CN111116095B - Autotrophic cement-based material solid air entraining agent and preparation method and application thereof - Google Patents
Autotrophic cement-based material solid air entraining agent and preparation method and application thereof Download PDFInfo
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- CN111116095B CN111116095B CN202010006041.7A CN202010006041A CN111116095B CN 111116095 B CN111116095 B CN 111116095B CN 202010006041 A CN202010006041 A CN 202010006041A CN 111116095 B CN111116095 B CN 111116095B
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- cement
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- absorbent resin
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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
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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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/304—Air-entrainers
Abstract
The invention discloses an autotrophic cement-based material solid air entraining agent, a preparation method and application thereof, belongs to the field of building materials, and aims to solve the problems that the existing cement-based composite material has weak capability of resisting freeze-thaw cycle damage and the cement-based material shrinks due to water loss. The autotrophic cement-based material solid air entraining agent comprises 1-20% of high molecular water-absorbent resin and 80-99% of hydrophobic treatment agent by mass, wherein the high molecular water-absorbent resin is polyacrylate high molecular water-absorbent resin, polyamide high molecular water-absorbent resin or mixed resin of the polyacrylate high molecular water-absorbent resin and the polyamide high molecular water-absorbent resin, and the hydrophobic treatment agent is sodium stearate saturated solution or water-soluble organic silicon solution. The autotrophic solid air entraining agent forms approximately spherical pores with the diameter less than 300 microns in uniform distribution in the cement-based composite material, improves the frost resistance of the cement-based composite material, and has a self-curing function.
Description
Technical Field
The invention belongs to the field of building materials, and particularly relates to a cement-based composite material solid air entraining agent with a self-curing function, and a preparation method and application thereof.
Background
Freeze-thaw cycle failure is a common failure mode of cement-based composites, and freeze resistance is a major and important property of cement-based composites. Although not fully explaining all of the failure phenomena, hydrostatic and osmotic theories are currently the generally accepted freeze-thaw cycle failure mechanisms. The spherical micropores artificially introduced into the cement-based composite material can be used as spaces for releasing hydrostatic pressure and osmotic pressure, and is the most effective method for improving the frost resistance. For example, chemical air entraining agents are incorporated during the mixing of cement concrete, and the surface activity of the chemical air entraining agents is utilized to reduce the surface tension of mixing water, so that a large number of tiny, stable and closed bubbles are generated in the concrete. It is generally considered that when the air content of fresh concrete reaches 4% to 5%, and the coefficient of the distance between air bubbles in hardened concrete is less than 250 μm, the concrete has sufficient frost resistance. Therefore, the air entraining agent is used as an indispensable additive of the cement-based composite material in a large amount in practical engineering, particularly in areas with severe environmental and climatic conditions. However, the chemical air-entraining agent has the following problems in addition to the improvement of the frost resistance.
The mixing amount of the chemical air entraining agent and the air content of the cement-based mixture have no determined corresponding relationship. During the stirring process of the cement-based composite material, a plurality of factors influence the gas content: the adsorption capacity of various raw materials to the chemical air entraining agent is different, and the variety and the dosage of the raw materials directly influence the mixing amount of the air entraining agent; the fluidity and viscosity of the cement-based mixture also influence the difficulty of generating bubbles; the mixing amount of the chemical air entraining agent is generally very small, about 0.01-0.1 percent of the dosage of the cementing material, and the mixing sequence and the mixing mode have certain influence on the air content of the cement-based material; in addition, the stirring manner, the stirring time, the stirring temperature and the like also influence the gas content of the cement-based material. The air content in the cement-based material cannot be quantitatively controlled by a direct method, and can only be indirectly controlled by adjusting the variety and the doping amount of the chemical air entraining agent, the air content is easy to fluctuate in a large range, once the air content is lower than a design value, the frost resistance of the cement-based composite material is insufficient, and the strength is greatly reduced due to the overhigh air content.
The air content of the mixture introduced by the chemical air entraining agent cannot ensure the air content, the bubble spacing coefficient and the frost resistance of the hardened cement-based composite material. Even though the mixing amount of the chemical air entraining agent can be adjusted through a large number of tests to generate enough air content in the mixture, the air bubbles can still have the phenomena of aggregation, floating, cracking and the like in different degrees in the construction processes of transportation, pouring, vibration, trowelling and the like, so that the air content is lost, and further the air content in the hardened cement-based material is reduced, and the size of the air bubbles and the space coefficient of the air bubbles are increased.
