CN105565326B - Self-dissolving type porous microsphere for self-repairing of concrete cracks and preparation method thereof - Google Patents
Self-dissolving type porous microsphere for self-repairing of concrete cracks and preparation method thereof Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 86
- 238000000034 method Methods 0.000 claims abstract description 80
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 58
- 238000009418 renovation Methods 0.000 claims abstract description 52
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 51
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 51
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 51
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 51
- 230000001681 protective effect Effects 0.000 claims abstract description 24
- 238000011068 loading method Methods 0.000 claims abstract description 22
- 230000008439 repair process Effects 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 85
- 230000008569 process Effects 0.000 claims description 57
- 238000001354 calcination Methods 0.000 claims description 36
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 34
- 239000012266 salt solution Substances 0.000 claims description 32
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 31
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 26
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 17
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical group CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 16
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 15
- 238000005119 centrifugation Methods 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 239000012670 alkaline solution Substances 0.000 claims description 14
- 229910021529 ammonia Inorganic materials 0.000 claims description 14
- 150000002148 esters Chemical class 0.000 claims description 14
- 239000004094 surface-active agent Substances 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 14
- 239000004115 Sodium Silicate Substances 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 239000011780 sodium chloride Substances 0.000 claims description 13
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 9
- 241001502050 Acis Species 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 7
- 150000002895 organic esters Chemical class 0.000 claims description 7
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 3
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 17
- 239000004568 cement Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 8
- 239000011707 mineral Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000003094 microcapsule Substances 0.000 abstract description 5
- 230000035876 healing Effects 0.000 abstract description 4
- 238000013268 sustained release Methods 0.000 abstract description 4
- 239000012730 sustained-release form Substances 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract description 2
- 230000007246 mechanism Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 description 19
- 239000003513 alkali Substances 0.000 description 4
- 238000005516 engineering process Methods 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
- 238000001556 precipitation Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 150000003839 salts Chemical class 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
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000011806 microball Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical group CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010011732 Cyst Diseases 0.000 description 1
- 241000790917 Dioxys <bee> Species 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
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 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
- 230000004075 alteration Effects 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000011805 ball Substances 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 208000031513 cyst Diseases 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 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
- 239000008187 granular material Substances 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
- 238000007654 immersion Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000004615 ingredient Substances 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
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 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
- 150000007522 mineralic acids Chemical class 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 235000019353 potassium silicate Nutrition 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
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 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
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003643 water by type Substances 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 present invention relates to self-dissolving type porous microspheres for self-repairing of concrete cracks and preparation method thereof, and this method passes sequentially through the loading of the preparation of self-dissolving microballoon, the reaming of self-dissolving microballoon, the load of renovation agent and protective film, and the self-dissolving type porous microsphere is made.Compared with prior art, preparation method of the present invention is simple, and controllability is good, at low cost, using porous SiO2Microballoon is as renovation agent load carriers, combine the characteristics of the characteristics of main body can also participate in repairing reaction and clear and definite microcapsules selfreparing sustained release incentive mechanism are repaired in mineral selfreparing, for the crack autogenous healing of cement-based material structure, and repair rate can be controlled according to specific environment, repairing effect can for a long time effectively.
Description
Technical field
The invention belongs to concrete works technical fields, are related to a kind of self-dissolving type porous microsphere and preparation method thereof, especially
Be be related to it is a kind of for self-dissolving type porous microsphere of self-repairing of concrete cracks and preparation method thereof.
Background technology
The self-healing of cement-based material mineral adds in part mineral material in cement-based material system, there is water at crack
In the case of infiltration, it can promote and encourage the diffusion, migration and reaction of wherein effective ion, effectively healing is generated at crack
Product completes self-healing function.Since basis material composition is different with mineral material ingredient, heal product also incomplete phase
Together, mainly include C-S-H gels, calcium carbonate crystal precipitation, calcium hydroxide etc..
At present, it is more for the research of different cement-based material self-healing methods, it is more biased towards in practice in use mineral certainly
Healing and the method for microcapsules self-healing.But mineral self-healing it is legal motivational techniques it is indefinite, cyst wall after microcapsules rupture
Material can have a negative impact to cement-based material.Above two method is further improved.
