CN105565326A - Autolysis type porous microsphere for self-repairing of concrete crack and preparation method thereof - Google Patents
Autolysis type porous microsphere for self-repairing of concrete crack and preparation method thereof Download PDFInfo
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- CN105565326A CN105565326A CN201610005049.5A CN201610005049A CN105565326A CN 105565326 A CN105565326 A CN 105565326A CN 201610005049 A CN201610005049 A CN 201610005049A CN 105565326 A CN105565326 A CN 105565326A
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- 239000004005 microsphere Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 208000035404 Autolysis Diseases 0.000 title abstract 5
- 206010057248 Cell death Diseases 0.000 title abstract 5
- 230000028043 self proteolysis Effects 0.000 title abstract 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 85
- 230000001681 protective effect Effects 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000011068 loading method Methods 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 85
- 238000000034 method Methods 0.000 claims description 83
- 238000009418 renovation Methods 0.000 claims description 79
- 230000008569 process Effects 0.000 claims description 61
- 239000012528 membrane Substances 0.000 claims description 44
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 41
- 238000001354 calcination Methods 0.000 claims description 37
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 34
- 239000012266 salt solution Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 28
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 22
- 238000005119 centrifugation Methods 0.000 claims description 21
- 230000009429 distress Effects 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 17
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical group CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 238000007598 dipping method Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 15
- 239000013543 active substance Substances 0.000 claims description 14
- 229910021529 ammonia Inorganic materials 0.000 claims description 14
- 239000003637 basic solution Substances 0.000 claims description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 14
- 150000002148 esters Chemical class 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 239000011780 sodium chloride Substances 0.000 claims description 13
- 239000004115 Sodium Silicate Substances 0.000 claims description 10
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- -1 silicon ester Chemical class 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 9
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 18
- 239000004568 cement Substances 0.000 abstract description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 9
- 239000011707 mineral Substances 0.000 abstract description 9
- 239000000377 silicon dioxide Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000003094 microcapsule Substances 0.000 abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000007246 mechanism Effects 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 230000005284 excitation Effects 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 238000013268 sustained release Methods 0.000 abstract 1
- 239000012730 sustained-release form Substances 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 18
- 238000001035 drying Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000006424 Flood reaction Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000035876 healing Effects 0.000 description 3
- 239000012716 precipitator Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 206010011732 Cyst Diseases 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 208000031513 cyst Diseases 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- 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
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/04—Alkali metal or ammonium silicate cements ; Alkyl silicate cements; Silica sol cements; Soluble silicate cements
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention relates to an autolysis type porous microsphere for self-repairing of concrete crack and a preparation method thereof. The autolysis type porous microsphere is prepared by steps of autolysis type microsphere preparation, hole reaming of autolysis type microsphere, repairing agent loading, and protective film loading. Compared with the prior art, the preparation method has the advantages of simpleness, good controllability, and low cost. Porous SiO2 microspheres are taken as the repairing agent supporting carrier. The microsphere has the characteristics that the mineral self-repairing main body can also participate in the repairing reactions and the self-repairing sustained-release excitation mechanism of the microcapsule is definite, so the microsphere can be applied to the self-repairing of cracks on a cement based material structure, moreover, the repairing speed can be controlled according to the specific environment, and the repairing effect can last for a long time.
Description
Technical field
The invention belongs to concrete works technical field, relate to a kind of self-dissolving type porous microsphere and preparation method thereof, especially relate to a kind of self-dissolving type porous microsphere for distress in concrete selfreparing and preparation method thereof.
Background technology
Namely the self-healing of cement-based material mineral adds part mineral material in cement-based material system, when crack place has water to infiltrate, can promote and encourage the diffusion of wherein effective ion, migration and reaction, produce at crack place the product that effectively heals, complete self-healing function.Because body material composition is different with mineral material composition, its healing product is also incomplete same, mainly comprises C-S-H gel, calcium carbonate crystal precipitation, calcium hydroxide etc.
At present, the research for different cement-based material self-healing method is more, is more partial to the method adopting mineral self-healing and microcapsule self-healing in reality.But the legal motivational techniques of mineral self-healing are indefinite, and after microcapsules rupture, cyst material can have a negative impact to cement-based material.Above-mentioned two kinds of methods are all further improved.
Porous SiO
2microballoon is due to advantages such as its specific surface area is large, porosity is high, good fluidities, easily dispersion, and it has now been widely used in the fields such as support of the catalyst, fractionation by adsorption, medicine storage and slowly-releasing.Based on amorphous porous SiO
2microballoon not only self to cement-based material without negative impact, but also there is secondary hydration activity; In addition, vesicular structure can load renovation agent; Meanwhile, its surface has abundant-OH group, is suitable as very much the bridge of modification, makes it carry out functional modification.Porous SiO
2microballoon can carry other materials also can be slowly dissolved in alkali environment, can be used for self-dissolving type self-healing system, and load renovation agent is used for cement-based material crack healing.
At present, SiO
2synthetic method can be divided into dry method and wet method two class, wherein dry method comprises vapor phase process, and wet method has the precipitator method, sol-gel method.
Vapor phase process is normally raw material with silicon tetrachloride, adopts silicon tetrachloride gas under hydrogen-oxygen air-flow high temperature, the SiO of the obtained smoke-like of hydrolysis
2, the Nano-meter SiO_2 that gas-phase process is produced
2, be SiO again
2aerogel, its product density is low, purity is high, particle diameter is little, specific surface area is large, chemical purity is high, dispersing property is good, porosity reaches as high as 98%, and the mesoporous nano structure of its uniqueness makes it have the performance of many excellences, and as low in thermal conductivity, the velocity of sound is low.
