CN110395884B - Bionic self-repairing concrete and preparation method thereof - Google Patents

Bionic self-repairing concrete and preparation method thereof Download PDF

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CN110395884B
CN110395884B CN201910786078.3A CN201910786078A CN110395884B CN 110395884 B CN110395884 B CN 110395884B CN 201910786078 A CN201910786078 A CN 201910786078A CN 110395884 B CN110395884 B CN 110395884B
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parts
bioactive glass
microspheres
concrete
mesoporous bioactive
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CN110395884A (en
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谢祥明
余青山
姚楚康
胡磊
李意
赵雅玲
邱晓艳
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Guangdong No 2 Hydropower Engineering Co Ltd
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Guangdong No 2 Hydropower Engineering Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/10—Forming beads
    • C03B19/108—Forming porous, sintered or foamed beads
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
    • C03C11/007—Foam glass, e.g. obtained by incorporating a blowing agent and heating
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/0095—Solution impregnating; Solution doping; Molecular stuffing, e.g. of porous glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • 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
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/022—Carbon
    • C04B14/026—Carbon of particular shape, e.g. nanotubes
    • 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
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/02—Agglomerated materials, e.g. artificial aggregates
    • C04B18/027—Lightweight materials
    • 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
    • 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
    • C04B20/1018—Coating or impregnating with organic materials
    • C04B20/1029—Macromolecular compounds
    • C04B20/1033—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C04B20/1018—Coating or impregnating with organic materials
    • C04B20/1029—Macromolecular compounds
    • C04B20/1037—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/06—Oxides, Hydroxides
    • C04B22/068—Peroxides, e.g. hydrogen peroxide
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength

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  • Manufacturing & Machinery (AREA)
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  • Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention discloses bionic self-repairing concrete and a preparation method thereof, and the bionic self-repairing concrete is characterized by comprising the following raw materials in parts by weight: 240-360 parts of cement, 180-250 parts of active admixture, 1300-1600 parts of aggregate, 60-90 parts of mesoporous bioactive glass composite microspheres, 20-30 parts of calcium peroxide microspheres, 20-30 parts of carbon nano-tubes, 8-16 parts of polycarboxylic acid water reducing agent and 190-220 parts of water. The bionic self-repairing concrete has the rapid self-repairing capability, can continuously and automatically repair micro cracks or micro damages of different deep layers in the concrete, promotes the continuous increase of the matrix strength after crack repair, improves the strength and the durability of the concrete, and has the advantages of wide repair range, rapid repair and lasting repair.

Description

Bionic self-repairing concrete and preparation method thereof
Technical Field
The invention relates to the technical field of building materials, in particular to bionic self-repairing concrete and a preparation method thereof.
Background
The inherent defect of large brittleness of concrete material seriously influences the crack resistance of the concrete material. Actual engineering often involves microscopic damage such as microcracking of the substrate, which is often not visible, and certainly not repaired. If the damaged parts cannot be repaired in time, the strength and the durability of the concrete material are influenced, the normal use performance of the structure is influenced, the service life is shortened, and macro cracks can be caused and brittle fracture can occur, so that serious catastrophic accidents can be caused. The repair mode of the traditional concrete material mainly comprises regular maintenance and after-repair, and the passive and passive repair mode has huge cost and poor effect and can not meet the requirements of modern multifunctional and intelligent buildings on the concrete material. The research and development of the bionic self-repairing concrete, which can automatically repair and recover damaged parts and improve the performance of concrete materials, has become the development trend of concrete technology. The bionic self-repairing of the concrete material is a function of simulating the healing of biological tissue damage, and special components are embedded in a cement matrix to form an intelligent self-repairing system. When the matrix generates damage cracks, the restoration system embedded in the matrix releases the restoration agent under the condition of force, heat or chemical damage, bonds and blocks the cracks, and prevents the cracks from further expanding, thereby achieving the purpose of restoration. Compared with the traditional repair technology, the method has the advantages of low cost, no dependence on external operation, reproducibility and the like.
