CN113354370A - Preparation method of concrete based on anti-corrosion reinforced fibers - Google Patents

Preparation method of concrete based on anti-corrosion reinforced fibers Download PDF

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CN113354370A
CN113354370A CN202110863146.9A CN202110863146A CN113354370A CN 113354370 A CN113354370 A CN 113354370A CN 202110863146 A CN202110863146 A CN 202110863146A CN 113354370 A CN113354370 A CN 113354370A
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concrete
powder
coupling agent
ceramic
waste
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CN113354370B (en
Inventor
马军委
吴俊�
张涛
张慧明
张钱平
叶璐
吴宇超
金兴国
黄侃
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Guangming Railroad Holding Co ltd
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions 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
    • C04B28/04Portland cements
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00241Physical properties of the materials not provided for elsewhere in C04B2111/00
    • C04B2111/00293Materials impermeable to liquids
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20Resistance against chemical, physical or biological attack
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/91Use of waste materials as fillers for mortars or concrete

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention relates to the technical field of concrete preparation, in particular to a preparation method of concrete based on anti-corrosion reinforced fibers3C2The powder and KH550 are used for modifying basalt fibers to obtain anticorrosion reinforced fibers, and then the anticorrosion reinforced fibers are compounded with ceramic powder, cement, sand, gravel and water which are modified by a fluorosilane coupling agent, and the mixture is uniformly stirred to obtain the concrete. The preparation method of the concrete is simple and easy to operate, and does not contain the addition of iron powder and other substances.

Description

Preparation method of concrete based on anti-corrosion reinforced fibers
Technical Field
The invention relates to the technical field of concrete preparation, in particular to a preparation method of concrete based on anticorrosion reinforcing fibers.
Background
Concrete is a generic term for engineering composites where aggregates are cemented into a whole by cementitious materials. The term concrete generally refers to cement as the cementing material and sand and stone as the aggregate; the cement concrete, also called as common concrete, is obtained by mixing with water (which may contain additives and admixtures) according to a certain proportion and stirring, and is widely applied to civil engineering. The concrete has the characteristics of rich raw materials, low price and simple production process, so that the consumption of the concrete is increased more and more. Meanwhile, the concrete also has the characteristics of high compressive strength, good durability, wide strength grade range and the like. These characteristics make it very widely used, not only in various civil engineering, that is shipbuilding, machinery industry, ocean development, geothermal engineering, etc., but also concrete is an important material.
The concrete has various types, for example, the Chinese patent with the publication number of CN101186471B discloses a concrete, and each cubic meter of the concrete comprises: 390-450 kg of cement, 695-730 kg of sand, 1035-1050 kg of stone, 190-200 kg of water, 60-70 kg of fly ash, 50-60 kg of UEA concrete expanding agent, 6.5-7.35 kg of SP403 pumping agent and 0.6-0.7 kg of Gray fiber; the concrete has good workability, plasticity and pumpability effect, and can effectively prevent the problem that the concrete in an overlong concrete structure is easy to crack.
The Chinese patent with the publication number of CN107489166B discloses a construction process of an anti-seepage corrosion-resistant precast concrete culvert, which solves the problem of seepage caused by deformation of a cold-proof joint and increases the anti-seepage effect of the joint by coating epoxy asphalt paint on the outer surface of the culvert and adding non-curing sizing material at the joint between adjacent culverts, and has the advantages of simple process, simple structure, strong anti-seepage capability, high corrosion resistance and the like. However, the epoxy asphalt paint is coated on the outer surface of the square culvert, the original anti-corrosion effect cannot be achieved due to the construction process, the paint falls off after long-term service and the like, the growth of microorganisms at the falling position of the paint can cause cracks and holes of the concrete square culvert, the defects are expanded, the invasion of the microorganisms is facilitated, and the strength of a concrete structure is threatened.
The above background disclosure is only for the purpose of assisting understanding of the inventive concept and technical solutions of the present invention, and does not necessarily belong to the prior art of the present patent application, and should not be used for evaluating the novelty and inventive step of the present application in the case that there is no clear evidence that the above content is disclosed at the filing date of the present patent application.
Disclosure of Invention
Technical problem to be solved
The invention aims to solve at least one technical problem in the background art, and provides a preparation method of concrete based on anti-corrosion reinforced fibers, which is simple and easy to operate, does not contain the addition of substances such as iron powder and the like, and has the advantages of high strength, strong mildew and algae prevention capability, high anti-permeability registration, low density and the like.
(II) technical scheme
In order to solve the above technical problems or achieve the above technical objects, the present invention provides the following aspects.