The crack problem of the cement-based material is a hot spot and a difficulty in engineering, the crack is generated due to a plurality of reasons, and the shrinkage of the cement-based material is one of the reasons. The root cause of shrinkage of cement-based materials is the consumption (hydration) and dissipation (evaporation) of water within them. The self-maintenance material can absorb water in advance, gradually release the water in the cement hydration process, reduce the shrinkage of the cement-based material and provide an effective technical means for solving the problem of cracks of the cement-based material.
Disclosure of Invention
The invention aims to solve the problems that the existing cement-based composite material has weak capability of resisting freeze-thaw cycle damage and the cement-based material shrinks due to dehydration, and provides an autotrophic cement-based material solid air-entraining agent, and a preparation method and application thereof.
The autotrophic cement-based material solid air entraining agent comprises 1-20% of high molecular water-absorbent resin and 80-99% of hydrophobic treatment agent by mass, wherein the high molecular water-absorbent resin is polyacrylate high molecular water-absorbent resin, polyamide high molecular water-absorbent resin or mixed resin of the polyacrylate high molecular water-absorbent resin and the polyamide high molecular water-absorbent resin, and the hydrophobic treatment agent is sodium stearate saturated solution or water-soluble organic silicon solution.
The preparation method of the autotrophic cement-based material solid air entraining agent is realized according to the following steps:
preparing a water-soluble organic silicon solution or a sodium stearate saturated solution with the mass concentration of 10-30% to obtain a hydrophobic treatment agent, uniformly dispersing high-molecular water-absorbent resin into the hydrophobic treatment agent, standing, and absorbing the hydrophobic treatment agent by the high-molecular water-absorbent resin to obtain an autotrophic cement-based material solid air-entraining agent;
wherein the high molecular water-absorbing resin is polyacrylate high molecular water-absorbing resin, polyamide high molecular water-absorbing resin or a mixed resin of the polyacrylate high molecular water-absorbing resin and the polyamide high molecular water-absorbing resin.
The application of the autotrophic cement-based material solid air entraining agent is that the autotrophic cement-based material solid air entraining agent is directly added or added along with mixing water in the stirring process when the cement-based composite material is used.
The invention provides a solid air-entraining agent with a self-curing function and a preparation method thereof, which can quantitatively control the air content of a cement-based material mixture without loss, and simultaneously has the self-curing function, can release water contained in particles, promote the hydration of cement around the particles, reduce the shrinkage of a cement-based composite material and reduce the risk of cracking. The autotrophic solid air entraining agent forms approximately spherical pores with the diameter less than 300 mu m in the cement-based composite material, and the approximately spherical pores are uniformly distributed, so that the frost resistance of the cement-based composite material is improved. Meanwhile, the cement-based composite material has a self-maintenance function, improves the early cement hydration degree of the set cement, can improve the relative humidity inside the cement-based composite material by 5-15%, and reduces the self-shrinkage at the 3d age by 20-60%.
The invention has greater superiority to the engineering which has frost resistance requirement and is in the area where water resources are deficient or can not be maintained by the conventional method.
Drawings
FIG. 1 is a graph showing a pore structure test of set cement in an example of use, wherein ■ represents a blank group,. smallcircle represents a dry-doped group,. ● represents a pre-imbibition sodium stearate saturated solution group,. lambada represents a pre-imbibition silicone solution group;
FIG. 2 is a self-shrinkage test chart of cement-based materials in an application example, wherein O represents a blank reference group, and A-solidup represents a pre-absorption sodium stearate saturated solution group.
Detailed Description
The first embodiment is as follows: the autotrophic cement-based material solid air entraining agent comprises, by mass, 1% -20% of a high-molecular water-absorbent resin and 80% -99% of a hydrophobic treatment agent, wherein the high-molecular water-absorbent resin is a polyacrylate high-molecular water-absorbent resin, a polyamide high-molecular water-absorbent resin or a mixed resin of the polyacrylate high-molecular water-absorbent resin and the polyamide high-molecular water-absorbent resin, and the hydrophobic treatment agent is a sodium stearate saturated solution or a water-soluble organic silicon solution.