According to different self-repairing mechanisms of concrete, the self-repairing modes of the concrete mainly comprise mineral self-repairing modes, microcapsule self-repairing modes, permeation crystallization self-repairing modes, electrochemical self-repairing modes, shape memory alloy self-repairing modes, microorganism self-repairing modes and the like, wherein the microorganism self-repairing concrete has good compatibility with a cement-based material due to the fact that calcium carbonate generated by microorganisms is induced by the microorganism self-repairing concrete, is environment-friendly, and is concerned by more people in recent years. Under the stimulation of specific environment and nutrient condition, the microbe can quickly separate out several mineral crystals, such as carbonate, phosphate, oxide and cell material. The calcium carbonate deposition can fill the cracks caused by concrete cracking to a certain extent, and the gelling property of the calcium carbonate can improve the strength and the durability of the cement-based material. However, the practical application of the current microbial self-repairing concrete still faces many problems, mainly including the following points: 1) most of concrete is in a high-alkali severe environment, microorganisms are directly mixed into the concrete, and the repairing effect cannot be exerted due to premature death of the microorganisms. 2) The micro cracks in the deep concrete have poor permeability to oxygen and water, and the microorganisms are difficult to activate in the oxygen-deficient and water-deficient environment, so that the repairing effect cannot be exerted. 3) The anaerobic microorganisms are adopted for repair, and ammonia gas is generated during the enzymatic action of anaerobic bacteria, so that the human health is harmed, and the ammonia gas can be converted into nitric acid to corrode reinforcing steel bars. 4) The microorganism recovers metabolism function after activation, carbon dioxide is generated by breathing, and the carbon dioxide reacts with calcium ions in the cement-based material in a humid environment to generate calcium carbonate so as to fill cracks. 5) The microcapsule loaded microorganism is adopted for repairing, once the microcapsule is broken to release the microorganism, a cavity is left in the concrete to reduce the strength of the concrete, the existing microcapsules are mostly high molecular polymers and are difficult to degrade in the natural environment of the concrete, and residues of the microcapsules can cause negative effects on a cement-based matrix.
The Chinese patent application with publication number CN 104261736A discloses a method for preparing a cement-based material with deep self-repairing function, which comprises the steps of firstly, fixedly loading carbonic anhydrase-producing bacteria and yeast powder in a carrier A, fixedly loading a substrate, nutrient substances and deionized water in a carrier B, then mixing a mixed carrier of the carrier A and the carrier B with materials such as cement, sand and water, stirring and molding, and carrying out standard maintenance to obtain the cement-based material, wherein the carrier A and the carrier B are ceramsite, clay or zeolite. The invention adopts a mode of respectively immobilizing bacteria, substrates and nutrient substances, not only limits the diffusion of the bacteria, the substrates and products and cannot ensure the quick reaction and the full reaction between the bacteria and the substances, but also the mixed carrier of the carrier A and the carrier B is directly blended into concrete as light aggregate to replace the use amount of partial aggregate, particularly the use of coarse aggregate, can cause great strength damage to the concrete, although the strength after the repair has certain recovery compared with the untreated state, the strength loss caused by the doped carrier can not be compensated far, and the application of the cement-based material in engineering practice is limited.
Disclosure of Invention
The invention aims to provide bionic self-repairing concrete and a preparation method thereof, the concrete has the rapid self-repairing capability, can continuously and automatically repair micro cracks or micro damages at different deep layers in the concrete, promotes the continuous increase of the matrix strength after crack repair, improves the strength and durability of the concrete, and has the advantages of wide repair range, rapid repair and lasting repair.
The technical scheme adopted by the invention is as follows:
the bionic self-repairing concrete comprises the following raw materials in parts by weight: 240-360 parts of cement, 180-250 parts of active admixture, 1300-1600 parts of aggregate, 60-90 parts of mesoporous bioactive glass composite microspheres, 20-30 parts of calcium peroxide microspheres, 20-30 parts of carbon nano-tubes, 8-16 parts of polycarboxylic acid water reducing agent and 190-220 parts of water.
Preferably, the mesoporous bioactive glass composite microspheres take mesoporous bioactive glass microspheres as carriers, aerobic alkaline-resisting bacillus is loaded in the mesoporous bioactive glass composite microspheres, and polyvinyl alcohol is coated outside the mesoporous bioactive glass composite microspheres.