Porous SiO2The advantages that microballoon is due to its large specific surface area, porosity height, good fluidity, easy dispersion, it is wide
It is general to be applied to the fields such as catalyst carrier, adsorbing separation, drug storage and sustained release.Based on amorphous porous SiO2Microballoon not only from
Body to cement-based material without negative effect, but also with secondary hydration activity；In addition, porous structure can load renovation agent；Together
When, surface has abundant-OH groups, is highly suitable as modified bridge, it is made to carry out functional modification.Porous SiO2
Microballoon, which can carry other substances, can also be slowly dissolved in alkali environment, and available for self-dissolving type self-healing system, load renovation agent is used for water
Cement-based material crack self-healing.
At present, SiO2Synthetic method can be divided into two class of dry and wet, wherein dry method includes vapor phase method, and wet method has precipitation
Method, sol-gel method.
Vapor phase method is typically using silicon tetrachloride as raw material, and using silicon tetrachloride gas under hydrogen-oxygen air-flow high temperature, hydrolysis is made
Obtain the SiO of smoke-like2, the Nano-meter SiO_2 of gas-phase process production2, it is called SiO2Aeroge, product density is low, purity is high, grain
Diameter is small, large specific surface area, chemical purity are high, dispersion performance is good, porosity reaches as high as 98%, unique mesoporous nano structure
Many excellent performances are made it have, such as thermal conductivity is low, the velocity of sound is low.
Sol-gel processing is using inorganic salts or metal alkoxide as predecessor, through the gradual gelation of hydrolytie polycondensation process, so
Required material is obtained by processing later (ageing, drying).Colloidal sol-gel technique prepares Nano-meter SiO_22There are many influence factor,
Mainly include：Reactant, water and NH3Concentration, type (TMOS, TEOS, TPOS etc.), type (methanol, the second of alcohol of esters of silicon acis
Alcohol, propyl alcohol, amylalcohol etc.), the type of catalyst (acid or alkali) and temperature etc..It can be obtained respectively by the adjusting to these factors
The nano-functional material of class formation.
The precipitation method refer to that silicate obtains SiO that is loose, finely divided, being precipitated out with flocculent structure by being acidified2Crystal.
At present, SiO is prepared based on the precipitation method2Technology mainly includes 5 classes：1) SiO of polymolecularity energy is prepared in organic solvent2；2) it is sour
Agent is reacted with aqueous silicate solution, and sediment prepares SiO through detaching, drying2；3) alkali silicate mixes shape with inorganic acid
Into SiO2The hydrosol, then be changed into gel particle and SiO is made through drying, hot water washing, re-dry, calcining2；4) carbon of waterglass
Each SiO is made in acidification2；5) the aspherical SiO of edge-smoothing is prepared by mist projection granulating2。
In addition, also arc process, microemulsion method, hypergravity reaction method and hydrothermal synthesis method etc..
At present, in porous SiO2In terms of the research of microballoon, it there is now many patented technology document reports.
For example, the Chinese invention patent application No. is 200810202772.8 discloses a kind of controllable mesoporous dioxy in aperture
The preparation method and application of SiClx microballoon, mainly using novel four-head quaternary cationics as structure directing
Agent under alkaline condition, passes through sol-gal process synthesizing mesoporous silicon dioxide microsphere in alcohol-water system.Two made from the patent
Silica is spheric granules, and monodispersity is good, large specific surface area, and the microballoon prepared is micron order, and grain size is larger, average pore size
It is smaller.
Application No. is 201110187685.1 Chinese invention patent, to disclose a kind of macroporous/mesoporous hollow silica micro-
Ball and preparation method thereof, the macroporous/mesoporous hollow microsphere are obtained with the organic polymeric microspheres of different-grain diameter by self assembly
To template, by in-situ preparation silica outer layer, then remove internal organic matter through calcining and obtain.It is micro- made from the patent
Ball internal cavities are controllable for 500-2000nm, and microsphere surface aperture is controllable for 10-100nm, forms macroporous/mesoporous hollow structure,
But microballoon preparation process is relatively complicated.
