CN110395884A - A kind of bionical self-repair concrete and preparation method thereof - Google Patents
A kind of bionical self-repair concrete and preparation method thereof Download PDFInfo
- Publication number
- CN110395884A CN110395884A CN201910786078.3A CN201910786078A CN110395884A CN 110395884 A CN110395884 A CN 110395884A CN 201910786078 A CN201910786078 A CN 201910786078A CN 110395884 A CN110395884 A CN 110395884A
- Authority
- CN
- China
- Prior art keywords
- parts
- microballoon
- bioactive glass
- concrete
- repair
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004567 concrete Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000005313 bioactive glass Substances 0.000 claims abstract description 58
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- 235000019402 calcium peroxide Nutrition 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000004568 cement Substances 0.000 claims abstract description 23
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
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- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
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- 239000010457 zeolite Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
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- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
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Classifications
-
- 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
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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
- 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
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- 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
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- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
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- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
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Abstract
The invention discloses a kind of bionical self-repair concretes and preparation method thereof, the bionical self-repair concrete, it is characterized in that, the raw material comprising following parts by weight: 240~360 parts of cement, 180~250 parts of active blend, 1300~1600 parts of aggregate, 60~90 parts of mesopore bioactive glass complex microsphere, 20~30 parts of calper calcium peroxide microballoon, 20~30 parts of carbon nanotubes, 8~16 parts of polycarboxylate water-reducer and 190~220 parts of water.Bionical self-repair concrete of the invention has quick self-reparing capability, it can continue the microcrack or micro-damage of different deep layers in self-healing concrete, matrix strength continues to increase after promoting crack to repair, improve the intensity and durability of concrete, it is wide with repair coverage, it repairs rapidly, repairs lasting advantage.
Description
Technical field
The present invention relates to building material technical fields, and in particular to a kind of bionical self-repair concrete and preparation method thereof.
Background technique
The big inherent shortcoming of concrete material brittleness, seriously affects its crack resistance.Often there is the micro- of matrix in Practical Project
The microscopic damages such as cracking, and this microcrack is usually not visible, certain let alone reparation.If these damage locations are not
It can repair in time, not only will affect the intensity and durability of concrete material, carry out the normal use performance and contracting that influence structure
Short service life, and may thus cause macrocrack and brittle fracture occur, generate serious catastrophic failure.Tradition is mixed
The reparation form of solidifying soil material is mainly periodic maintenance and correction maintenance, this passive, passively maintenance mode not only expense
Huge and ineffective, it is even more impossible to meet modern multi-functional and intelligent building to concrete material requirement.Research and
Bionical self-repair concrete is developed, automatically damage location can be repaired, restored and is improved concrete material
Performance has become the development trend of concrete technology.The bionical selfreparing of concrete material is mimic biology tissue damage healing
Function is embedded into particular components in cement matrix, forms intelligent self-repairing system.When matrix generates crack damage, bury
It plants to tie up under power, heat or chemical depletion in internal dummy and discharges renovation agent, cohere closure crackle, crackle is prevented further to expand
Exhibition, to reach reparation purpose.Compared with traditional recovery technique, it have it is low in cost, not against external operation, renewable
Etc. advantages.