Preferably, the mesoporous bioactive glass microspheres in the mesoporous bioactive glass composite microspheres have the particle size of 100-600 nm, the pore diameter of 2-50 nm and the specific surface area of 500-1000 m2(ii) in terms of/g. The mesoporous bioactive glass microsphere is CaO-SiO composed of oxides of calcium, silicon, aluminum and phosphorus2-Al2O3-P2O5The preparation method of the system adopts the existing template method for preparation, and specifically comprises the following steps: (1) the triblock copolymer Pluronic F127 (molecular formula EO)106PO70EO106EO is ethylene oxide and PO is propylene oxide; average molecular weight 12600) was dissolved in a mixed solvent composed of absolute ethyl alcohol and glacial acetic acid (volume ratio of absolute ethyl alcohol to glacial acetic acid is 5:2) wherein the mixing ratio of the Pluronic F127 to the mixed solvent is 1g:25mL, and the mixture is stirred and mixed uniformly to obtain a mixed solution A. (2) Adding an oxide precursor mixture into the mixed solution A obtained in the step (1), stirring and dissolving to obtain a mixed solution B, wherein the mass ratio of the oxide precursor mixture to the mixed solution A is 1: 3.5-4, the oxide precursor mixture is formed by mixing calcium nitrate tetrahydrate, methyl orthosilicate, aluminum nitrate nonahydrate and trimethyl phosphate, and the mixing ratio is as follows: SiO 22：Al2O3：P2O5Is calculated as 90:50:15: 5. (3) And (3) soaking a three-dimensional ordered macroporous-structure polystyrene template with the pore diameter of 470nm into the mixed solution B obtained in the step (2), placing the soaked mixed solution B in a 60 ℃ oven for sol gelation for 48-72 h to form a gel-like solid, drying the gel-like solid at 60-100 ℃, then placing the gel-like solid in a muffle furnace for calcination at 550-650 ℃ for 3-5 h, and controlling the heating rate at 0.5-3 ℃/min during calcination to obtain the mesoporous bioactive glass microsphere.
The composition system of the mesoporous bioactive glass microsphere is CaO-SiO2-Al2O3-P2O5Compared with the common bioactive glass composition system CaO-SiO2-P2O5By introducing Al2O3The components obviously improve the mechanical strength of the mesoporous bioactive glass, so that the mesoporous bioactive glass composite microspheres can not cause the reduction of the mechanical property of the concrete when being mixed into the concrete.
Preferably, the loading proportion of the aerobic alkali-resistant bacillus in the mesoporous bioactive glass composite microspheres is 1g of mesoporous bioactive glass microspheres: 2.5-5 mL of bacterial liquid, wherein the concentration of the bacterial liquid is (4-5) x 107one/mL.
The mesoporous bioactive glass composite microsphere is prepared by the following method:
(1) culturing aerobic alkali-resistant bacillus, centrifuging to obtain bacterial mud, and re-suspending the bacterial mud with a culture medium to obtain a suspension with a concentration of (4-5) x 107Bacterial liquid per mL; mesoporous bioactive glass microspheres prepared by vacuum impregnation methodSoaking the mixture and bacterial liquid according to the proportion of 1g: 2.5-5 mL, and drying at 30-40 ℃ to obtain mesoporous bioactive glass microspheres loaded with aerobic alkali-resistant bacillus inside;
(2) dissolving polyvinyl alcohol in water to prepare a solution with the mass fraction of 20-30%, uniformly spraying the solution on the surface of the mesoporous bioactive glass microsphere which is prepared in the step (1) and is loaded with aerobic alkali-resistant bacillus inside, wherein the mass ratio of the polyvinyl alcohol to the mesoporous bioactive glass microsphere is 3-4.5: 1, uniformly mixing, and drying at the temperature of 30-40 ℃ to obtain the mesoporous bioactive glass composite microsphere.
