CN115806421A - Modified composite fiber reinforced alkali-reducing cement-based material system and preparation method thereof - Google Patents
Modified composite fiber reinforced alkali-reducing cement-based material system and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
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- 229910002804 graphite Inorganic materials 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
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- 239000006028 limestone Substances 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Hair brushThe invention discloses a modified composite fiber reinforced alkali-reducing cement-based material system and a preparation method thereof, wherein the system is prepared by mixing the following raw materials in percentage by weight: 45 to 75 percent of cement cementing material, 0.1 to 0.3 percent of modified composite fiber, 0.3 to 0.5 percent of high-efficiency drag reducer and 25 to 55 percent of alkali reducing protective agent, wherein the modified composite fiber comprises modified basalt fiber and modified glass fiber, and both the modified basalt fiber and the modified glass fiber adopt nano SiO 2 The fiber surface coating is modified by epoxy compounding. The cement-based material system prepared by the invention can improve the alkaline environment of the cement-based material and the alkali resistance of the fibers doped in the cement-based material to a great extent, and realize the effect of enhancing the long-term performance stability of the cement-based material by the fibers.
Description
Technical Field
The invention belongs to the technical field of cement-based cementing material application, and particularly relates to a modified composite fiber reinforced alkali-reducing cement-based material system and a preparation method thereof.
Background
As a brittle material, the cement has the defects of low tensile strength, low tensile strain limit and the like, and the addition of the fiber can obviously improve the mechanical properties of the cement-based cementing material, such as tensile strength, bending resistance, impact resistance, cracking resistance, toughness and the like. At present, more fibers are used for cement-based cementing materials, but none of the fibers can occupy a dominant position, and certain performance defects exist, such as easy rusting of steel fibers, high price of carbon fibers, low elastic modulus of synthetic fibers and the like.
Basalt fiber and glass fiber are used as an inorganic non-metallic material with excellent performance, have the advantages of high tensile strength, high temperature resistance, good acid and alkali resistance, relatively low price and the like, and are powerful competitors of carbon fiber. However, basalt fibers and glass fibers still have some problems in the application research of reinforced cement-based cementing materials, and the fibers are damaged due to chemical corrosion and physical etching generated by crystals when being in the cement-based materials for a long time, so that the later-stage tensile strength of the set cement is reduced and other mechanical properties are influenced. Therefore, the development of the modified fiber reinforced alkali-reducing cement-based material has important significance for further popularization and application.
In the prior art, for example, the invention patent with the publication number of CN114477913A and the patent name of 'an alkali-resistant basalt fiber mortar material and a preparation method thereof' discloses an alkali-resistant basalt fiber mortar material, which comprises the following components in parts by weight: 20-35 parts of silicate cement material, 10-25 parts of mineral admixture, 1-3 parts of alkali-resistant basalt fiber, 36-55 parts of spherical active aggregate, 0.1-0.5 part of graphite-based hydrophobic material and 1-2.5 parts of latex powder; the basalt fiber mortar can effectively solve the problem of poor impact resistance and wear resistance of the existing material. However, the material only carries out alkali resistance treatment on the basalt fiber and does not carry out alkali reduction treatment protection on the mortar material, so when the basalt fiber is in the mortar material for a long time, the basalt fiber still suffers from alkali corrosion, and the performance of the material is reduced. For another example, the patent of invention with publication number CN113443844a and patent name "a glass fiber cement" is disclosed, the glass fiber cement of the patent is composed of the following raw materials in parts by weight: 65-75 parts of limestone, 10-15 parts of clay, 0.5-1.5 parts of iron ore, 8.5-10.5 parts of coal, 1-3 parts of defoaming agent, 0.5-2.5 parts of early strength agent, 5-10 parts of glass fiber and 5-10 parts of synthetic fiber; the invention leads the cement stone to have higher tensile strength and bending strength limit strength by introducing the synthetic fiber into the glass fiber cement, particularly the toughness is greatly improved.
Therefore, the development of a modified fiber reinforced alkali-reducing cement-based material becomes a technical problem to be solved in the technical field.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a modified composite fiber reinforced alkali-reducing cement-based material system and a preparation method thereof, which aim to solve the technical problems.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a modified composite fiber reinforced alkali-reducing cement-based material system and a preparation method thereof are disclosed, which comprises the following raw materials in percentage by weight:
the modified composite fiber comprises modified basalt fiber and modified glass fiber, and both the modified basalt fiber and the modified glass fiber adopt nano SiO 2 The fiber surface coating is modified by epoxy compounding.