Chinese invention patent application No. is 201410782248.8 discloses a kind of porous silica microsphere adsorbing agent
Preparation method and application, using ethyl orthosilicate (TEOS), ammonium hydroxide is catalyst for silicon source, and isopropanol is solvent, hydrolysis-contracting
It is poly- that silicon dioxide microsphere is obtained by the reaction, porous silica microsphere adsorbing agent is obtained by the reaction using a series of.It is mainly used
In wastewater treatment, especially sewage of the processing containing highly toxic organic pollution and heavy metal pollution.
Invention content
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of uniform particle sizes, single point
Dissipate property it is good for self-dissolving type porous microsphere of self-repairing of concrete cracks and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions：
For the preparation method of the self-dissolving type porous microsphere of self-repairing of concrete cracks, this method passes sequentially through self-dissolving microballoon
Preparation, the reaming of self-dissolving microballoon, the load of renovation agent and protective film loading, the self-dissolving type porous microsphere is made,
Specifically include following steps：
(1) preparation of self-dissolving microballoon
Organic solvent and deionized water are uniformly mixed by (1-1), add in surfactant, ultrasonic mixing；
(1-2) adds in alkaline solution, at 20-25 DEG C, stirs evenly；
(1-3) disposably injects organic esters of silicon acis, and is sufficiently stirred；
(1-4) stands 12-36 hour in 20-25 DEG C, filtering, retains solid, washing, drying, by calcination process, i.e.,
SiO is made2Microballoon；
In actual fabrication process, the time of the ultrasonic mixing in step (1-1) is controllable to 10-20 minutes, step (1-
2) mixing time in is controllable to 5-10 minutes, and after adding in organosilicon acid esters, control mixing time is 30-45 seconds；
(2) reaming of self-dissolving microballoon
(2-1) prepares complex salt solution；
(2-2) is by SiO2Microballoon is placed in crucible, adds in complex salt solution, uniform through ultrasonic mixing, is impregnated, drying, then into
Row calcination process；
After (2-3) treats calcination process, product is washed, and drying obtains the SiO after reaming2Microballoon；
In actual fabrication process, the dip time in step (2-2) may be controlled to 30-45 minutes, the temperature of drying
75-85 DEG C is may be controlled to, drying time is 2-3 hours；
(3) load of renovation agent
(3-1), which is prepared, repairs agent solution；
(3-2) is by the SiO after reaming2Microballoon, which is added to, to be repaired in agent solution, in 20-25 DEG C of immersion or mechanical agitation 24-
48 hours；
(3-3) is centrifuged, and removes supernatant liquor, and bottom microsphere solid is washed, after vacuum drying, and obtaining load has
The SiO of renovation agent2Microballoon；
In actual fabrication process, the vacuum drying temperature in step (3-3) may be controlled to 100-110 DEG C, the time
It is 2-3 hours；
(4) loading of protective film
(4-1) prepares protection coating solution；
(4-2) has the SiO of renovation agent by loading2Microballoon is immersed in protection coating solution, and in 90-120 DEG C, impregnates 2-5
Hour so that protective film, which is fully loaded into load, the SiO of renovation agent2On microsphere surface.
Organic solvent described in step (1-1) is isopropanol, and the surfactant is cetylamine, step (1-2)
Described in alkaline solution be ammonia spirit that mass fraction is 25-28%, the organosilicon acid esters described in step (1-3) is just
Silester, and the volume ratio of the isopropanol and deionized water, ammonia spirit, ethyl orthosilicate is 10-15:7-9:
0.1-0.15:The mass ratio of 0.5-0.7, the cetylamine and ethyl orthosilicate is 1:5-6.
The condition of calcination process described in step (1-4) is：Under air atmosphere, controlled at 500-700 DEG C, roasting
It is 4-8 hours to burn the time.
Complex salt solution described in step (2-1) is contains NaCl, LiCl, KNO3、Na2CO3、NH4HCO3Or NH3In two
The aqueous solution of kind or many kinds of substance.
The complex salt solution is contains NaCl, LiCl and KNO3Aqueous solution, and NaCl, LiCl, KNO3With the matter of water
Amount is than being 15-20:4-6:4-6:65-80.
SiO described in step (2-2)2Microballoon complex salt solution mass concentration for 1-2g/mL, the calcination process
Condition be：Under air atmosphere, controlled at 300-400 DEG C, roasting time is 3-5 hours.