Sol-gel processing be with inorganic salt or metal alkoxide for precursor, through the gelation gradually of hydrolytie polycondensation process, then obtain required material through aftertreatment (ageing, drying).Colloidal sol-gel technique prepares Nano-meter SiO_2
2influence factor is a lot, mainly comprises: reactant, water and NH
3concentration, the kind of the type (TMOS, TEOS, TPOS etc.) of silicon ester, the kind (methyl alcohol, ethanol, propyl alcohol, amylalcohol etc.) of alcohol, catalyzer (acid or alkali) and temperature etc.By can obtain the nano-functional material of each class formation to the adjustment of these factors.
The precipitator method refer to that silicate obtains SiO that is loose, finely divided, that be precipitated out with flocculent structure by acidifying
2crystal.At present, SiO is prepared based on the precipitator method
2technology mainly comprises 5 classes: the SiO 1) preparing high dispersive performance in organic solvent
2; 2) souring agent and aqueous silicate solution react, and sediment is through separation, dry preparation SiO
2; 3) alkalimetal silicate and mineral acid are mixed to form SiO
2the water-sol, then change gel particle drying, hot wash, the more obtained SiO of dry, calcining into
2; 4) each SiO of the carbonating system of water glass
2; 5) edge-smoothing aspherical SiO is prepared by mist projection granulating
2.
In addition, arc process, microemulsion method, hypergravity reaction method and hydrothermal synthesis method etc. are also had.
At present, at porous SiO
2the research aspect of microballoon, now existing a lot of patented technology bibliographical information.
Such as, application number be 200810202772.8 Chinese invention patent disclose preparation method and the application of the controlled mesoporous silicon dioxide micro-sphere in a kind of aperture, its mainly with novel four-head quaternary cationics for structure directing agent, in the basic conditions, in alcohol-water system, sol-gel method synthesizing mesoporous silicon dioxide microsphere is passed through.The silicon-dioxide that this patent system obtains is spheroidal particle, and monodispersity is good, and specific surface area is large, and the microballoon prepared is micron order, and particle diameter is comparatively large, and mean pore size is less.
Application number be 201110187685.1 Chinese invention patent disclose a kind of macroporous/mesoporous hollow silica microsphere and preparation method thereof, described macroporous/mesoporous hollow microsphere obtains template with the organic polymeric microspheres of different-grain diameter by self-assembly, by in-situ preparation silica outer layer, then obtain through calcining removing internal organic matter.The microballoon internal cavities that this patent system obtains is that 500-2000nm is controlled, and microsphere surface aperture is that 10-100nm is controlled, forms macroporous/mesoporous hollow structure, but microballoon preparation process is comparatively loaded down with trivial details.
Application number be 201410782248.8 Chinese invention patent disclose a kind of preparation method and application of porous silica microsphere adsorbing agent, tetraethoxy (TEOS) is adopted to be silicon source, ammoniacal liquor is catalyzer, Virahol is solvent, hydrolysis-condensation reaction obtains silicon dioxide microsphere, then is obtained by reacting porous silica microsphere adsorbing agent through a series of.It is mainly used in wastewater treatment, and especially process contains the sewage of highly toxic organic pollutant and heavy metal contamination.
Summary of the invention
Object of the present invention be exactly in order to overcome above-mentioned prior art exist defect and provide a kind of uniform particle sizes, self-dissolving type porous microsphere for distress in concrete selfreparing that monodispersity is good and preparation method thereof.
Object of the present invention can be achieved through the following technical solutions:
For the preparation method of the self-dissolving type porous microsphere of distress in concrete selfreparing; the method is successively by the loading of the preparation of self-dissolving microballoon, the reaming of self-dissolving microballoon, the load of renovation agent and protective membrane; obtained described self-dissolving type porous microsphere, specifically comprises the following steps:
(1) preparation of self-dissolving microballoon
(1-1) organic solvent and deionized water are mixed, add tensio-active agent, ultrasonic mixing;
(1-2) add basic solution, at 20-25 DEG C, stir;
(1-3) the organic silicon ester of disposable injection, and fully stir;
(1-4) in 20-25 DEG C, leave standstill 12-36 hour, filter, retain solid, washing, dry, by calcination process, i.e. obtained SiO
2microballoon;
In actual fabrication process, the time of the ultrasonic mixing in step (1-1) is controlled is made as 10-20 minute, churning time in step (1-2) is controlled is made as 5-10 minute, and after adding organosilicon acid esters, controlling churning time is 30-45 second;
(2) reaming of self-dissolving microballoon
(2-1) complex salt solution is prepared;
(2-2) by SiO
2microballoon is placed in crucible, adds complex salt solution, mixes through ultrasonic, dipping, dries, then carries out calcination process;
(2-3) after calcination process terminates, product, through washing, is dried, the SiO namely after obtained reaming
2microballoon;
In actual fabrication process, the dipping time in step (2-2) may be controlled to 30-45 minute, and the temperature of oven dry may be controlled to 75-85 DEG C, and drying time is 2-3 hour;
(3) load of renovation agent
(3-1) renovation agent solution is prepared;
(3-2) by the SiO after reaming
2microballoon joins in renovation agent solution, soaks or mechanical stirring 24-48 hour in 20-25 DEG C;
(3-3) centrifugation, removing supernatant liquid, bottom microsphere solid is after washing, vacuum-drying, and namely obtained load has the SiO of renovation agent
2microballoon;
In actual fabrication process, the vacuum drying temperature in step (3-3) may be controlled to 100-110 DEG C, and the time is 2-3 hour;
(4) loading of protective membrane
(4-1) protective membrane solution is prepared;
(4-2) load there is the SiO of renovation agent
2microballoon is immersed in protective membrane solution, and in 90-120 DEG C, dipping 2-5 hour, protective membrane is fully loaded into SiO that load has renovation agent
2on microsphere surface.