In a first aspect, a method of making an anti-corrosion reinforcing fiber, comprises:
1)Ti3AlC2fully grinding the powder, adding the powder into 35-40 vol% hydrofluoric acid solution in batches under stirring, performing ultrasonic treatment for at least 6 hours, and reacting at 35-40 ℃ for at least 48 hours; centrifuging for many times, washing with distilled water until pH is not lower than 6, adding distilled water, ultrasonic dispersing, vacuum filtering, and drying to obtain Ti3C2Powder;
2) ti of step 1)3C2Adding the powder and KH550 into 50-75% vol ethanol solution to obtain modifier, Ti3C2The content is not higher than 1 percent, and the content of KH550 is not higher than 4 percent; placing basalt fibers into a modifier according to the material-liquid ratio of 1: 20-50, stirring and modifying at the temperature of 35-40 ℃ for at least 30min, taking out, and drying to obtain the composite materialAnd (4) decomposing and reinforcing fibers.
According to a specific embodiment, the method for preparing the corrosion-resistant reinforcing fiber comprises at least one of the following features:
-wherein the stirring rate of step 1) is 1200-3000 r/min;
-wherein the amount of hydrofluoric acid solution of step 1) is Ti3AlC235-50 times of the weight of the powder;
-wherein the frequency of the ultrasound in the step 1) is 60-100 KHz, and the ultrasound density is 0.6-0.8W/cm2
-wherein said step 1) drying means drying to constant weight at a temperature not higher than 50 ℃;
-wherein said step 2) Ti3C2The weight ratio of the powder to the KH550 is 1: 1.5-3.0;
-wherein the stirring rate of the stirring modification in the step 2) is 300-900 r/min;
-wherein said step 2) drying means drying to constant weight at a temperature not higher than 50 ℃.
In the present invention, first, Ti is used3AlC2Powder preparation of Ti3C2The powder and KH550 are added into the basalt fiber according to a specific ratio to modify the basalt fiber, so as to prepare the anti-corrosion reinforced fiber, the preparation method is simple, the modified anti-corrosion reinforced fiber is combined to be added into concrete, the concrete can be endowed with excellent impermeability and antibacterial and mildewproof effects, the mildewproof and algae-proof capability of the concrete can be obviously improved, the corrosion of various microorganisms to a concrete structure can be effectively inhibited in practical application, the concrete structure can keep excellent structural strength, and the possible mechanisms comprise: during the modification at low temperature, part of Ti3C2Is oxidized to TiO2Has certain antibacterial and mildewproof effects, and the addition of KH550 can accelerate the addition of Ti3C2Is oxidized to TiO2In addition, compared with the smooth appearance of basalt fiber, the surface of the basalt fiber is coated with KH550 and Ti3C2The combined modified anticorrosion reinforcing fiber forms a large amount of Si-O groups and Ti on the surface3C2The particles can obviously improve the roughness of the surface of the basalt fiberAfter the anti-mildew and anti-algae agent is applied to concrete, the anti-mildew and anti-algae agent is beneficial to the bonding strength with other components, further improves the compactness of the concrete, prevents cracks, and improves the anti-mildew and anti-algae capability and the anti-permeability performance of a concrete structure.
In a second aspect, the anticorrosion reinforcing fiber prepared by the method of the first aspect is applied to concrete.
In a third aspect, a method for preparing a concrete based on anti-corrosion reinforced fibers comprises the following steps:
1) preparing a corrosion-resistant reinforcing fiber according to the method of the first aspect;
2) modifying the waste ceramic powder with a fluorosilane coupling agent to obtain modified ceramic powder;
3) adding fly ash into cement, mixing uniformly, adding anticorrosive reinforcing fiber and modified ceramic powder, compounding cement, sand, broken stone and water according to a conventional ratio, and stirring uniformly to obtain the cement.
According to a specific embodiment, the concrete based on the anticorrosion reinforcing fiber comprises the following components in parts by weight:
Figure BDA0003186509310000031
according to a specific embodiment, the modified ceramic powder is obtained by modifying waste ceramic powder with a fluorosilane coupling agent shown in formula (1).
Figure BDA0003186509310000032
According to a specific embodiment, the modified ceramic powder is prepared by modifying the waste ceramic powder with a fluorosilane coupling agent, and comprises the following specific steps:
1) cleaning, crushing, ball-milling and drying the waste ceramics to obtain ceramic particles with the particle size not higher than 3 mm;
2) adjusting the pH value of 75-90 vol% ethanol solution to 4-5 to obtain dispersion liquid, adding a fluorosilane coupling agent into the dispersion liquid according to 0.001-0.05 per mill of the weight of the ceramic particles, and uniformly dispersing to obtain fluorosilane coupling agent solution;
3) and (3) uniformly spraying the fluorosilane coupling agent solution obtained in the step 2) on the surface of the ceramic particles under stirring at room temperature, drying at 45-55 ℃ to constant weight, and grinding until the granularity is not higher than 0.5 mm.