According to the difference of concrete selfreparing mechanism, it mainly includes mineral self-healing, microcapsules that autogenous healing, which closes mode,
The modes such as self-healing, penetrant crystalline selfreparing, electrochemistry selfreparing, marmem selfreparing, microorganism selfreparing, wherein
The calcium carbonate and cement-based material that microorganism self-repair concrete is generated by its inducing microbial have good compatibility, and
With environment friendly, the concern by more and more people in recent years.Microorganism specific environment and nutritional condition stimulation under,
Multi mineral crystallization, such as carbonate, phosphate, oxide and born of the same parents' object is quickly precipitated.Tosca to a certain extent may be used
Crack caused by concrete cracking is filled up, gelling property can improve the intensity and endurance quality of cement base class material.However mesh
The practical application of preceding microorganism self-repair concrete still faces many problems, mainly includes the following: 1) concrete is mostly height
Microorganism, is directly incorporated into concrete by alkali adverse circumstances, and microorganism premature death fails to play repairing effect.2) in mixed
The permeability of the micro-cracks of solidifying soil depths, oxygen and water is bad, and microorganism is difficult to activate in the environment of anoxic water shortage, cannot
Play repairing effect.3) it is repaired using anaerobic type microorganism, anaerobic bacteria enzyme is turned into used time generation ammonia, not only endangers people
Body health, can also be converted to nitric acid, corrosion reinforcing bar.4) restore metabolic function after activation of microorganism, breathing generates titanium dioxide
Carbon, carbon dioxide is reacted with the calcium ion in cement-based material in moist environment generates calcium carbonate, with this filling cracks, produces
The premise of raw calcium carbonate is the calcium ion for needing to consume in inside concrete product, will lead to concrete structure stability decline.
5) it is repaired using microcapsules loading microorganisms, hole can be left in concrete after microcapsules rupture releasing microbe
Cause concrete strength to reduce, and existing microcapsules are mostly high molecular polymer, is difficult to drop in Concrete in Natural environment
Solution, residue can cause counter productive to cement base matrix.
The Chinese patent application of Publication No. CN 104261736A discloses a kind of cement with deep layer self-repair function
The preparation method of sill, this method will produce carbonic anhydrase bacterium first and saccharomycete powder is immobilized in carrier A, by substrate, battalion
It supports substance and deionized water is immobilized in carrier B, then carrier A and the materials such as the mixed carrier of carrier B and cement, sand and water
Mixing, stirring molding, standard curing obtain cement-based material, and the carrier A and carrier B are haydite, clay or zeolite.It should
Invention using bacterium, substrate and nutriment distinguish it is immobilized by the way of, not only limit the diffusion of bacterium, substrate and product, no
It can guarantee the fast reaction between bacterium and substance and sufficiently react, and carrier A and the mixed carrier of carrier B are as light bone
Material be directly incorporated into concrete, instead of the use of the dosage of aggregates, especially coarse aggregate, concrete can be caused compared with
Big strength damage, although repair after intensity relative to it is untreated when have certain recovery, far can not make up carrier incorporation
Loss of strength caused by afterwards limits the application of such cement-based material in engineering practice.
Summary of the invention
The object of the present invention is to provide a kind of bionical self-repair concrete and preparation method thereof, which has quickly certainly
Repair ability can continue the microcrack or micro-damage of different deep layers in self-healing concrete, matrix after promoting crack to repair
Intensity continues to increase, and improves the intensity and durability of concrete, has repair coverage wide, repairs rapidly, repairs lasting excellent
Point.
The technical solution adopted by the present invention is as follows:
A kind of bionical self-repair concrete, the raw material comprising following parts by weight: 240~360 parts of cement, active blend
180~250 parts, 1300~1600 parts of aggregate, 60~90 parts of mesopore bioactive glass complex microsphere, calper calcium peroxide microballoon 20~
30 parts, 20~30 parts of carbon nanotubes, 8~16 parts of polycarboxylate water-reducer and 190~220 parts of water.
It is preferred that the mesopore bioactive glass complex microsphere be using mesopore bioactive glass microballoon as carrier,
Its internal load has aerobic alkali-fast bacillus cereus, and outside is coated with polyvinyl alcohol.