Organic solvent described in step (1-1) is Virahol, described tensio-active agent is cetylamine, the ammonia soln of to be massfraction the be 25-28% of the basic solution described in step (1-2), organosilicon acid esters described in step (1-3) is tetraethoxy, and the volume ratio of described Virahol and deionized water, ammonia soln, tetraethoxy is 10-15:7-9:0.1-0.15:0.5-0.7, and described cetylamine and the mass ratio of tetraethoxy are 1:5-6.
The condition of the calcination process described in step (1-4) is: under air atmosphere, and control temperature is 500-700 DEG C, and roasting time is 4-8 hour.
Complex salt solution described in step (2-1) is for containing NaCl, LiCl, KNO
3, NaCO
3, NH
4hCO
3or NH
3in the aqueous solution of two or more materials.
Described complex salt solution is for containing NaCl, LiCl and KNO
3the aqueous solution, and NaCl, LiCl, KNO
3be 15-20:4-6:4-6:65-80 with the mass ratio of water.
SiO described in step (2-2)
2microballoon is 1-2g/mL in the mass concentration of complex salt solution, and the condition of described calcination process is: under air atmosphere, and control temperature is 300-400 DEG C, and roasting time is 3-5 hour.
The sodium silicate solution of to be massfraction the be 10-20% of the renovation agent solution described in step (3-1), the SiO after the reaming described in step (3-2)
2the mass ratio of microballoon and renovation agent solution is 1:40-60, and the condition of the centrifugation described in step (3-3) is: centrifugal rotational speed is 8000-9000r/min, and centrifugation time is 10-20min.
Protective membrane solution described in step (4-1) is PVP solution, and the load described in step (4-2) has the SiO of renovation agent
2in microballoon and PVP solution, the mol ratio of PVP is 1:8-12.
In described PVP solution, the relative molecular mass of PVP is 10000-60000.
Adopt the self-dissolving type porous microsphere for distress in concrete selfreparing that aforesaid method is prepared from.
The specific surface area of the self-dissolving type porous microsphere that the present invention obtains is about 60.06m
2/ g, average pore diameter is 32.17nm.
The present invention is based on amorphous porous SiO
2microballoon not only self to cement-based material without negative impact, but also there is secondary hydration activity, vesicular structure load renovation agent and its surface can have abundant-OH group in addition, and the bridge being suitable as very much modification makes the advantage of its functionalization, meanwhile, porous SiO
2microballoon can carry other materials also can be slowly dissolved in alkali environment, can be used for self-dissolving type self-healing system, and in conjunction with the advantage that mineral self-healing is legal and microcapsule self-healing is legal, obtained autolyzed microballoon, for the crack self-healing of cement-based material.
In preparation method of the present invention, described SiO
2microballoon is lightweight block, and using before complex salt solution reaming cannot grinding, can only sonic oscillation dispersion; In the process of carrying out load renovation agent, adopt pickling process load renovation agent, mild condition, controllability is good.
Compared with prior art, the present invention has following characteristics:
1) obtained self-dissolving type porous microsphere uniform particle sizes, monodispersity is good;
2) porous SiO is expanded
2the aperture of microballoon, makes porous SiO in theory
2the charge capacity of microballoon increases, and improves porous SiO
2the service efficiency of microballoon;
3) at SiO
2microsphere surface loads protective membrane, and can make microballoon not by quick corrosion in the alkali environment of inside concrete, reach slowly-releasing renovation agent, the effect of control self-dissolving speed, can be applied in underground water structure;
4) preparation method is simple, and controllability is good, and cost is low, adopts porous SiO
2microballoon is as renovation agent load carriers, combine mineral selfreparing and repair feature and the clear and definite feature of microcapsule selfreparing slowly-releasing incentive mechanism that main body also can participate in repairing reaction, for the crack autogenous healing of cement-based material structure, and repair that speed can control according to specific environment, repairing effect can be effective for a long time.
Accompanying drawing explanation
Fig. 1 is the porous SiO that embodiment 1 obtains
2the SEM spectrogram (scale is 500nm) of microballoon;
Fig. 2 is the porous SiO that embodiment 1 obtains
2the SEM spectrogram (scale is 2 μm) of microballoon;
Fig. 3 is the porous SiO that embodiment 1 obtains
2the XRD spectra (diffraction angle is 10-80 °) of microballoon;
Fig. 4 is the porous SiO that embodiment 1 obtains
2the XRD spectra (diffraction angle is 3-10 °) of microballoon
Fig. 5 is the SiO after the obtained reaming of embodiment 2
2the SEM spectrogram (scale is 500nm) of microballoon;
Fig. 6 is the SiO after the obtained reaming of embodiment 2
2the SEM spectrogram (scale is 1 μm) of microballoon;
Fig. 7 is the SiO that the obtained load of embodiment 3 has renovation agent
2the SEM spectrogram (scale is 1 μm) of microballoon;
Fig. 8 is the SiO that the obtained load of embodiment 4 has renovation agent
2microballoon loads the SEM spectrogram (scale is 1 μm) of protective membrane;
Fig. 9 is the SiO that the obtained load of embodiment 4 has renovation agent
2microballoon loads the SEM spectrogram (scale is 2 μm) of protective membrane.