The solid air entraining agent with the self-curing function in the embodiment is composed of a high-molecular water-absorbent resin component and a hydrophobic component.
The second embodiment is as follows: the difference between the present embodiment and the present embodiment is that the water absorption rate of the polymeric water-absorbent resin is (10 to 1000) g/g.
The third concrete implementation mode: the present embodiment is different from the first or second embodiment in that the average diameter of the dry particles of the water-absorbent polymer resin is 30 to 200. mu.m.
The fourth concrete implementation mode: the embodiment is different from the first to the third embodiment in that the autotrophic cement-based material solid air entraining agent consists of 1 to 5 mass percent of high molecular water-absorbing resin and 95 to 99 mass percent of hydrophobic treatment agent.
The fifth concrete implementation mode: the preparation method of the autotrophic cement-based material solid air entraining agent is implemented according to the following steps:
preparing a water-soluble organic silicon solution or a sodium stearate saturated solution with the mass concentration of 10-30% to obtain a hydrophobic treatment agent, uniformly dispersing high-molecular water-absorbent resin into the hydrophobic treatment agent, standing, and absorbing the hydrophobic treatment agent by the high-molecular water-absorbent resin to obtain an autotrophic cement-based material solid air-entraining agent;
wherein the high molecular water-absorbing resin is polyacrylate high molecular water-absorbing resin, polyamide high molecular water-absorbing resin or a mixed resin of the polyacrylate high molecular water-absorbing resin and the polyamide high molecular water-absorbing resin.
The water for preparing the hydrophobic treatment agent in the embodiment may be: drinking water, distilled water, deionized water and mixing water which meets the relevant standard and can be used for cement-based composite materials.
The preparation method of the solid air entraining agent is simple and convenient, and after material selection, the high molecular water-absorbent resin is uniformly dispersed into the hydrophobic treatment agent for pre-water absorption treatment and hydrophobic treatment.
The cement-based composite material solid air entraining agent with the self-curing function can release water pre-absorbed by the solid air entraining agent in the hydration process of the cement-based material, and the part of water can play a self-curing role, so that the internal relative humidity of the cement-based material is improved, and the self-shrinkage of the cement-based material is reduced.
The sixth specific implementation mode: the difference between this embodiment and the fifth embodiment is that the average particle size of the high molecular weight water absorbent resin after the standing treatment is increased by 2 to 5 times.
The seventh embodiment: the fifth or sixth embodiment is different from the fifth or sixth embodiment in that the standing treatment is carried out until the average particle diameter of the high molecular water absorbent resin becomes 200 to 300. mu.m.
The specific implementation mode is eight: the application of the autotrophic cement-based material solid air entraining agent in the embodiment is that the autotrophic cement-based material solid air entraining agent is directly added or added along with mixing water in the stirring process when the cement-based composite material is used.
The internal curing effect of the self-curing cement-based material solid air entraining agent can improve the internal relative humidity of the cement-based material and reduce self-shrinkage.
The specific implementation method nine: the difference between the embodiment and the eighth embodiment is that the volume mixing amount of the autotrophic cement-based material solid air entraining agent is 2.0-6.0% of the volume of the cement-based composite material.
The first embodiment is as follows: the preparation method of the autotrophic cement-based material solid air entraining agent of the embodiment is implemented according to the following steps:
preparing a saturated solution of sodium stearate to obtain a hydrophobic treatment agent, uniformly dispersing 100g of polyacrylate type high molecular water-absorbing resin with dry particles and particle size range of 70-87 mu m into 6.0kg of hydrophobic treatment agent, and fully and uniformly stirring to obtain the autotrophic cement-based material solid air-entraining agent.
The autotrophic cement-based material solid air entraining agent in the embodiment comprises 1.64% of high molecular water absorbent resin and 98.36% of hydrophobic treatment agent by mass.
Example two: the difference between the embodiment and the first embodiment is that the hydrophobic treatment agent is water-soluble organic silicon solution.
The application example is as follows: in this example, the solid air entraining agent of the autotrophic cement-based material prepared as described above was incorporated in an amount of 4.8% by volume of the cement-based composite material.