Preferably, the aerobic type alkali-fast Bacillus is Bacillus cohnii DSM 6307 or Bacillus pseudofirus DSM 8715, and the culture medium comprises: each liter of culture medium contains 1-5 g of peptone, 20-30 g of maltodextrin, 8-10 g of ammonium chloride, 1-4 g of sodium citrate, 0.5-1.5 g of magnesium sulfate and the balance of water.
Preferably, the particle size of the calcium peroxide microspheres is 1-5 μm, and the surfaces of the calcium peroxide microspheres are coated with a polybutylene succinate (PBS) protective film.
Preferably, the preparation of the calcium peroxide microspheres comprises the following steps: dissolving polybutylene succinate in chloroform to prepare a solution with the mass fraction of 5-10%, uniformly spraying the solution on the surface of calcium peroxide to enable the thickness of a film layer of the polybutylene succinate to be 20-40 nm, and performing vacuum drying and chloroform recovery to obtain the calcium peroxide microspheres.
Preferably, the active admixture is at least one selected from fly ash, slag powder, phosphorous slag powder, silica fume, zeolite powder, sepiolite powder and quartz powder.
Preferably, the aggregate is composed of fine aggregate and coarse aggregate according to a mass ratio of 1 (1.4-1.8); the fine aggregate is river sand, lake sand, mountain sand or desalted sea sand; the coarse aggregate is broken stone or pebble.
The bionic self-repairing concrete is prepared by the following method, and comprises the following steps: mixing cement, active admixture, aggregate, mesoporous bioactive glass composite microspheres, calcium peroxide microspheres, carbon nanotubes, polycarboxylic acid water reducing agent and water, uniformly stirring, pouring and molding, removing a mold, and maintaining to obtain the concrete.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the mesoporous bioactive glass composite microspheres are added into the concrete as a main repairing agent, so that the concrete has high-efficiency repairing capability. The mesoporous bioactive glass composite microsphere takes the mesoporous bioactive glass microsphere as a carrier, and the mesoporous bioactive glass has a highly ordered pore structure, uniform pore size distribution, high porosity and large specific surface area, can efficiently load aerobic alkali-resistant bacillus and nutrient components of a culture medium, and avoids the bacterial activity from being damaged by the concrete high-alkali severe environment. The mesoporous bioactive glass microsphere contains CaO and SiO2、Al2O3、P2O5The components not only provide a good microenvironment for the growth of microorganisms, but also provide an inorganic component source for the induced mineralization of bacteria, avoid the bacteria from meeting the demand of remineralization by consuming the internal products of concrete, and improve the stability of a concrete structure. When concrete is damaged, a large amount of water permeates into the microcracks, and alkali metal ions in the mesoporous bioactive glass and H in the aqueous solution+Ion exchange is carried out, then the silicon dioxide network is broken to form SiOH, the SiOH is condensed into Si-O-Si on the surface of the mesoporous bioactive glass to form a silicon-rich layer, and the silicon-rich layer adsorbs non-crystalline Ca and PO4、CO2The formation of the hydroxyapatite on the surface of the mesoporous bioactive glass can promote the healing of cracks and improve the strength of concrete, and can be used as a carrier to load bacillus again to maintain the activity of the bacillus, and when the cracks are formed again, the bacillus can play a role in repairing again. The apatite mineralization of the mesoporous bioactive glass and the calcium carbonate mineralization of the microorganisms are carried out simultaneously, so that the damage of the concrete is promoted to be quickly healed, and the bionic self-repairing concrete has the quick self-repairing capability.
(2) According to the invention, the carbon nanotubes are added into the concrete, so that the toughness of the concrete can be improved, the anti-cracking performance of the concrete can be improved, and the strength and the durability can be improved. Particularly, the polyvinyl alcohol on the surface of the mesoporous bioactive glass composite microsphere is used for promoting the formation of a stable three-dimensional network structure among the carbon nano-tubes, the mesoporous bioactive glass composite microsphere and the concrete, so that the development of cracks is delayed or inhibited, the physical and mechanical properties of the mortar can be enhanced, and the mechanical properties of the repaired cracks are promoted to be improved.