According to a more specific embodiment, the step of modifying the waste ceramic powder with a fluorosilane coupling agent to produce a modified ceramic powder includes at least one of the following features:
-wherein the step 1) scrap ceramic comprises:
such as various ceramic crafts, waste life ceramics of daily application ceramics and the like,
such as waste building ceramics of floor tiles, wall tiles, structural bricks and the like,
other ceramics such as ceramic semi-finished products, electrical insulating ceramics, chemical ceramics, and the like;
-wherein the pH of the dispersion of step 2) can be adjusted with acetic acid;
-wherein, the step 2) is uniformly dispersed, which means at 20-50 KHz, 0.3-0.6W/cm2Ultrasonic dispersion for at least 1h under the condition;
-wherein the stirring frequency of the step 3) is 60-300 r/min.
In the technical scheme of the invention, the waste ceramic is modified by applying the fluorosilane coupling agent shown in the formula (1) to prepare modified waste ceramic powder, the modified waste ceramic powder is added into concrete, after the concrete is formed, silicon oxygen groups are hydrolyzed to generate silicon alcohol groups, further form hydrogen bond with the surface of the inorganic substrate or condense with active groups such as hydroxyl to form-SiO-M covalent bond (M is inorganic surface), the adhesive effect of the ceramic powder and other components such as cement, fibers and the like can be remarkably improved, the mechanical strength of concrete is remarkably improved, the hydrophobicity of the concrete is further improved by the elimination effect of the modification of the fluorosilane coupling agent on the surface hydroxyl of the inorganic material, the local agglomeration phenomenon of the concrete is reduced, the density uniformity of the formed solid concrete is higher, the surface energy of the concrete can be remarkably reduced by the introduction of the fluorosilane coupling agent, and the self-cleaning performance and the mildew and algae prevention performance are improved.
According to a more specific embodiment, the cement may be selected from ordinary portland cements.
According to a more specific embodiment, the fly ash has a particle size of 80-200 mesh.
According to a more specific embodiment, the concrete based on the anticorrosion reinforcing fiber can be added with 5-10 parts by weight of a water reducing agent such as a polycarboxylic acid water reducing agent and 5-10 parts by weight of a water repellent agent such as an organosilicon solid water repellent agent per 100 parts by weight of cement.
The core of the technical scheme of the invention is Ti3C2The powder and KH550 participate in modification of basalt fiber according to a specific proportion to obtain anticorrosion reinforcing fiber, and the anticorrosion reinforcing fiber is added into concrete, so that excellent impermeability and antibacterial and mildewproof effects can be given to the concrete, the mildewproof and algae-proof capabilities of the concrete can be remarkably improved, the corrosion of various microorganisms to a concrete structure can be effectively inhibited in practical application, the modification is favorable for the bonding strength of the anticorrosion reinforcing fiber and other components, the compactness of the concrete is further improved, the generation of cracks is prevented, the mildewproof and algae-proof capabilities and the impermeability of the concrete structure are improved, and the excellent structural strength is kept; secondly, the bonding effect of the ceramic powder and other components such as cement, fibers and the like can be remarkably improved after the waste ceramic is modified by the fluorosilane coupling agent, the mechanical strength of concrete is remarkably improved, the hydrophobicity of the concrete is further improved by the elimination effect of the modification of the fluorosilane coupling agent on the surface hydroxyl of the inorganic material, the local agglomeration phenomenon of the concrete is reduced, the density uniformity of the formed solid concrete is higher, the surface energy of the concrete can be remarkably reduced by the introduction of the fluorosilane coupling agent, and the self-cleaning performance and the mildew and algae prevention capabilities are improved; thirdly, the preparation method of the concrete is simple and easy to operate, no production line is needed to be additionally arranged in factory production, no substances such as iron powder are added, and the concrete has the advantages of high strength, strong mildew and algae prevention capability, high anti-permeability registration, low density and the like.
The above-described preferred conditions may be combined with each other to obtain a specific embodiment, in accordance with common knowledge in the art.
The raw materials or reagents involved in the invention are all common commercial products, and the operations involved are all routine operations in the field unless otherwise specified.
(III) advantageous effects
The technical scheme of the invention has the following advantages:
1) the invention first provides a composition of Ti3C2The powder and KH550 participate in modification of basalt fiber according to a specific proportion to obtain anticorrosion reinforcing fiber, and the anticorrosion reinforcing fiber is added into concrete, so that excellent impermeability and antibacterial and mildewproof effects can be given to the concrete, the mildewproof and algae-proof capabilities of the concrete can be remarkably improved, the corrosion of various microorganisms to a concrete structure can be effectively inhibited in practical application, the modification is favorable for the bonding strength of the anticorrosion reinforcing fiber and other components, the compactness of the concrete is further improved, the generation of cracks is prevented, the mildewproof and algae-proof capabilities and the impermeability of the concrete structure are improved, and the excellent structural strength is kept;
2) the fluorosilane coupling agent can obviously improve the bonding effect of ceramic powder and other components such as cement, fibers and the like after modifying the waste ceramic, obviously improve the mechanical strength of concrete, further improve the hydrophobicity of the concrete by the elimination effect of the fluorosilane coupling agent modification on the surface hydroxyl of the inorganic material, reduce the local agglomeration phenomenon of the concrete, ensure that the density uniformity of the formed solid concrete is higher, and obviously reduce the surface energy of the concrete by introducing the fluorosilane coupling agent, thereby improving the self-cleaning performance and the mildew and algae prevention capability;
3) the preparation method of the concrete is simple and easy to operate, no production line is required to be additionally arranged in factory production, no substances such as iron powder are added, and the concrete has the advantages of high strength, strong mildew and algae prevention capability, high anti-permeability registration, low density and the like.
