CN113149541A - Environment-friendly anti-freezing concrete and preparation method thereof - Google Patents
Environment-friendly anti-freezing concrete and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/023—Chemical treatment
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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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/1055—Coating or impregnating with inorganic materials
- C04B20/1066—Oxides, Hydroxides
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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
- C04B40/0046—Premixtures of ingredients characterised by their processing, e.g. sequence of mixing the ingredients when preparing the premixtures
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/601—Agents for increasing frost resistance
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/29—Frost-thaw resistance
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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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Abstract
The application relates to the technical field of building materials, and particularly discloses environment-friendly anti-freezing concrete and a preparation method thereof. The environment-friendly anti-freezing concrete comprises the following components in parts by weight: cement 420-570, sand 572-656, stone 825-940, water 170-210, admixture 51-70, admixture 58.8-80.6, waste rubber particles 40-60 and antifreeze 45-60; the antifreeze agent comprises the following components: modified starch, graphene oxide, iron tailing powder, an eggshell membrane, sodium hydroxide, urea and cellulose; the preparation method comprises the following steps: adding the admixture and the antifreeze agent into water, and uniformly mixing to obtain a premix; and mixing the cement, the sand, the pebbles, the admixture and the waste rubber particles, adding the premix, and uniformly mixing to obtain the environment-friendly antifreezing concrete. The environment-friendly anti-freezing concrete has the advantages of recycling waste rubber, being anti-freezing and strong in anti-permeability performance, and being capable of purifying automobile exhaust.
Description
Technical Field
The application relates to the technical field of building materials, in particular to environment-friendly anti-freezing concrete and a preparation method thereof.
Background
With the rapid development of economy in China, environmental problems are increasingly severe, and the yield of various wastes is increased rapidly, so that the recycling of the wastes is an important way for protecting natural resources and promoting sustainable development. The yield of the waste tires in China reaches 3.3 hundred million in 2015, the recovery rate is only less than 50 percent, the waste tires are recovered as the concrete making raw materials, the recovery utilization amount is large, and the pavement performance of the concrete can be improved.
Concrete freeze-thaw damage is a common disease in concrete structure engineering in cold regions, particularly in coastal regions, wind power is high, temperature is low, and a concrete structure which is often in contact with water is subjected to freeze-thaw damage to different degrees locally or in a large area, so that performance degradation of the concrete structure is accelerated, and structural safety and durability of concrete are seriously affected.
At present, the main measures for improving the frost resistance of concrete include the following two measures, firstly, a large number of air holes are generated in the concrete by adding an air entraining agent, the ice expansion stress generated by the solid-liquid phase change of water is relieved, but the compactness of the concrete is reduced and the strength and the impermeability are poor due to the existence of the large number of air holes, and the other measure is that some salts are doped in an additive to reduce the freezing point of water, but the salt has small reduction range on the freezing point of water, can be generally maintained at minus several degrees without freezing, and is not suitable for underwater environments in lower-temperature areas such as west, north and the like.
In view of the above-mentioned related technologies, the inventor considers that the development of a concrete having excellent frost resistance using waste rubber is an urgent problem to be solved.
Disclosure of Invention
In order to recycle waste rubber and improve the frost resistance of concrete, the application provides the environment-friendly frost-resistant concrete and the preparation method thereof.
In a first aspect, the application provides an environment-friendly anti-freezing concrete, which adopts the following technical scheme:
the environment-friendly anti-freezing concrete comprises the following components in parts by weight: cement 420-570, sand 572-656, stone 825-940, water 170-210, admixture 51-70, admixture 58.8-80.6, waste rubber particles 40-60 and antifreeze 45-60;
the antifreeze agent comprises the following components in parts by weight: 5-10 parts of modified starch, 10-15 parts of graphene oxide, 2.4-5 parts of iron tailing powder, 4.3-6.5 parts of eggshell membrane, 2.5-5 parts of sodium hydroxide, 2.5-4 parts of urea and 5-8 parts of cellulose.
By adopting the technical scheme, as the waste rubber particles and the antifreeze prepared from the components of the modified starch, the graphene oxide, the eggshell membrane and the like are adopted, as the waste rubber particles are elastic materials and are mixed in the concrete, the waste rubber particles have stronger tensile and compressive deformation capacities, provide a buffer and pressure relief space for ice expansion stress, can reduce the development of freeze-thaw cracks, have rough surfaces, can introduce certain air and improve the frost resistance of the concrete, in addition, functional groups on the graphene oxide in the antifreeze can generate calcium salts with free calcium ions and are adsorbed on the surface of admixture, and the modified starch has good dispersion effect and the effect of inhibiting initial hydration, so that the graphene oxide and the modified starch can play the roles of fully hydrating the cement, more uniformly distributing hydration products and more compact grid structure, thereby improving the compactness and impermeability of the concrete, the sodium hydroxide and the urea can quickly dissolve cellulose to form fiber gel in a low-temperature environment, so that a buffer space is provided for ice expansion stress, and the frost resistance of concrete is improved; in addition, the modified starch has the characteristics of water absorption volume expansion and water loss volume drying shrinkage, and the graphene oxide has the characteristics of high porosity and large specific surface area, and can provide enough buffering and pressure relief space for ice expansion stress, so that the frost resistance of concrete is improved; the iron tailing powder can supplement powder in concrete, the compressive strength is increased, the iron tailing powder also has a micro-scale matching effect and a specific surface area effect, the micro-scale matching effect improves the fluidity, the specific surface area effect is beneficial to improving the cohesiveness and the water retention property, and the volcanic ash component in the iron tailing powder reacts with calcium hydroxide crystals to effectively block and communicate pores, reduce the content of calcium hydroxide in hardened concrete and prevent the occurrence of pores caused by the dissolution loss of the calcium hydroxide, so that the impermeability and the freezing resistance of the concrete are enhanced; the eggshell membrane can cover cement and admixture, reduces the water consumption for mixing, has no free water in concrete after the cement is hardened because of the reduction of the water consumption, can prevent the free water from volatilizing to leave a large number of pores, and blocks and communicates the pores, thereby improving the anti-permeability and anti-freezing performance of the concrete.