Reparation agent solution described in step (3-1) is the sodium silicate solution that mass fraction is 10-20%, step (3-2)
Described in reaming after SiO2Microballoon is 1 with the mass ratio for repairing agent solution:40-60, the centrifugation point described in step (3-3)
From condition be：Centrifugal rotational speed is 8000-9000r/min, centrifugation time 10-20min.
Protection coating solution described in step (4-1) is PVP solution, and the load described in step (4-2) has renovation agent
SiO2The molar ratio of microballoon and PVP in PVP solution are 1:8-12.
The relative molecular mass of PVP is 10000-60000 in the PVP solution.
The self-dissolving type porous microsphere for self-repairing of concrete cracks being prepared using the above method.
The specific surface area of self-dissolving type porous microsphere produced by the present invention is about 60.06m2/ g, average pore diameter are
32.17nm。
The present invention is based on amorphous porous SiO2Microballoon not only itself to cement-based material without negative effect, but also have
Secondary hydration activity, in addition porous structure, which can load renovation agent and its surface, has abundant-OH groups, is highly suitable as
Modified bridge makes the advantages of its functionalization, meanwhile, porous SiO2Microballoon, which can carry other substances, can also be slowly dissolved in alkali environment,
It is legal and the advantages of microcapsules self-healing is legal with reference to mineral self-healing available for self-dissolving type self-healing system, it is obtained autolyzed micro-
Ball, for the crack self-healing of cement-based material.
In preparation method of the present invention, the SiO2Microballoon is lightweight block, using cannot before complex salt solution reaming
Grinding, can only sonic oscillation dispersion；During load renovation agent is carried out, using infusion process load renovation agent, mild condition,
Controllability is good.
Compared with prior art, the invention has the characteristics that：
1) self-dissolving type porous microsphere uniform particle sizes made from, monodispersity are good；
2) porous SiO is expanded2The aperture of microballoon, theoretically so that porous SiO2The load capacity of microballoon increases, and improves more
Hole SiO2The service efficiency of microballoon；
3) in SiO2Microsphere surface loads protective film, can make microballoon in the alkali environment of inside concrete not by fast instant
Erosion reaches sustained release renovation agent, controls the effect of self-dissolving rate, can apply in the water-bound of underground；
4) preparation method is simple, and controllability is good, at low cost, using porous SiO2Microballoon is as renovation agent load carriers, knot
It has closed the characteristics of mineral selfreparing reparation main body can also participate in repairing reaction and microcapsules selfreparing sustained release incentive mechanism is specific
Feature, for the crack autogenous healing of cement-based material structure, and repair rate can be controlled according to specific environment, repairing effect can
With effective for a long time.
Description of the drawings
Fig. 1 is porous SiO made from embodiment 12The SEM spectrograms (engineer's scale 500nm) of microballoon；
Fig. 2 is porous SiO made from embodiment 12The SEM spectrograms of microballoon (engineer's scale is 2 μm)；
Fig. 3 is porous SiO made from embodiment 12The XRD spectra of microballoon (angle of diffraction is 10-80 °)；
Fig. 4 is porous SiO made from embodiment 12The XRD spectra of microballoon (angle of diffraction is 3-10 °)
Fig. 5 is the SiO after reaming made from embodiment 22The SEM spectrograms (engineer's scale 500nm) of microballoon；
Fig. 6 is the SiO after reaming made from embodiment 22The SEM spectrograms of microballoon (engineer's scale is 1 μm)；
Fig. 7 is the SiO that the load obtained of embodiment 3 has renovation agent2The SEM spectrograms of microballoon (engineer's scale is 1 μm)；
Fig. 8 is the SiO that the load obtained of embodiment 4 has renovation agent2Microballoon loads the SEM spectrograms (engineer's scale 1 of protective film
μm)；
Fig. 9 is the SiO that the load obtained of embodiment 4 has renovation agent2Microballoon loads the SEM spectrograms (engineer's scale 2 of protective film
μm)。
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also be based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under the spirit of the present invention.