The invention adopts the technical scheme for achieving the purpose, makes up the defects of the prior art, and has reasonable design and convenient operation.
Drawings
The foregoing and/or other objects, features, advantages and embodiments of the invention will be more readily understood from the following description taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic structural view of a fluorosilane coupling agent according to the present invention;
FIG. 2 is a schematic diagram showing the strength test results of the concrete according to the present invention;
FIG. 3 is a schematic diagram of the result of the uniformity quantitative determination of the concrete according to the present invention.
Detailed Description
Those skilled in the art can appropriately substitute and/or modify the process parameters to implement the present disclosure, but it is specifically noted that all similar substitutes and/or modifications will be apparent to those skilled in the art and are deemed to be included in the present invention. While the products and methods of making described herein have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the products and methods of making described herein may be made and utilized without departing from the spirit and scope of the invention.
Unless defined otherwise, 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. The present invention uses the methods and materials described herein; other suitable methods and materials known in the art may be used. The materials, methods, and examples described herein are illustrative only and are not intended to be limiting. All publications, patent applications, patents, provisional applications, database entries, and other references mentioned herein, and the like, are incorporated by reference herein in their entirety. In case of conflict, the present specification, including definitions, will control.
All percentages, parts, ratios, etc., are by weight unless otherwise indicated; additional instructions include, but are not limited to, "wt%" means weight percent, "mol%" means mole percent, "vol%" means volume percent.
The materials, methods, and examples described herein are illustrative only and not intended to be limiting unless otherwise specified. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.
The basalt fiber and the fly ash used in the technical proposal of the invention can be selected from the prior art or the market,for example, but not limited to, basalt staple fibers are commercially available and have the following properties: the density is 2.6-2.8 g/cm35-50 cm in length, 7-25 μm in diameter, 1050MPa in breaking strength, 35GPa in elastic modulus, 3.5% in elongation at break and 7.5% in alkali resistance.
The present invention is described in detail below.
Example 1: a concrete:
this example provides a concrete comprising sand, crushed stone and cement in conventional proportions with other components as shown in table 1.
TABLE 1 concrete Components
Components Parts by weight
Anti-corrosion reinforced fiber 20
Modified ceramic powder 50
42.5 Portland cement 475
Fly ash 75
Sand 500
Crushing stone 1000
Water (W) 180
The concrete of the embodiment is prepared by a method comprising the following steps:
1)Ti3AlC2fully grinding the powder, slowly adding the powder into 40% hydrofluoric acid solution for 4 times under the stirring of 1500r/min, wherein the weight of the hydrofluoric acid solution is Ti3AlC240 times of the powder weight at 65KHz and 0.7W/cm2Performing ultrasonic treatment for 12h under the condition, and reacting for 48h at the temperature of 38 ℃; centrifuging for several times, washing with distilled water until pH is not lower than 6, adding 20 times of distilled water, 65KHz, 0.7W/cm2Performing ultrasonic dispersion for 2h under the condition, performing suction filtration, and drying at 50 ℃ to constant weight to obtain Ti3C2Powder; according to Ti3C2The content of Ti is 0.5 percent and the content of KH550 is 1.2 percent respectively3C2Adding the powder and KH550 into a 60 vol% ethanol solution to obtain a modifier; placing basalt fibers into a modifier according to a material-liquid ratio of 1:20, stirring and modifying at 40 ℃ for 45min at a speed of 600r/min, taking out, and drying at 45 ℃ to constant weight to obtain the anticorrosion reinforced fibers;
2) the waste ceramic floor tiles are cleaned, crushed, ball-milled and dried to obtain ceramic particles with the particle size not higher than 3 mm; adjusting pH of 80 vol% ethanol solution to 4.5 with acetic acid to obtain dispersion, adding fluorosilane coupling agent shown in formula (1) into the dispersion according to 0.01 ‰ of ceramic particle weight, 35KHz, 0.5W/cm2Carrying out ultrasonic dispersion for 1h under the condition to obtain a fluorosilane coupling agent solution; uniformly spraying a fluorosilane coupling agent solution on the surface of the ceramic particles at room temperature under the stirring of 120r/min, drying at 45 ℃ to constant weight, and grinding until the particle size is not higher than 0.5mm to obtain modified ceramic powder;
3) adding fly ash into cement according to the formula amount, uniformly mixing, adding the anti-corrosion reinforcing fiber and the modified ceramic powder, compounding cement, sand, gravel and water, and uniformly stirring to obtain the anti-corrosion cement.