Embodiment
Below by way of specific specific examples, embodiments of the present invention are described, those skilled in the art the content disclosed by this specification sheets can understand other advantages of the present invention and effect easily.The present invention can also be implemented or be applied by embodiments different in addition, and the every details in this specification sheets also can based on different viewpoints and application, carries out various modification or change not deviating under spirit of the present invention.
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1:
100ml Virahol (analytical pure) and 90ml deionized water are mixed, add 1g cetylamine (analytical pure), ultrasonic mixing, then 1.4ml strong aqua (analytical pure) is added wherein, stir well under room temperature, finally 5.8ml tetraethoxy (TEOS analytical pure)-secondary property is injected in above-mentioned solution, stirs 30s.Left at room temperature one day, the product obtained filters rear ethanol and deionized water successively respectively washes several times.Surface-active agent cetylamine, by obtained product roasting 6h in 600 DEG C of air, can obtain SiO
2microballoon.
Composition graphs 1 and Fig. 2 known, SiO
2microsphere surface hole line width very little (mean pore size 9.17nm), sees it is ganoid spheroid from Electronic Speculum.Particle diameter is also between 1 ~ 2 μm.
Composition graphs 3 is known, porous SiO
2microballoon XRD figure only has the spectrum peak about 2 θ=22 °, and this is SiO
2characteristic diffraction peak, the SiO prepared by explanation
2microballoon is amorphous state material.And from Small angle XRD figure, as shown in Figure 4, sample has a spectrum peak about 2 θ=3 °, describe SiO
2there is meso-hole structure in microballoon inside.
Embodiment 2:
Prepare double salt (raw material is all analytical pure) solution 100g, H in mass ratio
2o:NaCl:LiCl:KNO
3=70:20:5:5, is added in deionized water by the salt taken, heating for dissolving, puts into reagent bottle stand-by after cooling.
The SiO that 1g is prepared
2crucible put into by microballoon, adds the complex salt solution that 10mL prepares, ultrasonic mixing, and dipping 30min, dries 6h at 65 DEG C.Then roasting 4h at air atmosphere 350 DEG C.
The product deionized water wash obtained three times, dries, can obtain the SiO after reaming
2microballoon, SEM figure is see Fig. 5 and Fig. 6.Composition graphs 5 and Fig. 6 known, the SiO after reaming
2there is Kong Wen in spherome surface, surface becomes very coarse, and microspherulite diameter is 32.17nm in the mean pore size of 1-2 μm, Kong Wen.
SiO after expanding treatment
2microballoon also has the phenomenon of little reunion, and as shown in Figure 6, part SiO
2microballoon hole line is more shallow.
Embodiment 3:
Take the sodium silicate solution 60g of 10% massfraction, take 1g reaming SiO
2reaming SiO non-with 1g
2immerse respectively in 60g (density 1.09g/ml, volume 55.04ml) sodium silicate solution, soak at room temperature 1d, will be immersed in the porous SiO in sodium silicate solution
2microballoon with isolate after the centrifugal 20min of 9000r/min bottom centrifugal go out microsphere solid, removing supernatant liquid.By solid with a small amount of water washing once, filtering separation, removing supernatant liquid, solid is 105 DEG C of dry 3h in vacuum drying oven, obtain porous (and reaming) SiO of load water glass
2microballoon.Composition graphs 7 is known, and the microsphere surface hole line of absorption water glass is capped, and can't see obvious crackle, surface is comparatively smooth, and particle diameter is still 1-2 μm.
Embodiment 4:
Adsorb porous (and reaming) SiO of water glass
2microballoon 1g be immersed in molecular weight be 40000 PVP solution in, PVP and SiO
2mol ratio be 10:1.Mixture keeps 3h at 100 DEG C, allows PVP have time enough to be loaded into SiO
2microsphere surface.Composition graphs 8 and Fig. 9 known, microsphere surface covers a skim, and make original hole line become creep fuzzy, surperficial nearly smooth, just forms articulamentum by this floor height molecular film in the middle of little reunion microballoon, particle diameter is still 1-2 μm.
Embodiment 5:
The present embodiment is used for the preparation method of the self-dissolving type porous microsphere of distress in concrete selfreparing; the method is successively by the loading of the preparation of self-dissolving microballoon, the reaming of self-dissolving microballoon, the load of renovation agent and protective membrane; obtained described self-dissolving type porous microsphere, specifically comprises the following steps:
(1) preparation of self-dissolving microballoon
(1-1) organic solvent and deionized water are mixed, add tensio-active agent, ultrasonic mixing;
(1-2) add basic solution, at 25 DEG C, stir;
(1-3) the organic silicon ester of disposable injection, and fully stir;
(1-4) in 25 DEG C, leave standstill 36 hours, filter, retain solid, washing, dry, by calcination process, i.e. obtained SiO
2microballoon;
In actual fabrication process, the time of the ultrasonic mixing in step (1-1) is controlled is made as 20 minutes, and the churning time in step (1-2) is controlled is made as 10 minutes, and after adding organosilicon acid esters, controlling churning time is 30 seconds;
(2) reaming of self-dissolving microballoon
(2-1) complex salt solution is prepared;
(2-2) by SiO
2microballoon is placed in crucible, adds complex salt solution, mixes through ultrasonic, dipping, dries, then carries out calcination process;
(2-3) after calcination process terminates, product, through washing, is dried, the SiO namely after obtained reaming
2microballoon;
In actual fabrication process, the dipping time in step (2-2) may be controlled to 45 minutes, and the temperature of oven dry may be controlled to 85 DEG C, and drying time is 2 hours;
(3) load of renovation agent
(3-1) renovation agent solution is prepared;
(3-2) by the SiO after reaming
2microballoon joins in renovation agent solution, soaks or mechanical stirring 24 hours in 25 DEG C;
(3-3) centrifugation, removing supernatant liquid, bottom microsphere solid is after washing, vacuum-drying, and namely obtained load has the SiO of renovation agent
2microballoon;
In actual fabrication process, the vacuum drying temperature in step (3-3) may be controlled to 110 DEG C, and the time is 2 hours;
(4) loading of protective membrane
(4-1) protective membrane solution is prepared;
(4-2) load there is the SiO of renovation agent
2microballoon is immersed in protective membrane solution, and in 120 DEG C, floods 2 hours, protective membrane is fully loaded into SiO that load has renovation agent
2on microsphere surface.