It is preferred that the partial size of the mesopore bioactive glass microballoon in the mesopore bioactive glass complex microsphere is
100~600nm, aperture are 2~50nm, and specific surface area is 500~1000m2/g.The mesopore bioactive glass microballoon is
The CaO-SiO being made of the oxide of calcium, silicon, aluminium, phosphorus2-Al2O3-P2O5System, preparation method are using existing template
It is prepared, specifically includes the following steps: (1) is by triblock copolymer Pluronic F127 (molecular formula EO106PO70EO106,
EO is ethylene oxide, and PO is propylene oxide；Average molecular weight 12600) it is dissolved in the mixed solvent of dehydrated alcohol and glacial acetic acid composition
In (volume ratio of dehydrated alcohol and glacial acetic acid is 5:2), the mixed proportion of the Pluronic F127 and mixed solvent is
1g:25mL is stirred and evenly mixed, and obtains mixed solution A.(2) oxide precursor is added into the mixed solution A that step (1) obtains
Mixture, stirring and dissolving obtain mixed solution B, and the mass ratio of the oxide precursor mixture and mixed solution A is 1:
3.5~4, oxide precursor mixture is mixed by calcium nitrate tetrahydrate, methyl orthosilicate, ANN aluminium nitrate nonahydrate, trimethyl phosphate
It is combined into, mixed proportion is by CaO:SiO2: Al2O3: P2O5Molar ratio be 90:50:15:5 calculate.(3) by three-dimensional order
Aperture be 470nm the polystyrene moulding of macroporous structure immerse in step (2) obtained mixed solution B, after impregnating for 24 hours,
It is placed in 60 DEG C of baking ovens and carries out 48~72h of collosol and gel formation gelatinous solid, gelatinous solid is done at 60~100 DEG C
It is dry, be subsequently placed in Muffle furnace in 550~650 DEG C and carry out 3~5h of calcining, when calcining control heating rate be 0.5~3 DEG C/
Min obtains mesopore bioactive glass microballoon.
The composition system of mesopore bioactive glass microballoon of the invention is CaO-SiO2-Al2O3-P2O5, compared to common
Bioactivity glass form system CaO-SiO2-P2O5, by introducing Al2O3Ingredient, hence it is evident that improve mesopore bioactive
The mechanical strength of glass makes that concrete mechanics will not be caused in mesopore bioactive glass complex microsphere incorporation concrete
The reduction of energy.
It is preferred that the load percentage of aerobic alkali-fast bacillus cereus is 1g in the mesopore bioactive glass complex microsphere
Mesopore bioactive glass microballoon: 2.5~5mL bacterium solution, the bacterial concentration are (4~5) × 107A/mL.
Mesopore bioactive glass complex microsphere of the invention is to be prepared by the following method to obtain:
(1) aerobic alkali-fast bacillus cereus is cultivated, bacterium mud is obtained after centrifugation, bacterium mud is resuspended with culture medium, is obtained
It is (4~5) × 10 to concentration7The bacterium solution of a/mL；Mesopore bioactive glass microballoon and bacterium solution are pressed using vacuum impregnation technology
The ratio of 1g:2.5~5mL is impregnated, and is dried at 30~40 DEG C, and obtaining internal load has aerobic alkali-fast bacillus cereus
Mesopore bioactive glass microballoon；
(2) polyvinyl alcohol is dissolved in water and the solution that mass fraction is 20~30% is made, be then uniformly sprayed on step (1)
Internal load obtained has on the mesopore bioactive glass microsphere surface of aerobic alkali-fast bacillus cereus, the polyvinyl alcohol
Mass ratio with mesopore bioactive glass microballoon is 3~4.5:1, mixes, dries at 30~40 DEG C, and it is living to obtain mesoporous biological
Property glass complex microsphere.
It is preferred that the aerobic alkali-fast bacillus cereus is Bacillus cohnii DSM 6307 or Bacillus
Pseudofirmus DSM 8715, culture medium composition are as follows: every liter of culture medium contains 1~5g peptone, 20~30g malt paste
Essence, 8~10g ammonium chloride, 1~4g sodium citrate, 0.5~1.5g magnesium sulfate, surplus are water.
It is preferred that the partial size of the calper calcium peroxide microballoon is 1~5 μm, surface is coated with poly butylene succinate
(PBS) protective film.
It is preferred that the preparation of the calper calcium peroxide microballoon is the following steps are included: be dissolved in chloroform for poly butylene succinate,
The solution that mass fraction is 5~10% is made, is then uniformly sprayed on calper calcium peroxide surface, makes poly butylene succinate
Thicknesses of layers is 20~40nm, is dried in vacuo and recycles chloroform, obtain calper calcium peroxide microballoon.