(3) The invention adds the calcium peroxide microspheres into the concrete, utilizes the coating effect of the poly butylene succinate to ensure that the calcium peroxide stably exists in the concrete, meanwhile, the influence of the calcium peroxide on the activity of the bacillus is blocked, when the concrete is damaged, a large amount of water penetrates into the concrete to form an alkaline solution, the poly (butylene succinate) is promoted to degrade, the exposed calcium peroxide can slowly release oxygen when meeting water to generate calcium hydroxide, the calcium hydroxide absorbs carbon dioxide released by metabolism of the bacillus or carbon dioxide penetrating into the concrete in the air to generate calcium carbonate precipitate, and the healing of concrete cracks is further promoted, meanwhile, the released oxygen can activate the bacillus, and is particularly helpful for activating the bacillus in the oxygen-deficient environment deep in the concrete cracks, breaking the dormancy of the bacillus and promoting the restoration of the bacillus deep in the cracks.
In conclusion, the bionic self-repairing concrete has the rapid self-repairing capability, can continuously and automatically repair micro cracks or micro damages at different deep layers in the concrete, promotes the continuous increase of the matrix strength after crack repair, improves the strength and durability of the concrete, and has the advantages of wide repair range, rapid repair and lasting repair.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof. In the following examples, all the raw materials were commercially available products unless otherwise specified.
EXAMPLE 1 preparation of mesoporous bioactive glass microspheres
The preparation method of the mesoporous bioactive glass microspheres by adopting a template method comprises the following steps:
(1) will threeBlock copolymer Pluronic F127 (formula EO)106PO70EO106EO is ethylene oxide and PO is propylene oxide; average molecular weight 12600) is dissolved in a mixed solvent composed of absolute ethyl alcohol and glacial acetic acid (the volume ratio of the absolute ethyl alcohol to the glacial acetic acid is 5:2), the mixing ratio of the Pluronic F127 to the mixed solvent is 1g:25mL, and the mixture is stirred and mixed uniformly to obtain a mixed solution A.
(2) And (2) adding 100g of an oxide precursor mixture into 400g of the mixed solution A obtained in the step (1), stirring and dissolving to obtain a mixed solution B, wherein the oxide precursor mixture is prepared by mixing 51.19g of calcium nitrate tetrahydrate, 18.33g of methyl orthosilicate, 27.11g of aluminum nitrate nonahydrate and 3.37g of trimethyl phosphate according to the mixing ratio of CaO: SiO 22：Al2O3：P2O5Is calculated as 90:50:15: 5.
(3) And (3) soaking a three-dimensional ordered macroporous-structure polystyrene template with the aperture of 470nm in the mixed solution B obtained in the step (2) for 24 hours, placing in a 60 ℃ oven for sol gelation for 72 hours to form a gel-like solid, drying the gel-like solid at 80 ℃, then placing in a muffle furnace for calcination at 600 ℃ for 3 hours, and controlling the heating rate to be 1.5 ℃/min during calcination to obtain the mesoporous bioactive glass microsphere.
EXAMPLE 2 preparation of mesoporous bioactive glass composite microspheres
The preparation method of the mesoporous bioactive glass composite microsphere comprises the following steps:
(1) inoculating aerobic alkaline-resisting Bacillus (Bacillus cohnii DSM 6307) into a culture medium (each liter of the culture medium contains 4.5g of peptone, 30g of maltodextrin, 10g of ammonium chloride, 2g of sodium citrate, 1g of magnesium sulfate and the balance of water, the pH value is 9-10), performing shaking culture at room temperature for 72 hours to obtain a bacterial liquid, centrifuging the bacterial liquid at 4000r/min for 20 minutes to obtain bacterial mud, and re-suspending the bacterial mud with the culture medium to obtain the bacterial mud with the concentration of (4-5) multiplied by 107Bacterial liquid per mL; dipping mesoporous bioactive glass microspheres (prepared in example 1) and bacterial liquid according to the proportion of 1g to 2.5mL by adopting a vacuum dipping method, and drying at 35 ℃ to obtain mesoporous bioactive glass microspheres loaded with aerobic alkali-resistant bacillus inside;
(2) dissolving polyvinyl alcohol in water to prepare a solution with the mass fraction of 30%, uniformly spraying the solution on the surface of the mesoporous bioactive glass microsphere which is prepared in the step (1) and is loaded with aerobic alkali-resistant bacillus, wherein the mass ratio of the polyvinyl alcohol to the mesoporous bioactive glass microsphere is 3:1, uniformly mixing, and drying at 35 ℃ to obtain the mesoporous bioactive glass composite microsphere.