In step (1-1), organic solvent is Virahol, tensio-active agent is cetylamine, in step (1-2), basic solution to be massfraction be 25% ammonia soln, in step (1-3), organosilicon acid esters is tetraethoxy, and the volume ratio of Virahol and deionized water, ammonia soln, tetraethoxy is 15:9:0.15:0.7, and the mass ratio of cetylamine and tetraethoxy is 1:6.
In step (1-4), the condition of calcination process is: under air atmosphere, and control temperature is 700 DEG C, and roasting time is 4 hours.
In step (2-1), complex salt solution is for containing NaCl, LiCl and KNO
3the aqueous solution, and NaCl, LiCl, KNO
3be 20:6:6:80 with the mass ratio of water.
In step (2-2), SiO
2microballoon is 2g/mL in the mass concentration of complex salt solution, and the condition of calcination process is: under air atmosphere, and control temperature is 400 DEG C, and roasting time is 5 hours.
In step (3-1), renovation agent solution to be massfraction be 20% sodium silicate solution, in step (3-2), the SiO after reaming
2the mass ratio of microballoon and renovation agent solution is 1:60, and in step (3-3), the condition of centrifugation is: centrifugal rotational speed is 9000r/min, and centrifugation time is 10min.
In step (4-1), protective membrane solution is PVP solution, and in step (4-2), load has the SiO of renovation agent
2in microballoon and PVP solution, the mol ratio of PVP is 1:12.Wherein, in PVP solution, the relative molecular mass of PVP is 60000.
Embodiment 6:
The present embodiment is used for the preparation method of the self-dissolving type porous microsphere of distress in concrete selfreparing; the method is successively by the loading of the preparation of self-dissolving microballoon, the reaming of self-dissolving microballoon, the load of renovation agent and protective membrane; obtained described self-dissolving type porous microsphere, specifically comprises the following steps:
(1) preparation of self-dissolving microballoon
(1-1) organic solvent and deionized water are mixed, add tensio-active agent, ultrasonic mixing;
(1-2) add basic solution, at 20 DEG C, stir;
(1-3) the organic silicon ester of disposable injection, and fully stir;
(1-4) in 20 DEG C, leave standstill 12 hours, filter, retain solid, washing, dry, by calcination process, i.e. obtained SiO
2microballoon;
In actual fabrication process, the time of the ultrasonic mixing in step (1-1) is controlled is made as 10 minutes, and the churning time in step (1-2) is controlled is made as 5 minutes, and after adding organosilicon acid esters, controlling churning time is 45 seconds;
(2) reaming of self-dissolving microballoon
(2-1) complex salt solution is prepared;
(2-2) by SiO
2microballoon is placed in crucible, adds complex salt solution, mixes through ultrasonic, dipping, dries, then carries out calcination process;
(2-3) after calcination process terminates, product, through washing, is dried, the SiO namely after obtained reaming
2microballoon;
In actual fabrication process, the dipping time in step (2-2) may be controlled to 30 minutes, and the temperature of oven dry may be controlled to 75 DEG C, and drying time is 3 hours;
(3) load of renovation agent
(3-1) renovation agent solution is prepared;
(3-2) by the SiO after reaming
2microballoon joins in renovation agent solution, soaks or mechanical stirring 48 hours in 20 DEG C;
(3-3) centrifugation, removing supernatant liquid, bottom microsphere solid is after washing, vacuum-drying, and namely obtained load has the SiO of renovation agent
2microballoon;
In actual fabrication process, the vacuum drying temperature in step (3-3) may be controlled to 100 DEG C, and the time is 3 hours;
(4) loading of protective membrane
(4-1) protective membrane solution is prepared;
(4-2) load there is the SiO of renovation agent
2microballoon is immersed in protective membrane solution, and in 90 DEG C, floods 5 hours, protective membrane is fully loaded into SiO that load has renovation agent
2on microsphere surface.
In step (1-1), organic solvent is Virahol, tensio-active agent is cetylamine, in step (1-2), basic solution to be massfraction be 28% ammonia soln, in step (1-3), organosilicon acid esters is tetraethoxy, and the volume ratio of Virahol and deionized water, ammonia soln, tetraethoxy is 10:7:0.1:0.5, and the mass ratio of cetylamine and tetraethoxy is 1:5.
In step (1-4), the condition of calcination process is: under air atmosphere, and control temperature is 500 DEG C, and roasting time is 8 hours.
In step (2-1), complex salt solution is for containing NaCl, LiCl and KNO
3the aqueous solution, and NaCl, LiCl, KNO
3be 15:4:4:65 with the mass ratio of water.
In step (2-2), SiO
2microballoon is 1g/mL in the mass concentration of complex salt solution, and the condition of calcination process is: under air atmosphere, and control temperature is 300 DEG C, and roasting time is 3 hours.