Further, the preparation of the modified composite fiber comprises the following steps:
step A, preparing deionized water, adding acetic acid to adjust the pH value to 3, then slowly dripping a silane coupling agent while stirring, and continuously stirring for 4 hours after dripping is finished until the silane coupling agent is completely hydrolyzed to obtain a silane aqueous solution;
step B, mixing the nano SiO 2 Mixing the emulsion with a silane water solution, and then stirring for 3 hours under the water bath condition of 50 ℃ to obtain a mixed solution; transferring the mixed solution to a water bath condition at 70 ℃, dropwise adding the film forming agent and the auxiliary film forming agent, stirring for 30min, adding the emulsifier, and continuously stirring until the solution is uniform;
step C, cooling to room temperature and stopping stirring to obtain a modified impregnating compound;
step D, mixing the basalt fibers or the glass fibers in a ratio of 1: and (3) putting the modified impregnating compound into the modified impregnating compound at a bath ratio of 10, stirring for 2 hours under the water bath condition of 50 ℃, naturally drying, putting into a dryer for drying, cooling at room temperature, sealing and storing to obtain the modified basalt fiber or the modified glass fiber.
Further, in the step B, the film forming agent is bisphenol A epoxy resin, the auxiliary film forming agent is water-soluble bisphenol A epoxy resin, and the emulsifier is a nonionic surfactant.
Further, in the step C, the solid content of the modified impregnating compound is 25wt%, the silane content is 0.06wt%, and the nano SiO is 2 The content is 4wt% and the addition amount of the emulsifier is 0.05wt%.
Further, the modified composite fiber comprises modified basalt fiber and modified glass fiber with the mass ratio of 1-2:1-2.
Further, the cement cementing material is one of portland cement, sulphoaluminate cement and slag sulphoaluminate cement.
Further, the high-efficiency drag reducer is one of a polycarboxylic acid high-efficiency drag reducer and a ketone-aldehyde condensation polymer drag reducer.
Further, the alkali-reducing protective agent is formed by mixing at least three of silica fume, ultrafine fly ash, slag, metakaolin, salt slurry and polysilicon byproducts.
Further, the silica fume is formed by acid treatment, and the acid treatment comprises the following steps: at room temperature, adding 6mol/L of excessive hydrochloric acid into a container containing silica fume, heating in water bath to 40 ℃, stirring for 3 hours to obtain a reaction mixture, neutralizing the reaction mixture with 2mol/L of NaOH solution until the pH value is 7, aging for 20 minutes, and finally filtering, washing, drying and grinding to more than 200 meshes.
Further, the specific surface area of the ultrafine fly ash is 600m 2 The 28d activity index was 96% per kg.
Compared with the prior art, the invention has the following beneficial effects:
the modified composite fiber reinforced alkali-reducing cement-based material system can improve the alkaline environment of the cement-based material and the alkali resistance of the fibers doped in the cement-based material to a great extent, namely, the effect of long-term performance stability of the fiber reinforced cement-based material is realized.
The invention adopts nano SiO 2 The fiber surface coating is modified by the modified impregnating compound which is subjected to flocculation treatment by the nonionic surfactant, and the impregnating compound has better storage stability, so that the modified composite fiber has higher surface energy, thereby showing the optimal interface bonding strength and having the effect of toughening for a long time in the impact-resistant cement-based cementing material; meanwhile, the modified impregnating compound acts on the surface of the fiber, and the mechanical property of the fiber is improved by repairing the defects on the surface of the fiber and wrapping the defects; the surface of the modified fiber is more compact, and Ca (OH) in a cement matrix is reduced 2 The probability of contact with the fiber itself, thereby improving the corrosion resistance of the fiber.
The alkali-reducing protective agent is added, so that the alkaline environment of the cement base material system in the hydration process is improved, the compression resistance of the modified composite fiber to cement mortar can be obviously prolonged,Aging of the flexural strength enhancing effect; meanwhile, the alkali protective agent material has certain potential activity, so that Ca (OH) in the system can be reduced to a certain degree 2 And the degree of corrosion of the fibers, and improves the interfacial properties between the fibers and the cement matrix.
The composite fiber can form a three-dimensional network structure in cement by being doped, so that the probability of generating internal cracks and defects of a cement matrix is reduced to a great extent, the mechanical property of the cement matrix is improved, and the long-term stability of a system is ensured.
Drawings
FIG. 1 is a microscopic view of a hydrated product of example 1 of the present invention.