Example 2: another concrete:
this example provides another concrete, which has substantially the same formulation and preparation method as example 1, except that the concrete of this example is prepared by a method comprising:
1) adding KH550 into 60 vol% ethanol solution according to the content of KH550 of 1.2% to obtain a modifier; placing basalt fibers into a modifier according to a material-liquid ratio of 1:20, stirring and modifying at 40 ℃ for 45min at 600r/min, taking out, and drying at 45 ℃ to constant weight to obtain the anticorrosive reinforced chemical fibers;
2) same as step 2) of example 1;
3) same as step 3 of example 1).
Example 3: another concrete:
this example provides another concrete, which has substantially the same formulation and preparation method as example 1, except that the concrete of this example is prepared by a method comprising:
1)Ti3AlC2fully grinding the powder, slowly adding the powder into 40% hydrofluoric acid solution for 4 times under the stirring of 1500r/min, wherein the weight of the hydrofluoric acid solution is Ti3AlC240 times of the powder weight at 65KHz and 0.7W/cm2Performing ultrasonic treatment for 12h under the condition, and reacting for 48h at the temperature of 38 ℃; centrifuging for several times, washing with distilled water until pH is not lower than 6, adding 20 times of distilled water, 65KHz, 0.7W/cm2Performing ultrasonic dispersion for 2h under the condition, performing suction filtration, and drying at 50 ℃ to constant weight to obtain Ti3C2Powder; according to Ti3C2The content of Ti is 0.5 percent and the content of KH550 is 1.2 percent respectively3C2Adding the powder and KH550 into a 60 vol% ethanol solution to obtain a modifier; placing basalt fibers into a modifier according to a material-liquid ratio of 1:20, stirring and modifying at 40 ℃ for 45min at a speed of 600r/min, taking out, and drying at 45 ℃ to constant weight to obtain the anticorrosion reinforced fibers;
2) same as step 2) of example 1;
3) same as step 3 of example 1).
Example 4: another concrete:
this example provides another concrete, which has substantially the same formulation and preparation method as example 1, except that the concrete of this example is prepared by a method comprising:
1)Ti3AlC2fully grinding the powder, slowly adding the powder into 40% hydrofluoric acid solution for 4 times under the stirring of 1500r/min, wherein the weight of the hydrofluoric acid solution is Ti3AlC240 times of the powder weight at 65KHz and 0.7W/cm2Performing ultrasonic treatment for 12h under the condition, and reacting for 48h at the temperature of 38 ℃; centrifuging for several times, washing with distilled water until pH is not lower than 6, adding 20 times of distilled water, 65KHz, 0.7W/cm2Performing ultrasonic dispersion for 2h under the condition, performing suction filtration, and drying at 50 ℃ to constant weight to obtain Ti3C2Powder; according to Ti3C2The content of Ti is 0.5 percent and the content of KH550 is 0.5 percent respectively3C2Adding the powder and KH550 into a 60 vol% ethanol solution to obtain a modifier; placing basalt fibers into a modifier according to a material-liquid ratio of 1:20, stirring and modifying at 40 ℃ for 45min at a speed of 600r/min, taking out, and drying at 45 ℃ to constant weight to obtain the anticorrosion reinforced fibers;
2) same as step 2) of example 1;
3) same as step 3 of example 1).
Example 5: another concrete:
this example provides another concrete, which has substantially the same formulation and preparation method as example 1, except that the concrete of this example is prepared by a method comprising:
1)Ti3AlC2fully grinding the powder, slowly adding the powder into 40% hydrofluoric acid solution for 4 times under the stirring of 1500r/min, wherein the weight of the hydrofluoric acid solution is Ti3AlC240 times of the powder weight at 65KHz and 0.7W/cm2Performing ultrasonic treatment for 12h under the condition, and reacting for 48h at the temperature of 38 ℃; centrifuging for several times, washing with distilled water until pH is not lower than 6, adding 20 times of distilled water, 65KHz, 0.7W/cm2Performing ultrasonic dispersion for 2h under the condition, performing suction filtration, and drying at 50 ℃ to constant weight to obtain Ti3C2Powder; according to Ti3C2The Ti content is 0.5 percent and the KH550 content is 3 percent respectively3C2Adding the powder and KH550 into a 60 vol% ethanol solution to obtain a modifier; placing basalt fiber in a modifier according to the material-liquid ratio of 1:20, and stirring at the temperature of 40 ℃ at 600r/minModifying for 45min, taking out, and drying at 45 ℃ to constant weight to obtain the anticorrosion reinforced fiber;
2) same as step 2) of example 1;
3) same as step 3 of example 1).
Example 6: another concrete:
this example provides another concrete, which has substantially the same formulation and preparation method as example 1, except that the concrete of this example is prepared by a method comprising:
1) according to Ti3AlC2The powder content is 0.5%, the KH550 content is 3% respectively3AlC2Adding the powder and KH550 into a 60 vol% ethanol solution to obtain a modifier; placing basalt fibers into a modifier according to a material-liquid ratio of 1:20, stirring and modifying at 40 ℃ for 45min at a speed of 600r/min, taking out, and drying at 45 ℃ to constant weight to obtain the anticorrosion reinforced fibers;
2) same as step 2) of example 1;
3) same as step 3 of example 1).