Preferably, the preparation method of the antifreeze agent is as follows: (1) mixing graphene oxide and modified starch, and dispersing for 1.5-2 hours by ultrasonic waves to obtain a graphene oxide/modified starch intercalation composite material;
(2) dissolving urea and sodium hydroxide with water respectively, mixing, adding the graphene oxide/modified starch intercalation composite material, performing ultrasonic treatment for 1-2h, cooling to the temperature of- (12-13) DEG C, adding cellulose and 2-epoxy-3 chloropropane, stirring uniformly at room temperature, adding the eggshell membrane and the iron tailing powder into a water bath at the temperature of 25-30 ℃ for 40-48h, drying and crushing to prepare the antifreeze agent.
By adopting the technical scheme, after the modified starch and the graphene oxide are subjected to ultrasonic treatment, the lamella spacing of the graphene oxide is increased, the modified starch has the water absorption expansion characteristic, when urea and sodium hydroxide are mixed, the modified starch absorbs the solution to expand, the lamella spacing of the graphene oxide is further increased, the iron tailings and the eggshell membrane are filled into the graphene oxide, in the process that cement is continuously hydrated, moisture in the modified starch disappears, the volume of the modified starch is reduced, but the lamella spacing of the graphene oxide is unchanged, a buffer space is provided for the ice expansion stress of the concrete, the frost resistance of the concrete is improved, in addition, cellulose is mixed with the urea and the sodium hydroxide and then dissolved at low temperature to form fiber sol, the effect of buffering the ice expansion stress is further improved, the frost resistance of the concrete is improved, and preferably, the waste rubber particles are pretreated by the following steps: (1) fully soaking waste rubber particles in a sodium hydroxide solution with the concentration of 0.01-0.2%, standing for 20-24h, cleaning, airing, putting the waste rubber particles into a silane coupling agent KH570 solution with the mass fraction of 0.1-0.2%, uniformly stirring, and airing for later use, wherein the mass ratio of the waste rubber particles to the sodium oxide solution to the silane coupling agent KH570 solution is 1:1.3-1.5: 1.3-1.5;
(2) taking silica sol, adding carbon black and alumina, and uniformly mixing to prepare composite gel, wherein the mass ratio of the silica sol to the carbon black to the alumina is 1:0.5-0.7: 0.7-0.9;
(3) adding the waste rubber particles prepared in the step (1) into the composite gel, stirring for 4-6h at 60-80 ℃, taking out the waste rubber particles, and drying by supercritical carbon dioxide, wherein the mass ratio of the composite gel to the waste rubber particles is 1: 20-30.
By adopting the technical scheme, the sodium hydroxide with the concentration of 0.01-0.2% etches the surfaces of the waste rubber particles, and the surface roughness is increased, so that the air entraining amount of the waste particles is increased, and the frost resistance of the concrete is further improved; and then coating the waste rubber particles with silica sol containing carbon black and alumina, wherein the nano silica particles are dispersed in the silica sol, so that the silica sol has small particle size and high dispersion degree, can permeate into pores on the surfaces of the waste rubber particles, and can be locked in the pores on the surfaces of the waste particles because the silica is insoluble in water, so that the toughness and hardness of the waste rubber particles are improved, the compressive strength of concrete is improved, and in addition, the silica sol can generate a C-S-H network structure in the pores of the concrete, so that the compactness and impermeability of the concrete are improved.
Preferably, the preparation method of the modified starch comprises the following steps: mixing 1.8-2.6 parts by weight of carboxymethyl starch with water, stirring for 2-3 hours at 80-90 ℃, cooling, adding 0.05-0.1 part by weight of ammonium persulfate, stirring for 15-20min, adding 1.4-2 parts by weight of acrylic acid, 1.2-2.5 parts by weight of acrylamide and 0.08-0.2 part by weight of N, N-methylene bisacrylamide, reacting for 2-2.5 hours at 70-80 ℃, washing, soaking in a sodium hydroxide solution, drying and crushing to obtain the modified starch.
By adopting the technical scheme, ammonium persulfate is used as an initiator to initiate hydroxyl on carboxymethyl starch to generate free radicals and generate active centers on a main chain of the carboxymethyl starch, so that polymerization of acrylamide and acrylic acid is initiated to generate polyacrylamide acrylic acid long chains, a large number of carboxyl functional groups are introduced, the carboxymethyl starch-acrylic acid-acrylamide are crosslinked into a three-dimensional network structure by a crosslinking agent N, N-methylene bisacrylamide, and after the carboxyl functional groups in the three-dimensional network are converted into ester groups after being treated by a sodium hydroxide solution, so that the three-dimensional network structure is negatively charged and is endowed with extremely strong electrostatic repulsion, the expansion capacity and swelling performance of the three-dimensional network structure are improved, the expansion capacity of the modified starch after meeting water is enhanced, the aperture is increased, and the adsorption capacity to gases such as phenol, ammonia and the like is enhanced, the purification effect on the nitrogen oxide is improved.
Preferably, the additive is an HTJS-3 type polycarboxylic acid high-performance water reducing agent and an expanding agent, and the mass ratio of the HTJS-3 type polycarboxylic acid high-performance water reducing agent to the expanding agent is 1: 3.57-3.59.
By adopting the technical scheme, the expanding agent can compensate the concrete shrinkage and improve the compactness and impermeability of the concrete, and the HTJS-3 type polycarboxylate-type high-performance water reducing agent takes a third-generation polycarboxylate water reducing agent as a master batch, is doped with various components such as an early strength agent, frost resistance, plastic protection and the like, has an early strength effect, can reduce the moisture freezing point of the surface of the concrete, and has the early strength and frost resistance effects.