EXAMPLE 3 calcium peroxide microsphere preparation
The preparation method of the calcium peroxide microspheres comprises the following steps: dissolving polybutylene succinate in chloroform to prepare a solution with the mass fraction of 5%, uniformly spraying the solution on the surface of calcium peroxide to enable the thickness of a film layer of the polybutylene succinate to be 20nm, and performing vacuum drying and chloroform recovery to obtain the calcium peroxide microspheres.
Example 4 preparation of Bionically self-repairing concrete
The bionic self-repairing concrete comprises the following raw materials in parts by weight: 325 parts of cement, 130 parts of fly ash, 90 parts of slag powder, 520 parts of river sand, 780 parts of broken stone, 90 parts of mesoporous bioactive glass composite microspheres, 20 parts of calcium peroxide microspheres, 20 parts of carbon nano-tubes, 8 parts of polycarboxylic acid water reducing agent and 200 parts of water.
The preparation method comprises the following steps: mixing cement, fly ash, slag powder, river sand, broken stone, mesoporous bioactive glass composite microspheres, calcium peroxide microspheres, carbon nano-tubes, a polycarboxylic acid water reducing agent and water, uniformly stirring, pouring and forming, removing a mold, and maintaining to obtain the concrete.
Example 5 preparation of Bionically self-repairing concrete
The bionic self-repairing concrete comprises the following raw materials in parts by weight: 275 parts of cement, 125 parts of phosphorus slag powder, 90 parts of slag powder, 667 parts of desalted sea sand, 933 parts of pebbles, 75 parts of mesoporous bioactive glass composite microspheres, 25 parts of calcium peroxide microspheres, 25 parts of carbon nano-tubes, 16 parts of polycarboxylic acid water reducing agent and 220 parts of water.
The preparation procedure is referred to example 4.
Example 6 preparation of Bionically self-repairing concrete
The bionic self-repairing concrete comprises the following raw materials in parts by weight: 280 parts of cement, 100 parts of fly ash, 40 parts of silica fume, 600 parts of river sand, 900 parts of pebbles, 80 parts of mesoporous bioactive glass composite microspheres, 25 parts of calcium peroxide microspheres, 25 parts of carbon nano-tubes, 12 parts of polycarboxylic acid water reducing agent and 190 parts of water.
The preparation procedure is referred to example 4.
Example 7 preparation of Bionically self-repairing concrete
The bionic self-repairing concrete comprises the following raw materials in parts by weight: 340 parts of cement, 145 parts of fly ash, 90 parts of quartz powder, 500 parts of mountain sand, 900 parts of broken stone, 60 parts of mesoporous bioactive glass composite microspheres, 20 parts of calcium peroxide microspheres, 20 parts of carbon nano-tubes, 10 parts of polycarboxylic acid water reducing agent and 195 parts of water.
The preparation procedure is referred to example 4.
Example 8 preparation of Bionically self-repairing concrete
The bionic self-repairing concrete comprises the following raw materials in parts by weight: 360 parts of cement, 150 parts of fly ash, 100 parts of zeolite powder, 500 parts of desalted sea sand, 800 parts of broken stone, 90 parts of mesoporous bioactive glass composite microspheres, 30 parts of calcium peroxide microspheres, 30 parts of carbon nano-tubes, 14 parts of polycarboxylic acid water reducing agent and 210 parts of water.
The preparation procedure is referred to example 4.
Comparative example 1 preparation of bionic self-repairing concrete
The bionic self-repairing concrete comprises the following raw materials in parts by weight: 325 parts of cement, 130 parts of fly ash, 90 parts of slag powder, 520 parts of river sand, 780 parts of broken stone, 90 parts of ceramsite-loaded aerobic alkali-resistant bacillus, 20 parts of carbon nano-tubes, 8 parts of polycarboxylic acid water reducer and 200 parts of water.