Example 7: a concrete:
this example provides a concrete comprising sand, crushed stone and cement in conventional proportions with other components as shown in table 2.
TABLE 2 concrete Components
Components Parts by weight
Basalt fiber 20
Modified ceramic powder 50
42.5 Portland cement 475
Fly ash 75
Sand 500
Crushing stone 1000
Water (W) 180
The concrete of the embodiment is prepared by a method comprising the following steps:
1) same as step 2) of example 1;
2) adding fly ash into cement according to the formula amount, uniformly mixing, adding basalt fiber and modified ceramic powder, compounding cement, sand, gravel and water, and uniformly stirring to obtain the cement.
Example 8: another concrete:
this example provides another concrete, which has substantially the same formulation and preparation method as example 1, except that the concrete of this example is prepared by a method comprising:
1) same as step 1) of example 1;
2) the waste ceramic floor tiles are cleaned, crushed, ball-milled and dried to obtain ceramic particles with the particle size not higher than 3 mm; adjusting pH of 80 vol% ethanol solution to 4.5 with acetic acid to obtain dispersion, adding A151 silane coupling agent into the dispersion according to 0.01 ‰ of ceramic particle weight, 35KHz, 0.5W/cm2Carrying out ultrasonic dispersion for 1h under the condition to obtain a fluorosilane coupling agent solution; uniformly spraying the fluorosilane coupling agent solution on the surface of the ceramic particles at room temperature under the stirring of 120r/min, drying at 45 ℃ to constant weight, and grinding to particlesThe degree is not higher than 0.5mm, and then the modified ceramic powder is obtained; (ii) a
3) Same as step 3 of example 1).
Example 9: another concrete:
this example provides another concrete, which has substantially the same formulation and preparation method as example 1, except that the concrete of this example is prepared by a method comprising:
1) same as step 1) of example 1;
2) the waste ceramic floor tiles are cleaned, crushed, ball-milled and dried to obtain ceramic particles with the particle size not higher than 3 mm; adjusting pH of 80 vol% ethanol solution to 4.5 with acetic acid to obtain dispersion, adding tridecafluorooctyltriethylsilane to the dispersion at 0.01 ‰ of ceramic particle weight, 35KHz, 0.5W/cm2Carrying out ultrasonic dispersion for 1h under the condition to obtain a fluorosilane coupling agent solution; uniformly spraying a fluorosilane coupling agent solution on the surface of the ceramic particles at room temperature under the stirring of 120r/min, drying at 45 ℃ to constant weight, and grinding until the particle size is not higher than 0.5mm to obtain modified ceramic powder;
3) same as step 3 of example 1).
Example 10: another concrete:
this example provides a concrete comprising sand, crushed stone and cement in conventional proportions with other components as shown in table 3.
TABLE 3 concrete Components
Components Parts by weight
Anti-corrosion reinforced fiber 20
Ceramic powder 50
42.5 Portland cement 475
Fly ash 75
Sand 500
Crushing stone 1000
Water (W) 180
The concrete of the embodiment is prepared by a method comprising the following steps:
1) same as step 1) of example 1;
3) adding fly ash into cement according to the formula amount, uniformly mixing, adding the anti-corrosion reinforced fiber and the ceramic powder, compounding cement, sand, gravel and water, and uniformly stirring to obtain the anti-corrosion cement.
Example 11: a concrete:
this example provides a concrete comprising sand, crushed stone and cement in conventional proportions with other components as shown in table 4.
TABLE 4 concrete Components
Components Parts by weight
Modified ceramic powder 50
42.5 Portland cement 475
Fly ash 75
Sand 500
Crushing stone 1000
Water (W) 180
The concrete of the embodiment is prepared by a method comprising the following steps:
1) the waste ceramic floor tiles are cleaned, crushed, ball-milled and dried to obtain ceramic particles with the particle size not higher than 3 mm; adjusting pH of 80 vol% ethanol solution to 4.5 with acetic acid to obtain dispersion, adding fluorine-containing silane coupling agent into the dispersion according to 0.01 ‰ of ceramic particle weight, 35KHz, 0.5W/cm2Carrying out ultrasonic dispersion for 1h under the condition to obtain a fluorosilane coupling agent solution; uniformly spraying a fluorosilane coupling agent solution on the surface of the ceramic particles at room temperature under the stirring of 120r/min, drying at 45 ℃ to constant weight, and grinding until the particle size is not higher than 0.5mm to obtain modified ceramic powder;
2) adding fly ash into cement according to the formula amount, uniformly mixing, adding modified ceramic powder, compounding cement, sand, broken stone and water, and uniformly stirring to obtain the cement.
Example 12: a concrete:
this example provides a concrete comprising sand, crushed stone and cement in conventional proportions with other components as shown in table 5.