FIG. 2 is a microscopic structure view of a hydration product of comparative example 1 of the present invention.
Figure 3 is a microstructure view of a comparative example 2 hydration product of the present invention.
Fig. 4 is a microscopic view of the hydration product of comparative example 3 of the present invention.
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 the accompanying drawings. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
As a preferred embodiment of the invention, the modified composite fiber reinforced alkali-reducing cement-based material system adopted in the implementation comprises the following raw materials in percentage by weight:
example 2
As a preferred embodiment of the invention, the modified composite fiber reinforced alkali-reducing cement-based material system adopted in the implementation comprises the following raw materials in percentage by weight:
example 3
As a preferred embodiment of the invention, the modified composite fiber reinforced alkali-reducing cement-based material system adopted in the implementation comprises the following raw materials in percentage by weight:
example 4
As a preferred embodiment of the invention, the modified composite fiber reinforced alkali-reducing cement-based material system adopted in the implementation comprises the following raw materials in percentage by weight:
example 5
As a preferred embodiment of the invention, the modified composite fiber reinforced alkali-reducing cement-based material system adopted in the implementation comprises the following raw materials in percentage by weight:
example 6
As a preferred embodiment of the invention, the modified composite fiber reinforced alkali-reducing cement-based material system adopted in the implementation comprises the following raw materials in percentage by weight:
example 7
As a preferred embodiment of the invention, the modified composite fiber reinforced alkali-reducing cement-based material system adopted in the implementation comprises the following raw materials in percentage by weight:
example 8
As a preferred embodiment of the invention, the modified composite fiber reinforced alkali-reducing cement-based material system adopted in the implementation comprises the following raw materials in percentage by weight:
in examples 1 to 8, the modified basalt fiber and the modified glass fiber were prepared by the method for preparing the modified composite fiber, and the silica fume was treated with the acid.
Comparative example 1
The cement-based material system adopted by the comparative example is prepared by mixing the following raw materials in percentage by weight:
99.7 percent of Portland cement;
0.3 percent of basalt fiber.
Comparative example 2
The cement-based material system adopted by the comparative example is prepared by mixing the following raw materials in percentage by weight:
99.7 percent of sulphoaluminate cement;
0.3 percent of basalt fiber.
Comparative example 3
The cement-based material system adopted by the comparative example is prepared by mixing the following raw materials in percentage by weight:
99.8 percent of slag sulphoaluminate cement;
0.1% of basalt fiber;
0.1 percent of glass fiber.
The modified composite fiber reinforced alkali-reducing cement-based material systems of examples 1-4 and the cement-based material systems of comparative examples 1-3 are tested by referring to the GB/T50081-2002 standard of the test method of the mechanical property of the common concrete, the performance test results are shown in Table 1, and the microstructures of the examples 1 and the comparative examples 1-3 are respectively shown in FIGS. 1-4.
TABLE 1
Remarking: wherein the curing temperatures of examples 1 to 4 and comparative examples 1 to 3 were 90 ℃ and the curing pressures were 20.7MPa.
As can be seen from table 1 and fig. 1, the systems of examples 1 to 4, in which the modified fibers were incorporated, had significantly superior mechanical properties after curing for 28d, and no corrosion mark was found in the microstructure of the hydration product of the system of example 1; as can be seen from table 1 and fig. 2-4, the systems of comparative example 1-comparative example 3, in which unmodified fibers were incorporated, had significantly reduced mechanical property parameters after curing for 28d compared to those of examples 1-example 4, and corrosion marks were observed on the fiber surface in the hydration product microstructure of the systems of comparative example 1-comparative example 3.
Therefore, the modified composite fiber reinforced alkali-reducing cement-based material system can greatly improve the alkaline environment of the cement-based material and the alkali resistance of the fibers doped in the cement-based material, and realize the effect of long-term performance stability of the fiber reinforced cement-based material.
Finally, it should be noted that: the above embodiments are only preferred embodiments of the present invention to illustrate the technical solutions of the present invention, but not to limit the technical solutions, and certainly not to limit the patent scope of the present invention; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention; that is, the technical problems to be solved by the present invention, which are not substantially changed or supplemented by the spirit and the concept of the main body of the present invention, are still consistent with the present invention and shall be included in the scope of the present invention; in addition, the technical scheme of the invention is directly or indirectly applied to other related technical fields, and the technical scheme is included in the patent protection scope of the invention.