The preparation method of the ceramsite loaded aerobic alkali-resistant bacillus comprises the following steps: inoculating aerobic alkaline-resisting Bacillus (Bacillus cohnii DSM 6307) into a culture medium (each liter of the culture medium contains 4.5g of peptone, 30g of maltodextrin, 10g of ammonium chloride, 2g of sodium citrate, 1g of magnesium sulfate and the balance of water, the pH value is 9-10), performing shaking culture at room temperature for 72 hours to obtain a bacterial liquid, centrifuging the bacterial liquid at 4000r/min for 20 minutes to obtain bacterial mud, and re-suspending the bacterial mud with the culture medium to obtain the bacterial mud with the concentration of (4-5) multiplied by 107Bacterial liquid per mL; impregnating ceramsite and bacterial liquid according to the proportion of 1g to 2.5mL by adopting a vacuum impregnation method, and drying at 35 ℃ to obtain ceramsite internally loaded with aerobic alkali-resistant bacillus;
concrete preparation procedure reference was made to example 4.
Comparative example 2 preparation of bionic self-repairing concrete
The bionic self-repairing concrete comprises the following raw materials in parts by weight: 325 parts of cement, 130 parts of fly ash, 90 parts of slag powder, 520 parts of river sand, 780 parts of broken stone, 90 parts of ceramsite-loaded aerobic alkali-resistant bacillus, 20 parts of calcium peroxide microspheres, 20 parts of carbon nano-tubes, 8 parts of polycarboxylic acid water reducer and 200 parts of water.
The preparation of the haydite loaded aerobic alkali-resistant bacillus is the same as that of comparative example 1.
Concrete preparation procedure reference was made to example 4.
Comparative example 3 preparation of bionic self-repairing concrete
The bionic self-repairing concrete comprises the following raw materials in parts by weight: 325 parts of cement, 130 parts of fly ash, 90 parts of slag powder, 520 parts of river sand, 780 parts of broken stone, 90 parts of mesoporous bioactive glass composite microspheres, 20 parts of carbon nano-tubes, 8 parts of polycarboxylic acid water reducing agent and 200 parts of water.
Concrete preparation procedure reference was made to example 4.
Test example I, Performance test
The bionic self-repairing concrete prepared in the embodiments 4-8 and the comparative examples 1-3 is subjected to impermeability and mechanical property tests and mechanical property after crack repairing, the concrete mechanical property test is in reference to GB/T50081-2002 concrete mechanical property test method standards, and the durability test is in reference to GB/T50082-2009 common concrete long-term property and durability test method standards, wherein the mechanical property test is to determine the compressive strength of the concrete after preparation and curing for 7d and 28d, and the mechanical property test after crack repairing is to determine that the concrete has the crack width of 0.2-0.4 mm after the crack repairing passes through the splitting tensile test, and the compressive strength of the concrete after curing for 7d and 28d is performed again.
The test results are shown in Table 1.
TABLE 1 Performance test results for each group of concretes
Figure BDA0002178070180000111
Figure BDA0002178070180000121
The result shows that the bionic self-repairing concrete prepared in the embodiments 4-8 of the invention has better anti-permeability performance and mechanical property, the compressive strength of the cured 7d is 30.7-35.4 MPa, the compressive strength of the cured 28d is 55.4-61.2 MPa, the compressive strength of the cured 7d is 33.5-38.2 MPa after the splitting tensile test is carried out, the compressive strength of the cured 28d is 58.3-64.4 MPa, and the compressive strength of the concrete after the concrete is cured again after the crack prefabrication is obviously improved compared with the integral strength of the concrete before the repair. And the crack repairing effect is good, the width of the crack is 0.07-0.19 mm when the crack is maintained for 7d again, compared with the width before repairing, the width of the crack is greatly reduced, the width of the crack is 0.000mm when the crack is maintained for 28d again, and the crack is completely repaired. The bionic self-repairing concrete prepared in the examples 4 to 8 is superior to the concrete prepared in the comparative examples 1 to 3 in impermeability, mechanical property and crack repairing effect.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.