TABLE 5 concrete Components
Figure BDA0003186509310000121
Figure BDA0003186509310000131
The concrete of the embodiment is prepared by a method comprising the following steps:
1)Ti3AlC2fully grinding the powder, slowly adding the powder into 40% hydrofluoric acid solution for 4 times under the stirring of 1500r/min, wherein the weight of the hydrofluoric acid solution is Ti3AlC240 times of the powder weight at 65KHz and 0.7W/cm2Performing ultrasonic treatment for 12h under the condition, and reacting for 48h at the temperature of 38 ℃; centrifuging for several times, washing with distilled water until pH is not lower than 6, adding 20 times of distilled water, 65KHz, 0.7W/cm2Performing ultrasonic dispersion for 2h under the condition, performing suction filtration, and drying at 50 ℃ to constant weight to obtain Ti3C2Powder; according to Ti3C2The content of Ti is 0.5 percent and the content of KH550 is 1.2 percent respectively3C2Adding the powder and KH550 into a 60 vol% ethanol solution to obtain a modifier; placing basalt fibers into a modifier according to a material-liquid ratio of 1:20, stirring and modifying at 40 ℃ for 45min at a speed of 600r/min, taking out, and drying at 45 ℃ to constant weight to obtain the anticorrosion reinforced fibers;
2) according to the formula amount, adding fly ash into cement, mixing uniformly, adding anti-corrosion reinforcing fiber, compounding cement, sand, gravel and water, and stirring uniformly to obtain the anti-corrosion cement.
Experimental example 1: and (3) testing the strength:
the concrete obtained in examples 1-12 of the present application was tested for compressive strength according to "GB/T50081 Standard for ordinary concrete mechanical Properties test methods", and the statistical results are shown in FIG. 2. As can be seen from FIG. 2, the concrete based on the reinforcing fibers has excellent compressive strength, the 7d compressive strength of the concrete obtained in the preferred embodiment example 1 exceeds 36KPa, and the 28d compressive strength exceeds 42 KPa; in addition, from the figures2, Ti in proper proportion according to the technical scheme of the application3O2The powder and the KH550 silane coupling agent are used for modifying basalt fibers, and the fluorosilane coupling agent disclosed by the formula (1) has important positive significance for modifying the mechanical strength of the final product concrete.
Experimental example 2: and (3) testing the impermeability and the mildew and algae resistance:
in this example, the impermeability is characterized by the impermeability grade, and the mildew and algae resistance is measured by the following method in the prior art: mixing a bacillus solution with activity of 70000U/mL, a mould solution with activity of 60000U/mL and a diatom solution with activity of 50000U/mL according to a volume ratio of 1:1:1, inoculating the mixture on the surface of the concrete obtained in examples 1-12, and observing how long the concrete can not grow mould and algae, thereby being used as a quantitative standard for the mould and algae prevention capacity. The test results are shown in table 6.
TABLE 6 impermeability and resistance to mildew and algae
Figure BDA0003186509310000132
Figure BDA0003186509310000141
In combination with the above table, it can be seen from examples 1 to 7 and 11 that Ti is present in a specific ratio3O2The powder and the KH550 silane coupling agent have a vital effect on improving the anti-permeability grade and the mildew-proof and algae-proof capability of the concrete when the basalt fibers are modified and added into the concrete, and in addition, the waste ceramic particles are modified by the A151 silane coupling agent in example 8, the waste ceramic particles are modified by the tridecafluorooctyltriethylsilane in example 9, the waste ceramic particles are not modified in example 10, and the modified ceramic powder is not added in example 12, so that the waste ceramic particles are modified by the fluorosilane coupling agent shown in the formula (1) and added into the concrete to improve the anti-permeability and the likeThe improvement of the level and the mildew and algae resistance also has obvious influence.
Experimental example 3: and (3) uniformity inspection:
the concrete obtained in examples 1 to 12 was examined for homogeneity as follows:
and (3) carrying out qualitative inspection on uniformity: splitting the completely hardened concrete block, and visually observing whether the components of the section are uniformly distributed;
and (3) carrying out uniformity quantitative inspection: taking a completely hardened concrete block (with the height of 1m), detecting the density rho of an upper layer (0-10 cm) and the average density rho of a lower layer (90-100 cm), and calculating a uniformity quantitative value by using a formula (2):
Figure BDA0003186509310000142
storage stability: and (3) storing the concrete block for 30 days at normal temperature and normal pressure, and observing whether the surface of the concrete block has cracks.
The results of the qualitative homogeneity test and the storage stability are shown in Table 7, and the results of the quantitative homogeneity test are shown in FIG. 3.