Claims (10)
1. A modified composite fiber reinforced alkali-reducing cement-based material system and a preparation method thereof are characterized by comprising the following raw materials in percentage by weight:
the modified composite fiber comprises modified basalt fiber and modified glass fiber, and both the modified basalt fiber and the modified glass fiber adopt nano SiO 2 The fiber surface coating is modified by epoxy compounding.
2. The modified composite fiber reinforced alkali-reducing cement-based material system and the preparation method thereof according to claim 1, wherein the preparation of the modified composite fiber comprises the following steps:
step A, preparing deionized water, adding acetic acid to adjust the pH value to 3, then slowly dripping a silane coupling agent while stirring, and continuously stirring for 4 hours after dripping is finished until the silane coupling agent is completely hydrolyzed to obtain a silane aqueous solution;
step B, mixing the nano SiO 2 Mixing the emulsion with an aqueous silane solution, and stirring the mixture in a water bath at 50 DEG CStirring for 3h to obtain a mixed solution; transferring the mixed solution to a water bath condition at 70 ℃, dropwise adding the film forming agent and the auxiliary film forming agent, stirring for 30min, adding the emulsifier, and continuously stirring until the solution is uniform;
step C, cooling to room temperature and stopping stirring to obtain a modified impregnating compound;
step D, mixing the basalt fibers or the glass fibers in a ratio of 1: and (3) putting the modified impregnating compound into the modified impregnating compound at a bath ratio of 10, stirring for 2 hours under the water bath condition of 50 ℃, naturally drying, putting into a dryer for drying, cooling at room temperature, sealing and storing to obtain the modified basalt fiber or the modified glass fiber.
3. The modified composite fiber reinforced alkali-reducing cement-based material system and the preparation method thereof as claimed in claim 2, wherein in said step B, the film forming agent is bisphenol A epoxy resin, the auxiliary film forming agent is water-soluble bisphenol A epoxy resin, and the emulsifier is nonionic surfactant.
4. The modified composite fiber reinforced alkali-reducing cement-based material system as claimed in claim 2, wherein in the step C, the solid content of the modified impregnating compound is 25wt%, the silane content is 0.06wt%, and the nano SiO is added 2 The content is 4wt% and the addition amount of the emulsifier is 0.05wt%.
5. The modified composite fiber reinforced alkali-reducing cement-based material system and the preparation method thereof as claimed in claim 1, wherein the modified composite fiber comprises modified basalt fiber and modified glass fiber in a mass ratio of 1-2:1-2.
6. The modified composite fiber reinforced alkali-reducing cement-based material system and the preparation method thereof as claimed in claim 1, wherein the cement gelling material is one of portland cement, sulphoaluminate cement, and slag sulphoaluminate cement.
7. The modified composite fiber reinforced alkali-reducing cement-based material system and the preparation method thereof according to claim 1, wherein the high-efficiency drag reducer is one of polycarboxylic acid high-efficiency drag reducers and ketone-aldehyde condensation polymer drag reducers.
8. The modified composite fiber reinforced alkali-reducing cement-based material system and the preparation method thereof as claimed in claim 1, wherein the alkali-reducing protective agent is formed by mixing at least three of silica fume, ultrafine fly ash, slag, metakaolin, salt slurry and polysilicon by-products.
9. The modified composite fiber reinforced alkali-reducing cement-based material system and the preparation method thereof as claimed in claim 8, wherein the silica fume is obtained by acid treatment, the acid treatment comprises: at room temperature, adding 6mol/L of excessive hydrochloric acid into a container containing silica fume, heating in water bath to 40 ℃, stirring for 3 hours to obtain a reaction mixture, neutralizing the reaction mixture with 2mol/L of NaOH solution until the pH value is 7, aging for 20 minutes, and finally filtering, washing, drying and grinding to more than 200 meshes.
10. The modified composite fiber reinforced alkali-reducing cement-based material system as claimed in claim 8, wherein the specific surface area of the ultrafine fly ash is 600m 2 The 28d activity index was 96% per kg.
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| WO2009135279A2 (en) * | 2008-05-09 | 2009-11-12 | Biobrasil Consultoria E Representções Ltda | Manufacturing process of fiber-cement composite materials using portland cement reinforced with inorganic fibers chemically modified by organoselanes |
| CN105541209A (en) * | 2015-12-21 | 2016-05-04 | 中民筑友有限公司 | Basalt fiber reinforced cement based material and preparation method therefor |
| CN111138093A (en) * | 2019-12-17 | 2020-05-12 | 北京中创时代科技有限公司 | SiO for basalt fiber composite rib2Nanoparticle modified thermosetting impregnating compound and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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