Preferably, the admixture is class II fly ash, the fineness (the residue of a 45-micron square-hole sieve) is less than or equal to 12 percent, the water demand ratio is 98 percent, the loss on ignition is less than or equal to 4.5 percent, and the specific surface area is 280-300m2Kg, density of 2.69-2.75g/cm3。
By adopting the technical scheme, more than 70% of particles in the fly ash are amorphous spherical glass bodies, the ball bearing effect is mainly achieved, the lubricating effect is achieved in the concrete mixture, the workability of the concrete mixture is improved, the fly ash and coarse aggregate form reasonable grading, the fly ash and the coarse aggregate are mutually filled, the compactness of the concrete can be effectively increased, and the compressive strength and the impermeability of the concrete are further improved.
Preferably, the sand comprises river sand and machine-made sand in a mass ratio of 1:0.9-1.1, wherein the river sand is sand in a zone II, the fineness modulus is 2.8, the mud content is 1.9%, the machine-made sand is coarse sand, the fineness modulus is 3.3, and the stone powder content is 3.6%.
By adopting the technical scheme, proper amount of stone powder in the machine-made sand can perfect gradation in the fine aggregate, plays roles of filling and lubricating, simultaneously increases the total specific surface area of solid particles of the mixture, weakens segregation and bleeding, improves cohesiveness and water-retaining property of the concrete mixture, increases compactness of the concrete, and further plays a role in improving comprehensive performance of the concrete.
Preferably, the stones are 5-21.5mm continuous graded broken stones, the mud content is 0.9%, the mud block content is 0.3%, and the apparent density is 2500-3The bulk density is 1400-1600kg/m3。
Through adopting above-mentioned technical scheme, needle slice granule content in the rubble is suitable, can effectively improve the intensity of concrete, and the rubble particle diameter is reasonable, avoids the granule great, causes the hole between the rubble great, causes the concrete to be lower at intensity under water, improves the compressive strength of concrete.
Preferably, the specific surface area of the iron tailing powder is 770-800m2/kg, wherein the content of silicon dioxide is 68.63%, and the content of aluminum oxide is 6.72%.
By adopting the technical scheme, the fine gradation of the concrete is perfected by the iron tailing powder, the slump is reduced, the cohesiveness is improved, the silica and the alumina can react with the calcium hydroxide to block the dissolution loss of the calcium hydroxide, prevent the occurrence of communicated pores, and improve the impermeability of the concrete.
In a second aspect, the application provides a preparation method of the environment-friendly anti-freezing concrete, which adopts the following technical scheme:
a preparation method of environment-friendly anti-freezing concrete comprises the following steps:
s1, adding the admixture and the anti-freezing anti-seepage agent into water, and uniformly mixing to obtain a premix;
s2, mixing cement, sand, pebbles, an admixture and waste rubber particles, adding a premix, and uniformly mixing to obtain the environment-friendly antifreezing concrete
Through adopting above-mentioned technical scheme, because modified starch has water swelling capacity among the antifreeze, along with cement hydration volume increase, form the extrusion to modified starch, modified starch water content reduces, the volume diminishes, it is complementary finally to form the volume, the compactness of concrete has been improved, part mix water is stored in modified starch in addition, the shared porosity of mix water in the concrete has been reduced, thereby improve the impervious of concrete, and modified starch is when losing water gradually, the lamella interval of oxidation graphite alkene is still great, it plays the cushioning effect to rise stress for the ice of concrete, thereby promote the frost resisting property of concrete.
In summary, the present application has the following beneficial effects:
1. because this application adopts waste rubber granule and antifreeze to mix in the concrete, prepare the frost resisting concrete, waste rubber can provide ice stress buffering and pressure release space for the concrete, in addition can introduce certain air, improve the frost resisting property of concrete, the antifreeze is made by oxidation graphite alkene, modified starch, eggshell membrane etc. because oxidation graphite alkene and modified starch hole are big, have adsorption effect, can absorb the tail gas of coming and going vehicle emission, air-purifying, and the hole of modified graphite alkene and modified starch can provide buffering and pressure release space for the expansion stress that the water in the concrete produced when freezing, prevent the inside inflation fracture of concrete, thereby improve the frost resisting property of concrete, in addition the eggshell membrane can reduce in the concrete free water volatilize and leave the intercommunication hole, block the intercommunication hole, improve the impervious and the frost resisting property of concrete.
2. The waste rubber particles are preferably pretreated by adopting sodium hydroxide and a silane coupling agent KH570, the surface roughness of the waste rubber particles can be increased due to the etching effect of the sodium hydroxide, the air entraining amount of the waste rubber particles is increased, the frost resistance of concrete is improved, the pretreated waste rubber particles are mixed with silica sol, carbon black and alumina, the porosity of the carbon black and the alumina is high, the adsorption force is strong, the particles of the silica sol are small, and the compactness, impermeability and air purification capacity of the concrete can be improved.
3. Ammonium persulfate is used as an initiator in the application, N, N-methylene bisacrylamide is a cross-linking agent, carboxymethyl starch is modified by acrylic acid and acrylamide, a carboxymethyl starch-acrylic acid-acrylamide cross-linked three-dimensional network structure is formed, after the carboxymethyl starch-acrylic acid-acrylamide cross-linked three-dimensional network structure is soaked by sodium hydroxide, the three-dimensional network structure bears load, and has strong electrostatic repulsion force, swelling performance and expansibility are enhanced, swelling stress is increased after the carboxymethyl starch-acrylic acid-acrylamide cross-linked three-dimensional network structure meets water, the interlayer spacing of graphene oxide is increased, the adsorption capacity of nitrogen oxide in tail gas is enhanced, the ice expansion stress buffering effect on concrete is enhanced, and the frost resistance is improved.
Detailed Description
Preparation example 1 of Eggshell Membrane
Preparation example 1: crushing 10kg of egg shell, adding 240L of water, adding 24L of 36% acetic acid, keeping the temperature at 45 ℃ for 1.5h, standing at normal temperature for 24h, filtering, washing with water, drying at 60 ℃ for 1.5h, chopping, adding 10L of 20% sulfuric acid, heating to 80 ℃ for reflux extraction for 5h, adding 3kg of calcium carbonate, filtering, spray drying, and crushing to 1um to obtain the eggshell membrane.