It is preferred that the active blend is selected from flyash, slag powders, phosphorus slag powder, silicon ash, zeolite powder, sepiolite powder, stone
At least one of English powder.
It is preferred that the aggregate is fine aggregate and coarse aggregate with 1:(1.4~1.8) mass ratio form；The thin bone
Material is river sand, lake sand, mountain sand or desalted sea sand；The coarse aggregate is rubble or cobble.
Bionical self-repair concrete of the invention is to be prepared by the following method to obtain comprising following steps: by cement,
Active blend, aggregate, mesopore bioactive glass complex microsphere, calper calcium peroxide microballoon, carbon nanotubes, polycarboxylate water-reducer and
Water mixing, after mixing evenly, pouring molding, demoulding conserve to get concrete is arrived.
Compared with prior art, the invention has the following advantages:
(1) mesopore bioactive glass complex microsphere is added as main renovation agent in the present invention in concrete, makes concrete
With efficient repair ability.The mesopore bioactive glass complex microsphere using mesopore bioactive glass microballoon as carrier,
There is pore structure, uniform pore-size distribution, high porosity and the big ratio table of high-sequential using mesopore bioactive glass
Area, can high-efficient carrier aerobic alkali-fast bacillus cereus and medium nutrient content, avoid concrete high-alkali adverse circumstances damage
Bacterial activity.The mesopore bioactive glass microballoon contains CaO, SiO2、Al2O3、P2O5Ingredient, the not only growth of microorganism
There is provided good microenvironment, moreover it is possible to provide inorganic matter ingredient origin for bacteria-induction mineralising, bacterium is avoided to pass through consumption concrete
Internal product meets the needs of remineralization, improves the stability of concrete structure.When concrete damages, a large amount of moisture
Microcrack is penetrated into, the H in alkali metal ion and aqueous solution in mesopore bioactive glass+Ion swaps, and subsequent two
Silica network rupture forms SiOH, and SiOH is polycondensed into Si-O-Si on mesopore bioactive glass surface and forms silicon-rich layer, rich
Silicon layer adsorbs amorphous Ca, PO4、CO2Form amorphous apatite layer, amorphous phosphorus lime stone continued growth and being changed into has
On the one hand the hydroxyapatite of crystal structure, the formation of mesopore bioactive glass surface hydroxyl apatite can promote being cured for crack
It closes, improves the intensity of concrete, on the other hand can be used as carrier and load bacillus again, keep the activity of bacillus, when
When crack is formed again, bacillus can play repair again.Since the apatite mine of mesopore bioactive glass is turned into
It is to carry out simultaneously with the calcium carbonate mineralization with microorganism, promotes the quick healing of concrete damage, makes bionical to review one's lessons by oneself compound
Solidifying soil has quick self-reparing capability.
(2) carbon nanotubes is added in the present invention in concrete, can improve the toughness of concrete, improve the cracking resistance of concrete
Can, improve intensity and durability.Especially by the glutinous poly- work of the polyvinyl alcohol on mesopore bioactive glass complex microsphere surface
With, promote to form firm tridimensional network between carbon nanotubes and mesopore bioactive glass complex microsphere and concrete,
It not only helps delay or inhibits the development in crack, and the physical and mechanical property of energy reinforced mortar, power after promoting crack to repair
Learn the promotion of performance.
(3) calper calcium peroxide microballoon is added in concrete and is made using the coating function of poly butylene succinate by the present invention
Calper calcium peroxide is stable in the presence of in concrete, while obstructing it to the active influence of bacillus, when concrete damages, greatly
The moisture penetration of amount enters concrete and forms alkaline solution, and poly butylene succinate is promoted to degrade, and the calper calcium peroxide exposed is met
Water can slow release oxygen, generate calcium hydroxide, calcium hydroxide absorb bacillus metabolism release carbon dioxide or sky
The carbon dioxide infiltrated through in concrete in gas generates precipitation of calcium carbonate, further promotes the healing of distress in concrete, releases simultaneously
The oxygen put can activate bacillus, be particularly useful to gemma of the activation in the environment that distress in concrete depths oxygen lacks
Bacillus breaks its suspend mode, promotes bacillus in the repair of crack depths.