The pore structure of the solid air entraining agent, namely the cement stone, of the autotrophic cement-based material obtained in the embodiment is detected by a mercury intrusion method, and the result shows that a large number of pores with the diameter of 10-100 microns are formed in the cement stone, as shown in fig. 1, wherein the dry doping group is formed by only doping the macromolecular water-absorbing resin and is not treated by the hydrophobic treatment agent. After the age of 1d, the hydration degree of the set cement is accelerated, and after 7d, the set cement tends to be stable.
The frost resistance of the cement concrete doped with the autotrophic cement-based material solid air entraining agent is obviously improved, and the maximum freeze-thaw resistance cycle times are increased from 60 times to 130 times compared with that of the undoped hollow concrete. The self-shrinkage value at 3d was reduced by 50% compared to the unblended white concrete, as shown in fig. 2.
Claims (8)
1. The autotrophic cement-based material solid air entraining agent is characterized by comprising 1-5% of macromolecular water-absorbent resin and 95-99% of hydrophobic treatment agent by mass, wherein the macromolecular water-absorbent resin is polyacrylate macromolecular water-absorbent resin, polyamide macromolecular water-absorbent resin or mixed resin of the polyacrylate macromolecular water-absorbent resin and the polyamide macromolecular water-absorbent resin, and the hydrophobic treatment agent is sodium stearate saturated solution or water-soluble organic silicon solution.
2. The autotrophic cement-based material solid air entraining agent according to claim 1, wherein the water absorption of the polymeric water absorbent resin is (10-1000) g/g.
3. The autotrophic cement-based material solid air entraining agent according to claim 1, wherein the average diameter of the dry particles of the high molecular water-absorbent resin is 30 μm to 200 μm.
4. The method for preparing the autotrophic cement-based material solid air entraining agent according to claim 1, characterized in that the method is implemented by the following steps:
preparing a water-soluble organic silicon solution or a sodium stearate saturated solution with the mass concentration of 10-30% to obtain a water repellent agent, uniformly dispersing high-molecular water-absorbent resin into the water repellent agent, standing, and absorbing the water repellent agent by the high-molecular water-absorbent resin to obtain an autotrophic cement-based material solid air entraining agent;
wherein the high molecular water-absorbing resin is polyacrylate high molecular water-absorbing resin, polyamide high molecular water-absorbing resin or a mixed resin of the polyacrylate high molecular water-absorbing resin and the polyamide high molecular water-absorbing resin.
5. The method for preparing the autotrophic cement-based material solid air entraining agent according to claim 4, wherein the average particle size of the high molecular weight water-absorbent resin is increased by 2-5 times after the standing treatment.
6. The method for producing an autotrophic cement-based material solid air entraining agent according to claim 4, wherein the standing treatment is carried out until the average particle diameter of the high molecular weight water-absorbent resin becomes 200 to 300. mu.m.
7. The use of the solid air entraining agent for an autotrophic cement-based material according to claim 1, wherein the solid air entraining agent is added directly or with the mixing water during the mixing process when the cement-based composite material is used.
8. The use of the solid air entraining agent for the autotrophic cement-based material according to claim 7, wherein the solid air entraining agent for the autotrophic cement-based material is present in an amount of 2.0-6.0% by volume of the cement-based composite material.
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| CN112125556A (en) * | 2020-10-15 | 2020-12-25 | 哈尔滨工业大学 | Cement concrete solid air entraining agent and preparation method and application thereof |
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| CN107188479A (en) * | 2017-07-14 | 2017-09-22 | 江苏中路工程技术研究院有限公司 | A kind of cement stabilized macadam base material based on health in super moisture absorbing resin and preparation method thereof |
| CN107382210A (en) * | 2017-08-24 | 2017-11-24 | 重庆三圣实业股份有限公司 | A kind of high flowability concrete and preparation method thereof and application method |
| CN108794063A (en) * | 2018-07-27 | 2018-11-13 | 刘翠芬 | Concrete autogenous curing agent and preparation method thereof and application method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107188479A (en) * | 2017-07-14 | 2017-09-22 | 江苏中路工程技术研究院有限公司 | A kind of cement stabilized macadam base material based on health in super moisture absorbing resin and preparation method thereof |
| CN107382210A (en) * | 2017-08-24 | 2017-11-24 | 重庆三圣实业股份有限公司 | A kind of high flowability concrete and preparation method thereof and application method |
| CN108794063A (en) * | 2018-07-27 | 2018-11-13 | 刘翠芬 | Concrete autogenous curing agent and preparation method thereof and application method |
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