Preparation example of antifreeze agent
In preparation examples 1 to 4, the modified carboxymethyl starch was selected from Haochun chemical Co., Ltd, model 021, the graphene oxide was selected from Hangzhou Zhi Ti purification technology Co., Ltd, the urea was selected from Beijing Kangpuhui vitamin technology Co., Ltd, model 012, and the cellulose was carboxymethyl cellulose was selected from Fuchun chemical Co., Ltd, model jy-006.
Preparation example 1: (1) mixing 10kg of graphene oxide and 5kg of modified starch, and dispersing for 1.5 hours by ultrasonic waves under the power of 600W to obtain a graphene oxide/modified starch intercalation composite material, wherein the modified starch is modified carboxymethyl starch;
(2) dissolving 2.5kg of urea and 2.5kg of sodium hydroxide with water respectively to form a urea solution with the concentration of 12% and a sodium hydroxide solution with the concentration of 7%, mixing the urea solution and the sodium hydroxide solution, adding a graphene oxide/modified starch intercalation composite material, carrying out ultrasonic treatment for 1h under the power of 500W, cooling to-12 ℃, adding 5kg of cellulose and 0.6kg of 2-epoxy-3 chloropropane, uniformly stirring at room temperature, adding 4.3kg of egg shell membrane and 2.4kg of iron tailing powder, carrying out water bath at 25 ℃ for 48h, drying for 2h at 60 ℃, crushing to prepare the antifreeze, wherein the egg shell membrane is selected from preparation example 1 of egg shell membrane, and the specific surface area of the iron tailing powder is 770m2The chemical composition of the fiber is shown in Table 1, and the cellulose is carboxymethyl cellulose.
TABLE 1 chemical composition of iron tailings in preparation examples 1-3
| Composition (I) | CaO | SiO2 | Al2O3 | Fe2O3 | MgO | K2O | Na2O | SO3 |
| w/％ | 2.76 | 68.63 | 6.72 | 11.99 | 3.82 | 1.98 | 1.60 | 1.91 |
Preparation example 2: (1) mixing 13kg of graphene oxide and 8kg of modified starch, and dispersing for 1.8 hours by ultrasonic waves under the power of 550W to obtain a graphene oxide/modified starch intercalation composite material, wherein the modified starch is modified carboxymethyl starch;
(2) dissolving 3.7kg of urea and 3.2kg of sodium hydroxide with water respectively to form a urea solution with the concentration of 12% and a sodium hydroxide solution with the concentration of 7%, mixing the urea solution and the sodium hydroxide solution, adding a graphene oxide/modified starch intercalation composite material, carrying out ultrasonic treatment for 1.5h under the power of 450W, cooling to-13 ℃, adding 6.5kg of cellulose and 0.8kg of 2-epoxy-3 chloropropane, uniformly stirring at room temperature, adding 5.4kg of egg shell membrane and 3.7kg of iron tailing powder, adding the mixture into a water bath at 28 ℃ for 44h, drying for 1.5h at 65 ℃, crushing to prepare the antifreeze, wherein the egg shell membrane is selected from preparation example 1 of the egg shell membrane, and the specific surface area of the iron tailing powder is 780m2The chemical composition of the fiber is shown in Table 1, and the cellulose is carboxymethyl cellulose.
Preparation example 3: (1) mixing 15kg of graphene oxide and 10kg of modified starch, and performing ultrasonic dispersion for 2 hours under the power of 450W to obtain a graphene oxide/modified starch intercalation composite material, wherein the modified starch is modified carboxymethyl starch;
(2) respectively dissolving 4kg of urea and 5kg of sodium hydroxide with water to form a urea solution with the concentration of 12% and a sodium hydroxide solution with the concentration of 7%, mixing the urea solution and the sodium hydroxide solution, adding a graphene oxide/modified starch intercalation composite material, carrying out ultrasonic treatment for 2h under the power of 400W, cooling to-13 ℃, adding 8kg of cellulose and 1.0kg of 2-epoxy-3 chloropropane, uniformly stirring at room temperature, adding 6.5kg of an egg shell membrane and 5kg of iron tailing powder, carrying out water bath at 30 ℃ for 40h, drying at 70 ℃ for 1.0h, crushing to prepare the antifreeze, wherein the egg shell membrane is selected from preparation example 1 of the egg shell membrane, and the specific surface area of the iron tailing powder is 800m2The chemical composition of the fiber is shown in Table 1, and the cellulose is carboxymethyl cellulose.
Preparation example 4: mixing 10kg of graphene oxide and 5kg of modified starch, adding 2.5kg of urea, 2.5kg of sodium hydroxide, 5kg of cellulose, 4.3kg of eggshell membrane and 2.4kg of iron tailing powder, and uniformly stirring to prepare the antifreeze agent.
Examples
In the following examples, the HTJS-3 type polycarboxylic acid high-performance water reducing agent is selected from Beijing Guwei building materials, Inc., the swelling agent is selected from Shanghai plastic materials, Inc., of Dongguan city, model is MS205D, the waste rubber particles are selected from Bocai mineral processing factories, Lingshan, model is 378, the silica sol is selected from Kohn silicon products, Inc., model is ZJN enhanced series silica sol, and the silane coupling agent KH570 is selected from Shanghai leaf Biotech, Inc.; acrylic acid is selected from Shanghai Deyue trade company, Cat number 40; the acrylamide is selected from new materials science and technology company, N, N-methylene bisacrylamide is selected from Shandong Deno chemical company, model number is DN-8T66, and carboxymethyl starch is selected from Haochun chemical company, and model number is RQHC.