In conclusion bionical self-repair concrete of the invention has quick self-reparing capability, self-healing can be continued
The microcrack or micro-damage of different deep layers in concrete, matrix strength continues to increase after promoting crack to repair, and improves concrete
Intensity and durability, have repair coverage it is wide, repair rapidly, repair lasting advantage.
Specific embodiment
The following examples are further illustrations of the invention, rather than limiting the invention.In following embodiments, such as
Without special instruction, raw material is commercial product.
The preparation of 1 mesopore bioactive glass microballoon of embodiment
The preparation of mesopore bioactive glass microballoon is carried out using template, specifically includes the following steps:
(1) by triblock copolymer Pluronic F127 (molecular formula EO106PO70EO106, EO is ethylene oxide, and PO is
Propylene oxide；Average molecular weight 12600) it is dissolved in mixed solvent (dehydrated alcohol and the glacial acetic acid of dehydrated alcohol and glacial acetic acid composition
Volume ratio be 5:2) in, the mixed proportion of the Pluronic F127 and mixed solvent is 1g:25mL, stirs and evenly mixs, obtains
To mixed solution A.
(2) the addition 100g oxide precursor mixture into the mixed solution A that 400g step (1) obtains, stirring and dissolving,
Obtain mixed solution B, the oxide precursor mixture by 51.19g calcium nitrate tetrahydrate, 18.33g methyl orthosilicate,
27.11g ANN aluminium nitrate nonahydrate, 3.37g trimethyl phosphate mixing composition, mixed proportion is by CaO:SiO2: Al2O3: P2O5's
Molar ratio is 90:50:15:5 calculating.
(3) polystyrene moulding immersion step (2) for the macroporous structure that the aperture of three-dimensional order is 470nm is obtained mixed
It closes in solution B, after impregnating for 24 hours, is placed in 60 DEG C of baking ovens and carries out collosol and gel 72h formation gelatinous solid, gel is consolidated
Body is dry at 80 DEG C, is subsequently placed in Muffle furnace in 600 DEG C and carries out calcining 3h, when calcining control heating rate be 1.5 DEG C/
Min obtains mesopore bioactive glass microballoon.
The preparation of 2 mesopore bioactive glass complex microsphere of embodiment
The preparation of mesopore bioactive glass complex microsphere the following steps are included:
(1) aerobic alkali-fast bacillus cereus (Bacillus cohnii DSM 6307) is inoculated in culture medium (every liter of training
Feeding base contains 4.5g peptone, and 30g maltodextrin, 10g ammonium chloride, 2g sodium citrate, 1g magnesium sulfate, surplus is water, pH value 9
~10) in, shaken cultivation 72h, obtains bacterium solution at room temperature, and bacterium solution is centrifuged 20min at 4000r/min, obtains bacterium mud, will
Bacterium mud is resuspended with culture medium, and obtaining concentration is (4~5) × 107The bacterium solution of a/mL；It is using vacuum impregnation technology that mesoporous biological is living
Property glass microsphere (embodiment 1 be made) and bacterium solution impregnated in the ratio of 1g:2.5mL, dried at 35 DEG C, obtain internal bear
It is loaded with the mesopore bioactive glass microballoon of aerobic alkali-fast bacillus cereus；
(2) polyvinyl alcohol is dissolved in water and the solution that mass fraction is 30% is made, be then uniformly sprayed on step (1) and be made
Internal load have on the mesopore bioactive glass microsphere surface of aerobic alkali-fast bacillus cereus, the polyvinyl alcohol and Jie
The mass ratio of hole bioactive glass microballoon is 3:1, mixes, dries at 35 DEG C, it is compound micro- to obtain mesopore bioactive glass
Ball.
