.883 | 0.762 |
| 28 days compressive strength (Mpa) | 81.4 | 45.5 | 27.0 | 18.9 | 11.2 | 5.5 |
| 56 days compressive strength (Mpa) | 96.5 | 55.1 | 36.8 | 22.2 | 13.8 | 5.9 |
The data in table 2 show that the silica dispersion can construct a large number of nano-pores in the cement-based material, so that the average pore diameter of the nano-pores in the cement-based porous material is reduced, the cumulative pore volume and the specific surface area are increased, the content of the nano-pores in the cement-based porous material is obviously increased along with the increase of the doping amount of the silica dispersion, and the construction of a large number of nano-pores in the cement slurry is realized. However, too high mixing amount of the silicon dioxide dispersion liquid can also cause too high water-gel ratio, so that too much free water is introduced into the cement-based material, communication holes in the cement-based material can be formed, sub-micron holes are formed, the strength of the framework is insufficient, and the structure collapse is caused; meanwhile, the silicon dioxide dispersion liquid participates in hydration reaction to weaken the refining effect on the pore diameter, so that the average pore diameter of the nano-pores is increased.
The 28-day strength is adopted to compare the compressive strength of the silica-based cement-based porous material and the aerated concrete with different densities, which are obtained under the same matrix material and the same curing system, and the data result is shown in figure 1, wherein the mechanical properties of the two materials are reduced along with the reduction of the density; however, it can be seen from the curves that the compressive strength of the cement-based porous material based on silica is entirely higher than that of aerated concrete under different dry densities, which is mainly due to the fact that the cement-based porous material has more nano-pores, relatively concentrated pore size distribution and small pore size, stress unevenness of a test block under the action of external force is relieved, and the nano-pore structure has less harm to mechanical properties, so that the cement-based porous material represents a higher mechanical material, and therefore, the compressive strength is higher than that of light aggregate concrete and aerated concrete.
The above is an embodiment of the present invention. The embodiments and specific parameters in the embodiments are only for the purpose of clearly illustrating the verification process of the invention and are not intended to limit the scope of the invention, which is defined by the claims, and all equivalent structural changes made by using the contents of the specification and the drawings of the present invention should be covered by the scope of the present invention.
Claims (5)
1. A silica-based cement-based porous material characterized by: the cement-based porous material is mainly prepared by uniformly mixing cement, an admixture, water, an additive and a silicon dioxide dispersion liquid, and then coagulating and hardening the mixture; wherein, the water cement ratio is 0.2-2, and the dosage of the admixture is 0-30% of the mass of the cement and the admixture; the silica dispersion is a dispersion system formed by dispersing silica particles in water;
the admixture is 0-99% of the total mass of cement and admixture, and the admixture is mainly any one or more of slag, fly ash, silica fume, expanding agent or fiber;
the admixture comprises any one or more of a water reducing agent, a shrinkage reducing agent, a retarder or an early strength admixture.
2. The cement-based porous material of claim 1, wherein: the dry density of the cement-based porous material is 50-1800kg/m3The porosity is 20-98%, the average pore diameter is 2-100nm, and the cumulative pore volume is 0.13-19.50 cc/g.
3. The cement-based porous material of claim 2, wherein: the dry density of the cement-based porous material is 700-1250kg/m3Porosity of 50-75%, average pore diameter of 25-35nm, cumulative pore volume of 0.45-1.45 cc/g; wherein the average pore diameter of the nano pores is 7-15nm, and the volume of the nano pores is 0.16-0.90 cc/g.
4. A method for the preparation of a cement-based porous material based on silica, for the preparation of a cement-based porous material according to any one of claims 1 to 3, characterized in that it comprises the following steps:
s1, adding the silicon dioxide powder into water, and dispersing the silicon dioxide in the water by adopting any one or more modes of mechanical stirring, ultrasonic dispersion, water reducing agent addition or surfactant addition to form a silicon dioxide dispersion liquid;
s2, weighing cement, admixture, water and admixture according to the proportion, and uniformly stirring to obtain a base material;
s3, mixing and stirring the prepared silicon dioxide dispersion liquid and a base material uniformly according to any ratio to prepare intermediate slurry;
and S4, forming and maintaining the intermediate slurry, and drying to obtain the cement-based porous material.
5. The method for preparing a silica-based cement-based porous material according to claim 4, characterized in that: the ratio of the silica dispersion liquid to the matrix material in the step S3 is calculated by a volume substitution method, wherein the volume substitution range of the silica dispersion liquid is 0-95% of the total volume of the cement-based porous material.
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