Claims (8)

1. The bionic self-repairing concrete is characterized by comprising the following raw materials in parts by weight: 240-360 parts of cement, 180-250 parts of active admixture, 1300-1600 parts of aggregate, 60-90 parts of mesoporous bioactive glass composite microspheres, 20-30 parts of calcium peroxide microspheres, 20-30 parts of carbon nano-tubes, 8-16 parts of polycarboxylic acid water reducing agent and 190-220 parts of water;
the mesoporous bioactive glass composite microspheres take mesoporous bioactive glass microspheres as carriers, aerobic alkaline-resisting bacillus is loaded in the mesoporous bioactive glass composite microspheres, and polyvinyl alcohol is coated outside the mesoporous bioactive glass composite microspheres;
the particle size of the calcium peroxide microspheres is 1-5 mu m, and the surfaces of the calcium peroxide microspheres are coated with a polybutylene succinate protective film.
2. The bionic self-repairing concrete of claim 1, wherein the mesoporous bioactive glass microspheres in the mesoporous bioactive glass composite microspheres are CaO-SiO composed of oxides of calcium, silicon, aluminum and phosphorus2-Al2O3-P2O5The system has a particle size of 100 to 600nm, a pore diameter of 2 to 50nm, and a specific surface area of 500 to 1000m2/g。
3. The bionic self-repairing concrete of claim 1 or 2, wherein the loading ratio of aerobic alkaline-resisting bacillus in the mesoporous bioactive glass composite microsphere is 1g of mesoporous bioactive glass microsphere: 2.5-5 mL of bacterial liquid, wherein the concentration of the bacterial liquid is (4-5) x 107one/mL.
4. The bionic self-repairing concrete of claim 3, wherein the preparation of the mesoporous bioactive glass composite microspheres comprises the following steps:
(1) culturing aerobic alkali-resistant bacillus, centrifuging to obtain bacterial mud, and re-suspending the bacterial mud with a culture medium to obtain a suspension with a concentration of (4-5) x 107Bacterial liquid per mL; dipping the mesoporous bioactive glass microspheres and the bacterial solution by a vacuum dipping method according to the proportion of 1g: 2.5-5 mL, and drying at 30-40 ℃ to obtain mesoporous bioactive glass microspheres loaded with aerobic alkali-resistant bacillus inside;
(2) dissolving polyvinyl alcohol in water to prepare a solution with the mass fraction of 20-30%, uniformly spraying the solution on the surface of the mesoporous bioactive glass microsphere which is prepared in the step (1) and is loaded with aerobic alkali-resistant bacillus inside, wherein the mass ratio of the polyvinyl alcohol to the mesoporous bioactive glass microsphere is 3-4.5: 1, uniformly mixing, and drying at the temperature of 30-40 ℃ to obtain the mesoporous bioactive glass composite microsphere.
5. The bionic self-repairing concrete of claim 1, wherein the preparation of the calcium peroxide microspheres comprises the following steps: dissolving polybutylene succinate in chloroform to prepare a solution with the mass fraction of 5-10%, uniformly spraying the solution on the surface of calcium peroxide to enable the thickness of a film layer of the polybutylene succinate to be 20-40 nm, and performing vacuum drying and chloroform recovery to obtain the calcium peroxide microspheres.
6. The bionic self-repairing concrete according to claim 1, characterized in that the active admixture is selected from at least one of fly ash, slag powder, phosphorous slag powder, silica fume, zeolite powder, sepiolite powder and quartz powder.
7. The bionic self-repairing concrete of claim 1, wherein the aggregate is composed of fine aggregate and coarse aggregate in a mass ratio of 1 (1.4-1.8); the fine aggregate is river sand, lake sand, mountain sand or desalted sea sand; the coarse aggregate is broken stone or pebble.
8. A method for preparing the bionic self-repairing concrete as claimed in any one of claims 1 to 7, which is characterized by comprising the following steps: mixing cement, active admixture, aggregate, mesoporous bioactive glass composite microspheres, calcium peroxide microspheres, carbon nanotubes, polycarboxylic acid water reducing agent and water, uniformly stirring, pouring and molding, removing a mold, and maintaining to obtain the concrete.
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