The preparation of 3 calper calcium peroxide microballoon of embodiment
Quality point is made the following steps are included: poly butylene succinate is dissolved in chloroform in the preparation of calper calcium peroxide microballoon
The solution that number is 5%, is then uniformly sprayed on calper calcium peroxide surface, makes the thicknesses of layers of poly butylene succinate
20nm is dried in vacuo and recycles chloroform, obtains calper calcium peroxide microballoon.
The preparation of the bionical self-repair concrete of embodiment 4
A kind of bionical self-repair concrete, the raw material comprising following parts by weight: 325 parts of cement, 130 parts of flyash, slag
90 parts of powder, 520 parts of river sand, 780 parts of rubble, 90 parts of mesopore bioactive glass complex microsphere, calper calcium peroxide microballoon 20 part, nanometer
20 parts of carbon pipe, 8 parts of polycarboxylate water-reducer and 200 parts of water.
Preparation step: by cement, flyash, slag powders, river sand, rubble, mesopore bioactive glass complex microsphere, peroxide
Change calcium microballoon, carbon nanotubes, polycarboxylate water-reducer and water mixing, after mixing evenly, pouring molding, demoulding conserves mixed to get arriving
Solidifying soil.
The preparation of the bionical self-repair concrete of embodiment 5
A kind of bionical self-repair concrete, the raw material comprising following parts by weight: 275 parts of cement, phosphorus slag powder 125, slag powders
90 parts, 667 parts of desalted sea sand, 933 parts of cobble, 75 parts of mesopore bioactive glass complex microsphere, 25 parts of calper calcium peroxide microballoon, receive
25 parts of rice carbon pipe, 16 parts of polycarboxylate water-reducer and 220 parts of water.
Preparation step reference implementation example 4.
The preparation of the bionical self-repair concrete of embodiment 6
A kind of bionical self-repair concrete, the raw material comprising following parts by weight: 280 parts of cement, 100 parts of flyash, silicon ash
40 parts, 600 parts of river sand, 900 parts of cobble, 80 parts of mesopore bioactive glass complex microsphere, 25 parts of calper calcium peroxide microballoon, nano-sized carbon
25 parts of pipe, 12 parts of polycarboxylate water-reducer and 190 parts of water.
Preparation step reference implementation example 4.
The preparation of the bionical self-repair concrete of embodiment 7
A kind of bionical self-repair concrete, the raw material comprising following parts by weight: 340 parts of cement, 145 parts of flyash, quartz
90 parts of powder, 500 parts of mountain sand, 900 parts of rubble, 60 parts of mesopore bioactive glass complex microsphere, calper calcium peroxide microballoon 20 part, nanometer
20 parts of carbon pipe, 10 parts of polycarboxylate water-reducer and 195 parts of water.
Preparation step reference implementation example 4.
The preparation of the bionical self-repair concrete of embodiment 8
A kind of bionical self-repair concrete, the raw material comprising following parts by weight: 360 parts of cement, 150 parts of flyash, zeolite
100 parts of powder, 500 parts of desalted sea sand, 800 parts of rubble, 90 parts of mesopore bioactive glass complex microsphere, calper calcium peroxide microballoon 30
Part, 30 parts of carbon nanotubes, 14 parts of polycarboxylate water-reducer and 210 parts of water.
Preparation step reference implementation example 4.
The preparation of the bionical self-repair concrete of comparative example 1
A kind of bionical self-repair concrete, the raw material comprising following parts by weight: 325 parts of cement, 130 parts of flyash, slag
90 parts of powder, 520 parts of river sand, 780 parts of rubble, haydite load 90 parts of aerobic alkali-fast bacillus cereus, 20 parts of carbon nanotubes, polycarboxylic acids
8 parts and 200 parts of water of water-reducing agent.