Example 1: the preparation method of the environment-friendly antifreezing concrete comprises the following steps of:
s1, adding an additive and an anti-freezing and anti-seepage agent into water, and uniformly mixing to obtain a premix, wherein the additive comprises an HTJS-3 type polycarboxylic acid high-performance water reducing agent and an expanding agent with the mass ratio of 1:3.57, and the dosage of the HTJS-3 type polycarboxylic acid high-performance water reducing agent is 14.8kg/m3The amount of the expanding agent used is 53kg/m3The antifreeze agent is prepared from preparation example 4 of the antifreeze agent;
s2, mixing cement, sand, gravel, admixture and waste rubber particles, adding premix, and uniformly mixing to obtain the environment-friendly antifreezing concrete, wherein the cement is P.O42.5 portland cement, the sand comprises river sand and machine-made sand in a mass ratio of 1:0.9, the river sand is medium sand in a zone II, the fineness modulus is 2.8, the mud content is 1.9%, the machine-made sand is coarse sand, the fineness modulus is 3.3, the stone powder content is 3.6%, the gravel is 5-21.5mm continuous graded broken stone, the mud content is 0.9%, the mud block content is 0.3%, and the apparent density is 2500kg/m3Bulk density of 1400kg/m3The admixture is class II fly ash, the fineness (the screen residue of a 45 mu m square hole screen) is less than or equal to 12 percent, the water demand ratio is 98 percent, the loss on ignition is less than or equal to 4.5 percent, and the specific surface area is 280m2Kg, density 2.69g/cm3The particle size of the waste rubber particles is 40 meshes.
TABLE 2 raw material amounts of environmentally friendly antifreeze concrete in examples 1 to 6
Example 2: an environment-friendly antifreeze concrete is different from the concrete of example 1 in that the antifreeze agent is selected from the concrete of preparation example 1 of the antifreeze agent.
Example 3: an environment-friendly antifreeze concrete is different from the concrete of example 2 in that the raw materials are used in the amount shown in Table 2, wherein the admixture comprises an HTJS-3 type polycarboxylic acid type high-performance water reducing agent and an expanding agent in a mass ratio of 1:3.59, and the amount of the HTJS-3 type polycarboxylic acid type high-performance water reducing agent is 12.8kg/m3The amount of the expanding agent is 46kg/m3The gravel is 5-21.5mm continuous graded broken stone, the mud content is 0.9%, the mud block content is 0.3%, and the apparent density is 2700kg/m3Bulk density of 1600kg/m3The admixture is class II fly ash, the fineness (the screen residue of a 45 mu m square hole screen) is less than or equal to 12 percent, the water demand ratio is 98 percent, the loss on ignition is less than or equal to 4.5 percent, and the specific surface area is 300m2Kg, density 2.75g/cm3Examples 4 to 6: an environmentally friendly frost resistant concrete differs from example 2 in that the raw materials are used in the amounts shown in Table 2.
Example 7: an environment-friendly antifreeze concrete is different from the concrete of example 2 in that an antifreeze agent is prepared from the concrete of preparation example 2 of the antifreeze agent.
Example 8: an environment-friendly antifreeze concrete is different from the concrete of example 2 in that an antifreeze agent is prepared by the preparation example 3 of the antifreeze agent.
Example 9: an environment-friendly antifreezing concrete is different from the embodiment 2 in that the waste rubber particles in the antifreezing agent are pretreated by the following steps: (1) fully soaking waste rubber particles in a sodium hydroxide solution with the concentration of 0.01%, standing for 24 hours, cleaning, airing, putting the cleaned and aired waste rubber particles into a silane coupling agent KH570 solution with the mass fraction of 0.1%, uniformly stirring, airing for later use, wherein the mass ratio of the waste rubber particles to the sodium oxide solution to the silane coupling agent KH570 solution is 1:1.3: 1.3;
(2) taking silica sol, adding carbon black and alumina, and uniformly mixing to obtain composite gel, wherein the mass ratio of the silica sol to the carbon black to the alumina is 1:0.5: 0.7;
(3) adding the waste rubber particles prepared in the step (1) into the composite gel, stirring for 6 hours at 60 ℃, taking out the waste rubber particles, drying by using supercritical carbon dioxide, wherein the mass ratio of the composite gel to the waste rubber particles is 1:20, and the method for drying the waste rubber particles by using the supercritical carbon dioxide comprises the following steps: transferring the waste rubber particles into a high-pressure reaction kettle, introducing pure nitrogen to completely remove residual air in the reaction kettle, introducing liquid carbon dioxide, drying for 11h under the conditions that the critical temperature is 33 ℃ and the critical pressure is 7.8MPa, releasing gas at the rate of 0.3MPa/min, and naturally cooling to room temperature when the pressure in the reaction kettle is reduced to be more than 0.1 MPa.
Example 10: an environment-friendly antifreezing concrete is different from the embodiment 2 in that the waste rubber particles in the antifreezing agent are pretreated by the following steps: (1) fully soaking the waste rubber particles in a sodium hydroxide solution with the concentration of 0.1%, standing for 22h, cleaning, airing, then putting the waste rubber particles into a silane coupling agent KH570 solution with the mass fraction of 0.2%, uniformly stirring, airing for later use, wherein the mass ratio of the waste rubber particles to the sodium oxide solution to the silane coupling agent KH570 solution is 1:1.4: 1.4;
(2) taking silica sol, adding carbon black and alumina, and uniformly mixing to obtain composite gel, wherein the mass ratio of the silica sol to the carbon black to the alumina is 1:0.6: 0.8;
(3) adding the waste rubber particles prepared in the step (1) into the composite gel, stirring for 5 hours at 70 ℃, taking out the waste rubber particles, drying by using supercritical carbon dioxide, wherein the mass ratio of the composite gel to the waste rubber particles is 1:25, and the method for drying the waste rubber particles by using the supercritical carbon dioxide comprises the following steps: transferring the waste rubber particles into a high-pressure reaction kettle, introducing pure nitrogen to completely remove residual air in the reaction kettle, introducing liquid carbon dioxide, drying for 11h under the conditions that the critical temperature is 33 ℃ and the critical pressure is 7.8MPa, releasing gas at the rate of 0.3MPa/min, and naturally cooling to room temperature when the pressure in the reaction kettle is reduced to be more than 0.1 MPa.