TABLE 7 concrete homogeneity
Examples Qualitative test for homogeneity Storage stability
1 Uniformity Without cracks
2 Uniformity Without cracks
3 Uniformity Without cracks
4 Uniformity Without cracks
5 Uniformity Without cracks
6 Uniformity Without cracks
7 Uniformity Without cracks
8 Slightly uneven Without cracks
9 Slightly uneven Without cracks
10 Slightly uneven Without cracks
11 Slightly uneven Without cracks
12 Unevenness of Without cracks
As can be seen from Table 7 and FIG. 3, the concrete of example 1, which is a preferred embodiment of the present invention, has excellent uniformity and storage stability, and the cured cross section has uniform distribution of the components, no cracks on the appearance after 30 days of storage, and a small quantitative value of uniformity, indicating that the concrete has uniform solid density after molding. In addition from embodiment 8 ~ 12, can also see that the fluorine silane coupling agent has apparent influence to the homogeneity of concrete to the abandonment ceramic particles is modified, compares in utilizing with A151 silane coupling agent or tridecafluorooctyltriethylsilane, uses this application fluorine silane coupling agent is favorable to promoting the density homogeneity of solid concrete after the shaping more to the abandonment ceramic particles is modified.
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
While the above detailed description has shown, described, and pointed out novel features as applied to various embodiments, it will be understood that various omissions, substitutions, and changes in the form and details of the device or method illustrated may be made without departing from the spirit of the disclosure. In addition, the various features and methods described above may be used independently of one another, or may be combined in various ways. All possible combinations and sub-combinations are intended to fall within the scope of the present disclosure. Many of the embodiments described above include similar components, and thus, these similar components are interchangeable in different embodiments. While the invention has been disclosed in the context of certain embodiments and examples, it will be understood by those skilled in the art that the invention extends beyond the specifically disclosed embodiments to other alternative embodiments and/or uses and obvious modifications and equivalents thereof. Accordingly, the invention is not intended to be limited by the specific disclosure of preferred embodiments herein.
The invention is not the best known technology.

Claims (8)

1. A method for preparing corrosion-resistant reinforcing fibers, comprising:
1)Ti3AlC2fully grinding the powder, adding the powder into 35-40% vol hydrofluoric acid solution in batches under stirring, performing ultrasonic treatment for at least 6 hours, and reacting at 35-40 ℃ for at least 48 hours; centrifuging for many times, washing with distilled water until pH is not lower than 6, adding distilled water, ultrasonic dispersing, vacuum filtering, and drying to obtain Ti3C2Powder;
2) ti of step 1)3C2Adding the powder and KH550 into 50-75% vol ethanol solution to obtain modifier, Ti3C2The content is not higher than 1 percent, and the content of KH550 is not higher than 4 percent; the basalt fibers are placed in a modifier according to the material-liquid ratio of 1: 20-50, stirred and modified at the temperature of 35-40 ℃ for at least 30min, and taken out and dried to obtain the anti-corrosion reinforced fibers.
2. The method of claim 1, wherein: step 1) the amount of the hydrofluoric acid solution is Ti3AlC235-50 times of the weight of the powder.
3. The method according to claim 1 or 2, characterized in that: step 2) Ti3C2The weight ratio of the powder to the KH550 is 1: 1.5-3.0.
4. The use of the corrosion-resistant reinforcing fiber prepared by the method of any one of claims 1 to 3 in concrete.
5. A method for preparing concrete based on the anti-corrosion reinforcing fiber prepared by the method of any one of claims 1 to 3, comprising the following steps:
1) preparing anticorrosion reinforcing fiber;
2) modifying the waste ceramic powder with a fluorosilane coupling agent to obtain modified ceramic powder;
3) adding fly ash into cement, mixing uniformly, adding anticorrosive reinforcing fiber and modified ceramic powder, compounding cement, sand, broken stone and water according to a conventional ratio, and stirring uniformly to obtain the cement.
6. The method of claim 5, wherein: the modified ceramic powder is obtained by modifying waste ceramic powder with a fluorosilane coupling agent shown in formula (1).
Figure FDA0003186509300000011
7. The method according to claim 5 or 6, characterized in that: the method for preparing the modified ceramic powder by modifying the waste ceramic powder with the fluorosilane coupling agent comprises the following specific steps:
1) cleaning, crushing, ball-milling and drying the waste ceramics to obtain ceramic particles with the particle size not higher than 3 mm;
2) adjusting the pH value of 75-90 vol% ethanol solution to 4-5 to obtain dispersion liquid, adding a fluorosilane coupling agent into the dispersion liquid according to 0.001-0.05 per mill of the weight of the ceramic particles, and uniformly dispersing to obtain fluorosilane coupling agent solution;
3) and (3) uniformly spraying the fluorosilane coupling agent solution obtained in the step 2) on the surface of the ceramic particles under stirring at room temperature, drying at 45-55 ℃ to constant weight, and grinding until the granularity is not higher than 0.5 mm.
8. The method of claim 7, wherein: step 1) the waste ceramic comprises:
such as various ceramic crafts, waste life ceramics of daily application ceramics and the like,
such as waste building ceramics of floor tiles, wall tiles, structural bricks and the like,
such as ceramic semi-finished products, electrical insulating ceramics, chemical ceramics, and the like.
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