The preparation of the haydite load aerobic alkali-fast bacillus cereus is the following steps are included: by the alkaline-resisting gemma bar of aerobic
Bacterium (Bacillus cohnii DSM 6307) is inoculated in culture medium, and (every liter of culture medium contains 4.5g peptone, 30g malt paste
Essence, 10g ammonium chloride, 2g sodium citrate, 1g magnesium sulfate, surplus are water, and pH value is 9~10) in, shaken cultivation 72h at room temperature,
Bacterium solution is obtained, bacterium solution is centrifuged 20min at 4000r/min, bacterium mud is obtained, bacterium mud is resuspended with culture medium, obtaining concentration is
(4~5) × 107The bacterium solution of a/mL；Haydite and bacterium solution are impregnated in the ratio of 1g:2.5mL using vacuum impregnation technology, In
It is dried at 35 DEG C, obtains the haydite that internal load has aerobic alkali-fast bacillus cereus；
The preparation step reference implementation example 4 of concrete.
The preparation of the bionical self-repair concrete of comparative example 2
A kind of bionical self-repair concrete, the raw material comprising following parts by weight: 325 parts of cement, 130 parts of flyash, slag
90 parts of powder, 780 parts of rubble, 90 parts of aerobic alkali-fast bacillus cereus of haydite load, 20 parts of calper calcium peroxide microballoon, is received 520 parts of river sand
20 parts of rice carbon pipe, 8 parts of polycarboxylate water-reducer and 200 parts of water.
Haydite loads the preparation of aerobic alkali-fast bacillus cereus with comparative example 1.
The preparation step reference implementation example 4 of concrete.
The preparation of the bionical self-repair concrete of comparative example 3
A kind of bionical self-repair concrete, the raw material comprising following parts by weight: 325 parts of cement, 130 parts of flyash, slag
90 parts of powder, 520 parts of river sand, 780 parts of rubble, 90 parts of mesopore bioactive glass complex microsphere, 20 parts of carbon nanotubes, polycarboxylic acids subtract
8 parts and 200 parts of water of aqua.
The preparation step reference implementation example 4 of concrete.
Test example one, performance detection
Bionical self-repair concrete is made to embodiment 4-8 and comparative example 1-3 respectively and carries out impervious, mechanical property and crack
Mechanical property is tested after reparation, and the mechanical performance of concrete test experiments are referring to GB/T50081-2002 concrete mechanics
Method for testing performance standard, durability test are tested with reference to GB/T50082-2009 normal concrete long-term behaviour and endurance quality
Method standard, wherein Mechanics Performance Testing is that the compression strength of 7d, 28d, power after crack is repaired are conserved after measuring concrete preparation
Learning performance test is measurement by splitting tensile test, so that concrete is had the fracture width of 0.2~0.4mm, is supported again
Protect the compression strength of 7d, 28d.
Test result is shown in Table 1.
The performance test results of 1 each group concrete of table
The results show that bionical self-repair concrete made from 4-8 of the embodiment of the present invention has preferable anti-permeability performance and power
Performance is learned, the compression strength for conserving 7d is 30.7~35.4MPa, and the compression strength for conserving 28d is 55.4~61.2MPa, is carried out
The compression strength for conserving 7d after splitting tensile test again is 33.5~38.2MPa, and the compression strength for conserving 28d again is 58.3
~64.4MPa, concrete carries out the compression strength after being conserved behind prefabricated crack again and significantly improves, more whole than concrete before repairing
Enhanced strength.And crack repairing effect is good, and fracture width is 0.07~0.19mm when conserving 7d again, compared with before reparation,
Fracture width is greatly reduced, and fracture width when conserving 28d again is 0.000mm, and crack is repaired completely.Embodiment 4-8 is made
Bionical self-repair concrete either anti-permeability performance, mechanical property and crack repairing effect be superior to made from comparative example 1-3
Concrete.
The above is only the preferred embodiment of the present invention, it is noted that above-mentioned preferred embodiment is not construed as pair
Limitation of the invention, protection scope of the present invention should be defined by the scope defined by the claims..For the art
For those of ordinary skill, without departing from the spirit and scope of the present invention, several improvements and modifications can also be made, these change
It also should be regarded as protection scope of the present invention into retouching.