Example 11: an environment-friendly antifreezing concrete is different from the embodiment 2 in that the waste rubber particles in the antifreezing agent are pretreated by the following steps: (1) fully soaking the waste rubber particles in a sodium hydroxide solution with the concentration of 0.2%, standing for 20h, cleaning, airing, putting the cleaned and aired waste rubber particles into a silane coupling agent KH570 solution with the mass fraction of 0.1%, uniformly stirring, airing for later use, wherein the mass ratio of the waste rubber particles to the sodium oxide solution to the silane coupling agent KH570 solution is 1:1.5: 1.5;
(2) taking silica sol, adding carbon black and alumina, and uniformly mixing to obtain composite gel, wherein the mass ratio of the silica sol to the carbon black to the alumina is 1:0.7: 0.9;
(3) adding the waste rubber particles prepared in the step (1) into the composite gel, stirring for 4 hours at 80 ℃, taking out the waste rubber particles, drying by using supercritical carbon dioxide, wherein the mass ratio of the composite gel to the waste rubber particles is 1:30, and the method for drying the waste rubber particles by using the supercritical carbon dioxide comprises the following steps: transferring the waste rubber particles into a high-pressure reaction kettle, introducing pure nitrogen to completely remove residual air in the reaction kettle, introducing liquid carbon dioxide, drying for 11h under the conditions that the critical temperature is 33 ℃ and the critical pressure is 7.8MPa, releasing gas at the rate of 0.3MPa/min, and naturally cooling to room temperature when the pressure in the reaction kettle is reduced to be more than 0.1 MPa.
Example 12: an environment-friendly antifreeze concrete is different from the concrete of example 9 in that the waste rubber particles are not subjected to the step (1) in the pretreatment.
Example 13: an environment-friendly antifreeze concrete is different from the concrete of example 9 in that the waste rubber particles are not subjected to the step (2) in the pretreatment.
Example 14: an environment-friendly antifreeze concrete is different from the concrete of example 2 in that the modified starch in the antifreeze agent is prepared by the following method: mixing 1.8kg of carboxymethyl starch with 2kg of water, stirring for 3h at 80 ℃, cooling, adding 0.05kg of ammonium persulfate, stirring for 15min, adding 1.4kg of acrylic acid, 1.2kg of acrylamide and 0.08kg of N, N-methylene bisacrylamide, reacting for 2.5h at 70 ℃, washing, soaking for 20h by using 1moL/L of sodium hydroxide solution, drying to constant weight at 60 ℃, and crushing to obtain the modified starch.
Example 15: an environment-friendly antifreeze concrete is different from the concrete of example 2 in that the modified starch in the antifreeze agent is prepared by the following method: mixing 2.1kg of carboxymethyl starch with 2.5kg of water, stirring for 2.5h at 85 ℃, cooling, adding 0.08kg of ammonium persulfate, stirring for 20min, adding 1.7kg of acrylic acid, 1.8kg of acrylamide and 0.14kg of N, N-methylene-bisacrylamide, reacting for 2.2h at 75 ℃, washing, soaking for 20h by using 1moL/L of sodium hydroxide solution, drying to constant weight at 60 ℃, and crushing to obtain the modified starch.
Example 16: an environment-friendly antifreeze concrete is different from the concrete of example 2 in that the modified starch in the antifreeze agent is prepared by the following method: mixing 2.6kg of carboxymethyl starch with 3kg of water, stirring for 2h at 90 ℃, cooling, adding 0.1kg of ammonium persulfate, stirring for 20min, adding 2kg of acrylic acid, 2.5kg of acrylamide and 0.2kg of N, N-methylene bisacrylamide, reacting for 2h at 80 ℃, washing, soaking for 20h by using 1moL/L of sodium hydroxide solution, drying to constant weight at 60 ℃, and crushing to obtain the modified starch.
Example 17: an environment-friendly antifreeze concrete is different from the concrete in example 9 in that the modified starch in the modified antifreeze agent is prepared by the following method: mixing 2.6kg of carboxymethyl starch with 3kg of water, stirring for 2h at 90 ℃, cooling, adding 0.1kg of ammonium persulfate, stirring for 20min, adding 2kg of acrylic acid, 2.5kg of acrylamide and 0.2kg of N, N-methylene bisacrylamide, reacting for 2h at 80 ℃, washing, soaking for 20h by using 1moL/L of sodium hydroxide solution, drying to constant weight at 60 ℃, and crushing to obtain the modified starch.
Comparative example
Comparative example 1: an environment-friendly antifreeze concrete is different from the concrete of example 2 in that modified starch is not added in the antifreeze agent.
Comparative example 2: an environment-friendly antifreezing concrete is different from the environment-friendly antifreezing concrete in example 2 in that graphene oxide is not added into the antifreezing agent.
Comparative example 3: an environment-friendly antifreeze concrete is different from the antifreeze concrete in example 2 in that an eggshell membrane is not added in the antifreeze agent.
Comparative example 4: an environment-friendly antifreeze concrete is different from the antifreeze concrete in example 2 in that iron tailing powder is not added into the antifreeze agent.
Comparative example 5: an environment-friendly antifreeze concrete is different from the antifreeze concrete in example 2 in that urea, sodium hydroxide and cellulose are not added in the antifreeze agent.
Comparative example 6: a preparation method of frost-resistant concrete comprises the following steps: weighing 320kg of cement, 110kg of fly ash, 620kg of fine aggregate, 1150kg of coarse aggregate, 5kg of water reducing agent, 4kg of antifreeze agent and 150kg of water according to the following mixture ratio; adding a water reducing agent and an antifreeze agent into a stirring barrel filled with water, starting a stirrer to stir materials in the stirring barrel, controlling the stirring speed at 3000r/min, and uniformly mixing to obtain an additive solution; uniformly stirring the fine aggregate and the coarse aggregate to obtain an aggregate mixture; stirring and mixing cement and fly ash to obtain a sizing material mixture; uniformly mixing the sizing mixture and the aggregate mixture to obtain a premix; and adding the additive solution into the premix, and uniformly stirring to obtain the antifreezing concrete.