In step (3-1), renovation agent solution to be massfraction be 10% sodium silicate solution, in step (3-2), the SiO after reaming
2the mass ratio of microballoon and renovation agent solution is 1:40, and in step (3-3), the condition of centrifugation is: centrifugal rotational speed is 8000r/min, and centrifugation time is 20min.
In step (4-1), protective membrane solution is PVP solution, and in step (4-2), load has the SiO of renovation agent
2in microballoon and PVP solution, the mol ratio of PVP is 1:8.Wherein, in PVP solution, the relative molecular mass of PVP is 40000.
Embodiment 7:
The present embodiment is used for the preparation method of the self-dissolving type porous microsphere of distress in concrete selfreparing; the method is successively by the loading of the preparation of self-dissolving microballoon, the reaming of self-dissolving microballoon, the load of renovation agent and protective membrane; obtained described self-dissolving type porous microsphere, specifically comprises the following steps:
(1) preparation of self-dissolving microballoon
(1-1) organic solvent and deionized water are mixed, add tensio-active agent, ultrasonic mixing;
(1-2) add basic solution, at 24 DEG C, stir;
(1-3) the organic silicon ester of disposable injection, and fully stir;
(1-4) in 24 DEG C, leave standstill 24 hours, filter, retain solid, washing, dry, by calcination process, i.e. obtained SiO
2microballoon;
In actual fabrication process, the time of the ultrasonic mixing in step (1-1) is controlled is made as 15 minutes, and the churning time in step (1-2) is controlled is made as 8 minutes, and after adding organosilicon acid esters, controlling churning time is 40 seconds;
(2) reaming of self-dissolving microballoon
(2-1) complex salt solution is prepared;
(2-2) by SiO
2microballoon is placed in crucible, adds complex salt solution, mixes through ultrasonic, dipping, dries, then carries out calcination process;
(2-3) after calcination process terminates, product, through washing, is dried, the SiO namely after obtained reaming
2microballoon;
In actual fabrication process, the dipping time in step (2-2) may be controlled to 40 minutes, and the temperature of oven dry may be controlled to 82 DEG C, and drying time is 2.5 hours;
(3) load of renovation agent
(3-1) renovation agent solution is prepared;
(3-2) by the SiO after reaming
2microballoon joins in renovation agent solution, soaks 36 hours in 24 DEG C;
(3-3) centrifugation, removing supernatant liquid, bottom microsphere solid is after washing, vacuum-drying, and namely obtained load has the SiO of renovation agent
2microballoon;
In actual fabrication process, the vacuum drying temperature in step (3-3) may be controlled to 105 DEG C, and the time is 2.5 hours;
(4) loading of protective membrane
(4-1) protective membrane solution is prepared;
(4-2) load there is the SiO of renovation agent
2microballoon is immersed in protective membrane solution, and in 110 DEG C, floods 3 hours, protective membrane is fully loaded into SiO that load has renovation agent
2on microsphere surface.
In step (1-1), organic solvent is Virahol, tensio-active agent is cetylamine, in step (1-2), basic solution to be massfraction be 27% ammonia soln, in step (1-3), organosilicon acid esters is tetraethoxy, and the volume ratio of Virahol and deionized water, ammonia soln, tetraethoxy is 12:8:0.13:0.6, and the mass ratio of cetylamine and tetraethoxy is 1:5.6.
In step (1-4), the condition of calcination process is: under air atmosphere, and control temperature is 600 DEG C, and roasting time is 6 hours.
In step (2-1), complex salt solution is for containing NaCl, LiCl and KNO
3the aqueous solution, and NaCl, LiCl, KNO
3be 17:5:5:73 with the mass ratio of water.
In step (2-2), SiO
2microballoon is 1.5g/mL in the mass concentration of complex salt solution, and the condition of calcination process is: under air atmosphere, and control temperature is 360 DEG C, and roasting time is 4 hours.
In step (3-1), renovation agent solution to be massfraction be 15% sodium silicate solution, in step (3-2), the SiO after reaming
2the mass ratio of microballoon and renovation agent solution is 1:48, and in step (3-3), the condition of centrifugation is: centrifugal rotational speed is 8500r/min, and centrifugation time is 15min.
In step (4-1), protective membrane solution is PVP solution, and in step (4-2), load has the SiO of renovation agent
2in microballoon and PVP solution, the mol ratio of PVP is 1:10.Wherein, in PVP solution, the relative molecular mass of PVP is 50000.