Claims (10)
1. a kind of bionical self-repair concrete, which is characterized in that the raw material comprising following parts by weight: 240~360 parts of cement is lived
Property 180~250 parts of admixture, 1300~1600 parts of aggregate, 60~90 parts of mesopore bioactive glass complex microsphere, calper calcium peroxide
20~30 parts of microballoon, 20~30 parts of carbon nanotubes, 8~16 parts of polycarboxylate water-reducer and 190~220 parts of water.
2. bionical self-repair concrete according to claim 1, which is characterized in that the mesopore bioactive glass is multiple
Closing microballoon is using mesopore bioactive glass microballoon as carrier, and internal load has aerobic alkali-fast bacillus cereus, outside packet
It is covered with polyvinyl alcohol.
3. bionical self-repair concrete according to claim 2, which is characterized in that the mesopore bioactive glass is multiple
Close the CaO-SiO that the mesopore bioactive glass microballoon in microballoon is made of the oxide of calcium, silicon, aluminium, phosphorus2-Al2O3-P2O5
System, partial size are 100~600nm, and aperture is 2~50nm, and specific surface area is 500~1000m2/g。
4. bionical self-repair concrete according to claim 2 or 3, which is characterized in that the mesopore bioactive glass
The load percentage of aerobic alkali-fast bacillus cereus is 1g mesopore bioactive glass microballoon: 2.5~5mL bacterium in glass complex microsphere
Liquid, the bacterial concentration are (4~5) × 107A/mL.
5. bionical self-repair concrete according to claim 4, which is characterized in that the mesopore bioactive glass is multiple
Close microballoon preparation the following steps are included:
(1) aerobic alkali-fast bacillus cereus is cultivated, bacterium mud is obtained after centrifugation, bacterium mud is resuspended with culture medium, is obtained dense
Degree is (4~5) × 107The bacterium solution of a/mL；Mesopore bioactive glass microballoon and bacterium solution are pressed by 1g:2.5 using vacuum impregnation technology
The ratio of~5mL is impregnated, and is dried at 30~40 DEG C, and the mesoporous life that internal load has aerobic alkali-fast bacillus cereus is obtained
Object activity glass microballoon；
(2) polyvinyl alcohol is dissolved in water and the solution that mass fraction is 20~30% is made, be then uniformly sprayed on step (1) and be made
Internal load have on the mesopore bioactive glass microsphere surface of aerobic alkali-fast bacillus cereus, the polyvinyl alcohol and Jie
The mass ratio of hole bioactive glass microballoon is 3~4.5:1, mixes, dries at 30~40 DEG C, obtain mesopore bioactive glass
Glass complex microsphere.
6. bionical self-repair concrete according to claim 1, which is characterized in that the partial size of the calper calcium peroxide microballoon
It is 1~5 μm, surface is coated with poly butylene succinate protective film.
7. bionical self-repair concrete according to claim 6, which is characterized in that the preparation of the calper calcium peroxide microballoon
The following steps are included: poly butylene succinate is dissolved in chloroform, the solution that mass fraction is 5~10% is made, then uniformly
It is sprayed on calper calcium peroxide surface, makes 20~40nm of thicknesses of layers of poly butylene succinate, be dried in vacuo and recycle chlorine
It is imitative, obtain calper calcium peroxide microballoon.
8. bionical self-repair concrete according to claim 1, which is characterized in that the active blend is selected from fine coal
At least one of ash, slag powders, phosphorus slag powder, silicon ash, zeolite powder, sepiolite powder, silica flour.
9. bionical self-repair concrete according to claim 1, which is characterized in that the aggregate is fine aggregate and thick bone
Expect with 1:(1.4~1.8) mass ratio form；The fine aggregate is river sand, lake sand, mountain sand or desalted sea sand；Described is thick
Aggregate is rubble or cobble.
10. a kind of method for preparing any bionical self-repair concrete of claim 1-9, which is characterized in that including with
Lower step: by cement, active blend, aggregate, mesopore bioactive glass complex microsphere, calper calcium peroxide microballoon, carbon nanotubes,
Polycarboxylate water-reducer and water mixing, after mixing evenly, pouring molding, demoulding conserve to get concrete is arrived.
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