Comparative example 7: the antifreeze concrete is obtained by the following method: uniformly mixing 250kg of cement, 100kg of mineral powder, 70kg of fly ash, 660kg of artificial sand, 80kg of steel slag, 1100kg of broken stone, 3.4kg of aliphatic alcohol sulfonate air entraining agent, 4.8kg of polycarboxylic acid high-performance water reducing agent, 30kg of organosilicon waterproofing agent, 90kg of polypropylene fiber and 100kg of water; wherein, the grain diameter of the steel slag is 1-3mm, the length of the polypropylene fiber is 6mm, and the steel slag is subjected to the following hydrophobic treatment: s1, dissolving sodium methylsiliconate in water to prepare a sodium methylsiliconate solution with the weight percentage of 0.1%, and then adding portland cement into the sodium methylsiliconate solution to enable the weight percentage of the portland cement to be 30% to prepare an impregnation solution; s2, dipping the steel slag in the dipping solution for 3 seconds; and S3, airing the steel slag dipped in the S2 at room temperature.
Performance test
The concrete mixtures prepared in the examples and comparative examples were tested for their performance and the results are reported in table 3.
1. Strength loss rate and mass loss rate: detecting according to section 4.1 in GB/T50082-1009 test method and standard for long-term performance and durability of common concrete;
2. compressive strength: and (3) manufacturing a standard test block according to GB/T50081-2016 standard of test methods for mechanical properties of common concrete, and measuring the compressive strength of the standard test block after 7d and 28d of maintenance.
3. Anti-permeability performance: detecting according to GB/T50082-2009 test method standards for long-term performance and durability of common concrete, wherein the osmotic pressure is 2MPa, and the pressurizing time is 48 h;
4. detection of purification rate of nitrogen oxides: concrete slurry was prepared according to the methods of examples and comparative examples and cured and molded under standard conditions to prepare 20cm × 20cm test pieces, 10 pieces of each of the concrete test pieces prepared in examples and comparative examples were taken and placed in sealed glass containers of the same specifications, nitrogen oxide of the same solubility was charged into each glass container, the initial concentration was recorded as c1, the concentration of nitrogen oxide in each glass container at 24 hours and 48 hours was measured as c2 with a naphthyl ethylenediamine hydrochloride spectrophotometer, and the purification rate (%) of nitrogen oxide was calculated according to the following formula: (c1-c2)/c 1X 100%, and the test results of 10 concrete test pieces prepared in the same example or comparative example were averaged.
TABLE 3 Performance test results for environmentally friendly anti-freeze concrete
As can be seen by combining the data in examples 1-8 and Table 3, the antifreeze prepared in preparation example 4 in which the antifreeze was incorporated in example 1 has a mass loss rate of 0.53% and a strength loss rate of 9.46% after 100 freeze-thaw cycles, while the antifreeze prepared in examples 2-8 in which the antifreeze was incorporated in preparation examples 1-3 has a mass loss rate of 0.32-0.39% and a strength loss rate of 8.06-8.63% after 100 freeze-thaw cycles, and has significantly improved antifreeze performance, and after the antifreeze prepared in the present application, the concrete has a performance of adsorbing nitrogen oxides, can purify air, and has improved impermeability.
In examples 9 to 11, after the waste rubber particles are pretreated, the mass loss rate of the prepared concrete after freeze-thaw cycles is significantly reduced to only 0.24% and the compressive strength loss rate is 7.24%, which indicates that the pretreated waste rubber particles can significantly enhance the frost resistance of the concrete, and the adsorption performance of the concrete to nitrogen oxides is improved and the purification effect is significant due to the addition of alumina and carbon black when the waste rubber particles are pretreated.
In example 12, when the waste rubber particles are pretreated, sodium hydroxide and the silane coupling agent KH570 are not used, and after the concrete prepared in example 12 is subjected to freeze-thaw cycling, the mass loss rate is 0.31% and the compressive strength loss rate is 8.07%, compared with examples 9-11, the anti-freezing performance is significantly reduced, which indicates that the anti-freezing performance of the concrete can be effectively improved by treating the waste rubber particles with sodium hydroxide and the silane coupling agent KH 570.
In example 13, when the waste rubber particles are pretreated, silica sol, carbon black and alumina are not used, the water penetration height of the concrete prepared in example 13 is 0.39cm, and the elimination rate of nitrogen oxides is significantly reduced compared with example 9, which shows that the pretreatment of the waste rubber particles with the silica sol, carbon black and alumina not only can enhance the impermeability of the concrete, but also can increase the adsorption and purification effects of the concrete on nitrogen oxides.
Compared with the example 2, the modified starch prepared in the application is adopted, and the detection data in the table 3 show that the concrete prepared in the examples 14 to 16 is reduced in mass loss rate and compressive strength loss rate after freeze-thaw cycling, and the absorption rate of the modified starch to nitrogen oxides is increased, which shows that the modified starch prepared in the application can not only enhance the frost resistance of the concrete, but also improve the purification capacity of the concrete to nitrogen oxides in automobile exhaust.
Example 17 compared with example 2, not only the waste rubber particles are pretreated, but also the modified starch prepared in the application is adopted, and as can be seen from the detection data in table 2, compared with example 2, example 9 and example 14, the concrete prepared in example 17 has improved frost resistance, impermeability and nitrogen oxide purifying capacity, and is the best example of the application.
Comparative example 1 because modified starch is not added to the antifreeze, the concrete prepared in comparative example 1 has reduced impermeability and frost resistance, and the absorption rate of nitrogen oxide is reduced, which shows that the addition of the modified starch can reduce the inner pores of the concrete, increase the compactness, improve the impermeability, provide expansion stress for water freezing at low temperature, and improve the frost resistance.