Embodiment 8:
The present embodiment is used for the preparation method of the self-dissolving type porous microsphere of distress in concrete selfreparing; the method is successively by the loading of the preparation of self-dissolving microballoon, the reaming of self-dissolving microballoon, the load of renovation agent and protective membrane; obtained described self-dissolving type porous microsphere, specifically comprises the following steps:
(1) preparation of self-dissolving microballoon
(1-1) organic solvent and deionized water are mixed, add tensio-active agent, ultrasonic mixing;
(1-2) add basic solution, at 22 DEG C, stir;
(1-3) the organic silicon ester of disposable injection, and fully stir;
(1-4) in 22 DEG C, leave standstill 18 hours, filter, retain solid, washing, dry, by calcination process, i.e. obtained SiO
2microballoon;
In actual fabrication process, the time of the ultrasonic mixing in step (1-1) is controlled is made as 18 minutes, and the churning time in step (1-2) is controlled is made as 6 minutes, and after adding organosilicon acid esters, controlling churning time is 38 seconds;
(2) reaming of self-dissolving microballoon
(2-1) complex salt solution is prepared;
(2-2) by SiO
2microballoon is placed in crucible, adds complex salt solution, mixes through ultrasonic, dipping, dries, then carries out calcination process;
(2-3) after calcination process terminates, product, through washing, is dried, the SiO namely after obtained reaming
2microballoon;
In actual fabrication process, the dipping time in step (2-2) may be controlled to 35 minutes, and the temperature of oven dry may be controlled to 78 DEG C, and drying time is 3 hours;
(3) load of renovation agent
(3-1) renovation agent solution is prepared;
(3-2) by the SiO after reaming
2microballoon joins in renovation agent solution, soaks 30 hours in 22 DEG C;
(3-3) centrifugation, removing supernatant liquid, bottom microsphere solid is after washing, vacuum-drying, and namely obtained load has the SiO of renovation agent
2microballoon;
In actual fabrication process, the vacuum drying temperature in step (3-3) may be controlled to 108 DEG C, and the time is 2 hours;
(4) loading of protective membrane
(4-1) protective membrane solution is prepared;
(4-2) load there is the SiO of renovation agent
2microballoon is immersed in protective membrane solution, and in 115 DEG C, floods 4 hours, protective membrane is fully loaded into SiO that load has renovation agent
2on microsphere surface.
In step (1-1), organic solvent is Virahol, tensio-active agent is cetylamine, in step (1-2), basic solution to be massfraction be 27% ammonia soln, in step (1-3), organosilicon acid esters is tetraethoxy, and the volume ratio of Virahol and deionized water, ammonia soln, tetraethoxy is 14:8:0.14:0.5, and the mass ratio of cetylamine and tetraethoxy is 1:5.8.
In step (1-4), the condition of calcination process is: under air atmosphere, and control temperature is 630 DEG C, and roasting time is 7 hours.
In step (2-1), complex salt solution is for containing LiCl, NaCO
3and NH
3the aqueous solution, and LiCl, NaCO
3, NH
3be 20:5:5:70 with the mass ratio of water.
In step (2-2), SiO
2microballoon is 1.8g/mL in the mass concentration of complex salt solution, and the condition of calcination process is: under air atmosphere, and control temperature is 340 DEG C, and roasting time is 5 hours.
In step (3-1), renovation agent solution to be massfraction be 18% sodium silicate solution, in step (3-2), the SiO after reaming
2the mass ratio of microballoon and renovation agent solution is 1:56, and in step (3-3), the condition of centrifugation is: centrifugal rotational speed is 8600r/min, and centrifugation time is 18min.
In step (4-1), protective membrane solution is PVP solution, and in step (4-2), load has the SiO of renovation agent
2in microballoon and PVP solution, the mol ratio of PVP is 1:9.Wherein, in PVP solution, the relative molecular mass of PVP is 10000.
Embodiment 9:
The present embodiment is used for the preparation method of the self-dissolving type porous microsphere of distress in concrete selfreparing, specifically comprises the following steps:
(1) preparation of self-dissolving microballoon
(1-1) organic solvent and deionized water are mixed, add tensio-active agent, ultrasonic mixing;
(1-2) add basic solution, at 20 DEG C, stir;
(1-3) the organic silicon ester of disposable injection, and fully stir;
(1-4) in 20 DEG C, leave standstill 18 hours, filter, retain solid, washing, dry, by calcination process, i.e. obtained SiO
2microballoon;
In actual fabrication process, the time of the ultrasonic mixing in step (1-1) is controlled is made as 18 minutes, and the churning time in step (1-2) is controlled is made as 6 minutes, and after adding organosilicon acid esters, controlling churning time is 30 seconds;
(2) reaming of self-dissolving microballoon
(2-1) complex salt solution is prepared;
(2-2) by SiO
2microballoon is placed in crucible, adds complex salt solution, mixes through ultrasonic, dipping, dries, then carries out calcination process;
(2-3) after calcination process terminates, product, through washing, is dried, the SiO namely after obtained reaming
2microballoon;
In actual fabrication process, the dipping time in step (2-2) may be controlled to 40 minutes, and the temperature of oven dry may be controlled to 80 DEG C, and drying time is 3 hours;
(3) load of renovation agent
(3-1) renovation agent solution is prepared;
(3-2) by the SiO after reaming
2microballoon joins in renovation agent solution, soaks 30 hours in 20 DEG C;
(3-3) centrifugation, removing supernatant liquid, bottom microsphere solid is after washing, vacuum-drying, and namely obtained load has the SiO of renovation agent
2microballoon;
In actual fabrication process, the vacuum drying temperature in step (3-3) may be controlled to 106 DEG C, and the time is 2 hours;
(4) loading of protective membrane
(4-1) protective membrane solution is prepared;
(4-2) load there is the SiO of renovation agent
2microballoon is immersed in protective membrane solution, and in 106 DEG C, floods 5 hours, protective membrane is fully loaded into SiO that load has renovation agent
2on microsphere surface.
In step (1-1), organic solvent is Virahol, tensio-active agent is cetylamine, in step (1-2), basic solution to be massfraction be 28% ammonia soln, in step (1-3), organosilicon acid esters is tetraethoxy, and the volume ratio of Virahol and deionized water, ammonia soln, tetraethoxy is 11:9:0.1:0.6, and the mass ratio of cetylamine and tetraethoxy is 1:5.
In step (1-4), the condition of calcination process is: under air atmosphere, and control temperature is 680 DEG C, and roasting time is 5 hours.
In step (2-1), complex salt solution is for containing LiCl and NH
4hCO
3the aqueous solution, and LiCl, NH
4hCO
3be 18:5:68 with the mass ratio of water.