Compared with the concrete prepared by the embodiment 2, the concrete prepared by adding no graphene oxide in the antifreeze agent has the advantages of reduced compressive strength, reduced frost resistance and reduced adsorption effect on nitrogen oxides, and the graphene oxide can enhance the compressive strength, the frost resistance and the purification effect of the concrete.
Compared with the concrete prepared in the example 2, the concrete prepared in the comparative examples 3 and 4 has lower anti-permeability performance because the egg shell membrane is not added in the antifreeze, and the iron tailing powder is not added in the antifreeze in the comparative example 4.
In comparative example 5, sodium hydroxide and urea were not added, the compressive strength of the concrete was reduced, the impermeability was reduced, and the porosity of the concrete was increased, the porosity connectivity was increased, and the impermeability was reduced due to the reduced water storage capacity of the antifreeze.
Comparative example 6 and comparative example 7 are prior art prepared frost resistant concrete, its frost resistance is inferior to this application, and its purification effect to nitrogen oxide is relatively poor.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The environment-friendly anti-freezing concrete is characterized by comprising the following components in parts by weight: cement 420-570, sand 572-656, stone 825-940, water 170-210, admixture 51-70, admixture 58.8-80.6, waste rubber particles 40-60 and antifreeze 45-60;
the antifreeze agent comprises the following components in parts by weight: 5-10 parts of modified starch, 10-15 parts of graphene oxide, 2.4-5 parts of iron tailing powder, 4.3-6.5 parts of eggshell membrane, 2.5-5 parts of sodium hydroxide, 2.5-4 parts of urea and 5-8 parts of cellulose.
2. The environmentally friendly antifreeze concrete of claim 1, wherein: the preparation method of the antifreeze agent comprises the following steps: (1) mixing graphene oxide and modified starch, and dispersing for 1.5-2 hours by ultrasonic waves to obtain a graphene oxide/modified starch intercalation composite material;
(2) dissolving urea and sodium hydroxide with water respectively, mixing, adding the graphene oxide/modified starch intercalation composite material, performing ultrasonic treatment for 1-2h, cooling to the temperature of- (12-13) DEG C, adding cellulose and 2-epoxy-3 chloropropane, stirring uniformly at room temperature, adding the eggshell membrane and the iron tailing powder into a water bath at the temperature of 25-30 ℃ for 40-48h, drying and crushing to prepare the antifreeze agent.
3. The environmentally friendly antifreeze concrete of claim 2, wherein said waste rubber particles are pretreated by: (1) fully soaking waste rubber particles in a sodium hydroxide solution with the concentration of 0.01-0.2%, standing for 20-24h, cleaning, airing, putting the waste rubber particles into a silane coupling agent KH570 solution with the mass fraction of 0.1-0.2%, uniformly stirring, and airing for later use, wherein the mass ratio of the waste rubber particles to the sodium oxide solution to the silane coupling agent KH570 solution is 1:1.3-1.5: 1.3-1.5;
(2) taking silica sol, adding carbon black and alumina, and uniformly mixing to prepare composite gel, wherein the mass ratio of the silica sol to the carbon black to the alumina is 1:0.5-0.7: 0.7-0.9;
(3) adding the waste rubber particles prepared in the step (1) into the composite gel, stirring for 4-6h at 60-80 ℃, taking out the waste rubber particles, and drying by supercritical carbon dioxide, wherein the mass ratio of the composite gel to the waste rubber particles is 1: 20-30.
4. The environmentally friendly antifreeze concrete of claim 2, wherein said modified starch is prepared by the following steps: mixing 1.8-2.6 parts by weight of carboxymethyl starch with water, stirring for 2-3 hours at 80-90 ℃, cooling, adding 0.05-0.1 part by weight of ammonium persulfate, stirring for 15-20min, adding 1.4-2 parts by weight of acrylic acid, 1.2-2.5 parts by weight of acrylamide and 0.08-0.2 part by weight of N, N-methylene bisacrylamide, reacting for 2-2.5 hours at 70-80 ℃, washing, soaking in a sodium hydroxide solution, drying and crushing to obtain the modified starch.
5. The environment-friendly antifreeze concrete as claimed in claim 1, wherein the admixture is HTJS-3 type polycarboxylic acid high-performance water reducing agent and expanding agent, and the mass ratio of the HTJS-3 type polycarboxylic acid high-performance water reducing agent to the expanding agent is 1: 3.57-3.59.
6. The environment-friendly antifreeze concrete as claimed in claim 1, wherein the admixture is class II fly ash, the fineness (45 μm square mesh screen residue) is less than or equal to 12%, the water demand ratio is 98%, the loss on ignition is less than or equal to 4.5%, and the specific surface area is 280-300 m-2Kg, density of 2.69-2.75g/cm3。
7. The environment-friendly antifreeze concrete of claim 1, wherein the sand comprises river sand and machine-made sand in a mass ratio of 1:0.9-1.1, the river sand is sand in zone II, the fineness modulus is 2.8, the mud content is 1.9%, the machine-made sand is coarse sand, the fineness modulus is 3.3, and the stone powder content is 3.6%.
8. The environmentally friendly antifreeze concrete of claim 1, wherein said gravel comprises 5-21.5mm continuous graded crushed stone, has a mud content of 0.9%, a mud cake content of 0.3%, and an apparent density of 2500-3The bulk density is 1400-1600kg/m3。
9. The environmentally friendly antifreeze concrete of claim 1, wherein the specific surface area of said iron tailings powder is 770-800m2Per kg, the silica content was 68.63%, the alumina content was 6.72%.
10. A method for preparing an environmentally friendly frost resistant concrete according to any of claims 1-9, comprising the steps of:
s1, adding the admixture and the anti-freezing anti-seepage agent into water, and uniformly mixing to obtain a premix;
and S2, mixing the cement, the sand, the pebbles, the admixture and the waste rubber particles, adding the premix, and uniformly mixing to obtain the environment-friendly antifreezing concrete.
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