In step (2-2), SiO
2microballoon is 1.2g/mL in the mass concentration of complex salt solution, and the condition of calcination process is: under air atmosphere, and control temperature is 380 DEG C, and roasting time is 4 hours.
In step (3-1), renovation agent solution to be massfraction be 12% sodium silicate solution, in step (3-2), the SiO after reaming
2the mass ratio of microballoon and renovation agent solution is 1:48, and in step (3-3), the condition of centrifugation is: centrifugal rotational speed is 9000r/min, and centrifugation time is 12min.
In step (4-1), protective membrane solution is PVP solution, and in step (4-2), load has the SiO of renovation agent
2in microballoon and PVP solution, the mol ratio of PVP is 1:10.Wherein, in PVP solution, the relative molecular mass of PVP is 42000.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.
Claims (10)
1. for the preparation method of the self-dissolving type porous microsphere of distress in concrete selfreparing; it is characterized in that; the method is successively by the loading of the preparation of self-dissolving microballoon, the reaming of self-dissolving microballoon, the load of renovation agent and protective membrane, and obtained described self-dissolving type porous microsphere, specifically comprises the following steps:
(1) preparation of self-dissolving microballoon
(1-1) organic solvent and deionized water are mixed, add tensio-active agent, ultrasonic mixing;
(1-2) add basic solution, at 20-25 DEG C, stir;
(1-3) the organic silicon ester of disposable injection, and fully stir;
(1-4) in 20-25 DEG C, leave standstill 12-36 hour, filter, retain solid, washing, dry, by calcination process, i.e. obtained SiO
2microballoon;
(2) reaming of self-dissolving microballoon
(2-1) complex salt solution is prepared;
(2-2) by SiO
2microballoon is placed in crucible, adds complex salt solution, mixes through ultrasonic, dipping, dries, then carries out calcination process;
(2-3) after calcination process terminates, product, through washing, is dried, the SiO namely after obtained reaming
2microballoon;
(3) load of renovation agent
(3-1) renovation agent solution is prepared;
(3-2) by the SiO after reaming
2microballoon joins in renovation agent solution, soaks or mechanical stirring 24-48 hour in 20-25 DEG C;
(3-3) centrifugation, removing supernatant liquid, bottom microsphere solid is after washing, vacuum-drying, and namely obtained load has the SiO of renovation agent
2microballoon;
(4) loading of protective membrane
(4-1) protective membrane solution is prepared;
(4-2) load there is the SiO of renovation agent
2microballoon is immersed in protective membrane solution, and in 90-120 DEG C, dipping 2-5 hour, protective membrane is fully loaded into SiO that load has renovation agent
2on microsphere surface.
2. the preparation method of the self-dissolving type porous microsphere for distress in concrete selfreparing according to claim 1, it is characterized in that, organic solvent described in step (1-1) is Virahol, described tensio-active agent is cetylamine, the ammonia soln of to be massfraction the be 25-28% of the basic solution described in step (1-2), organosilicon acid esters described in step (1-3) is tetraethoxy, and described Virahol and deionized water, ammonia soln, the volume ratio of tetraethoxy is 10-15:7-9:0.1-0.15:0.5-0.7, described cetylamine and the mass ratio of tetraethoxy are 1:5-6.
3. the preparation method of the self-dissolving type porous microsphere for distress in concrete selfreparing according to claim 1, it is characterized in that, the condition of the calcination process described in step (1-4) is: under air atmosphere, and control temperature is 500-700 DEG C, and roasting time is 4-8 hour.
4. the preparation method of the self-dissolving type porous microsphere for distress in concrete selfreparing according to claim 1, is characterized in that, the complex salt solution described in step (2-1) is for containing NaCl, LiCl, KNO
3, NaCO
3, NH
4hCO
3or NH
3in the aqueous solution of two or more materials.
5. the preparation method of the self-dissolving type porous microsphere for distress in concrete selfreparing according to claim 4, is characterized in that, described complex salt solution is for containing NaCl, LiCl and KNO
3the aqueous solution, and NaCl, LiCl, KNO
3be 15-20:4-6:4-6:65-80 with the mass ratio of water.
6. the preparation method of the self-dissolving type porous microsphere for distress in concrete selfreparing according to claim 1, is characterized in that, the SiO described in step (2-2)
2microballoon is 1-2g/mL in the mass concentration of complex salt solution, and the condition of described calcination process is: under air atmosphere, and control temperature is 300-400 DEG C, and roasting time is 3-5 hour.
7. the preparation method of the self-dissolving type porous microsphere for distress in concrete selfreparing according to claim 1, it is characterized in that, the sodium silicate solution of to be massfraction the be 10-20% of the renovation agent solution described in step (3-1), the SiO after the reaming described in step (3-2)
2the mass ratio of microballoon and renovation agent solution is 1:40-60, and the condition of the centrifugation described in step (3-3) is: centrifugal rotational speed is 8000-9000r/min, and centrifugation time is 10-20min.
8. the preparation method of the self-dissolving type porous microsphere for distress in concrete selfreparing according to claim 1; it is characterized in that; protective membrane solution described in step (4-1) is PVP solution, and the load described in step (4-2) has the SiO of renovation agent
2in microballoon and PVP solution, the mol ratio of PVP is 1:8-12.
9. the preparation method of the self-dissolving type porous microsphere for distress in concrete selfreparing according to claim 8, it is characterized in that, in described PVP solution, the relative molecular mass of PVP is 10000-60000.
10. the self-dissolving type porous microsphere for distress in concrete selfreparing that the method as described in any one of claim 1 to 9 is prepared from.
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