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1：
100ml isopropanols (analysis is pure) and 90ml deionized waters are uniformly mixed, add in 1g cetylamines (analysis is pure), ultrasound
Then mixing adds in 1.4ml concentrated ammonia liquors (analysis is pure), stirs well at room temperature, finally by 5.8ml ethyl orthosilicates (TEOS thereto
Analyze pure)-secondary property is injected into above-mentioned solution, stir 30s.Stand one day at room temperature, after the filtering of obtained product with ethyl alcohol and
Deionized water is successively respectively washed several times.Obtained product is roasted 6h by face activating agent cetylamine in 600 DEG C of air, you can
To SiO2Microballoon.
With reference to Fig. 1 and Fig. 2 it is found that SiO2Microsphere surface hole line width very little (average pore size 9.17nm), from Electronic Speculum under
It is the smooth sphere in surface.Grain size is also between 1~2 μm.
With reference to Fig. 3 it is found that porous SiO2For microballoon XRD diagram only there are one the spectral peak of 2 θ=22 ° or so, this is SiO2Feature
Diffraction maximum illustrates prepared SiO2Microballoon is amorphous state material.And from low-angle XRD diagram, as shown in figure 4, sample is in 2 θ
=3 ° or so have a spectral peak, illustrate SiO2There are meso-hole structures inside microballoon.
Embodiment 2：
Double salt (raw material is all pure to analyze) solution 100g, H is prepared in mass ratio2O：NaCl：LiCl：KNO3=70:20:5:
5, the salt weighed is added in deionized water, is dissolved by heating, is put into after cooling in reagent bottle for use.
The SiO that 1g is prepared2Microballoon is put into crucible, adds in the complex salt solution that 10mL is prepared, ultrasonic mixing, dipping
30min dries 6h at 65 DEG C.Then 4h is roasted at 350 DEG C of air atmosphere.
Obtained product is washed with deionized three times, drying, you can obtain the SiO after reaming2Microballoon, SEM figures referring to
Fig. 5 and Fig. 6.With reference to Fig. 5 and Fig. 6 it is found that SiO after reaming2There is Kong Wen in spherome surface, and surface becomes very coarse, framboid
For diameter at 1-2 μm, the average pore size of Kong Wen is 32.17nm.
SiO after expanding treatment2Microballoon also has the phenomenon that small reunion, and as shown in fig. 6, part SiO2Microballoon hole line compared with
It is shallow.
Embodiment 3：
The sodium silicate solution 60g of 10% mass fraction is weighed, weighs 1g reamings SiO2With the non-reaming SiO of 1g2It immerses respectively
In 60g (density 1.09g/ml, volume 55.04ml) sodium silicate solution, soak at room temperature 1d is more in sodium silicate solution by being immersed in
Hole SiO2Microballoon removes supernatant liquor to isolate the microsphere solid that bottom is centrifuged out after 9000r/min centrifugations 20min.It will be solid
Body is washed with a small amount once, is separated by filtration, and removes supernatant liquor, and solid 105 DEG C of dry 3h in vacuum drying oven are loaded
Porous (and reaming) SiO of sodium metasilicate2Microballoon.With reference to Fig. 7 it is found that the microsphere surface hole line of absorption sodium metasilicate is coated
Lid, can't see apparent crackle, surface is more smooth, and grain size is still 1-2 μm.
Embodiment 4：
Porous (and reaming) SiO of sodium metasilicate is adsorbed2In the PVP solution that it is 40000 by molecular weight that microballoon 1g, which is immersed in,
PVP and SiO2Molar ratio be 10:1.Mixture keeps 3h at 100 DEG C, and PVP is allowed to have time enough to be loaded into SiO2Microballoon table
Face.With reference to Fig. 8 and Fig. 9 it is found that microsphere surface covers a tunic so that hole line originally becomes creep and obscures, and surface is close to light
It is sliding, articulamentum is just formed by this floor height molecular film among small reunion microballoon, grain size is still 1-2 μm.
Embodiment 5：
The present embodiment is used for the preparation method of the self-dissolving type porous microsphere of self-repairing of concrete cracks, and this method passes sequentially through
The preparation of self-dissolving microballoon, the reaming of self-dissolving microballoon, the load of renovation agent and the loading of protective film, the self-dissolving type for being made described are more
Hole microballoon, specifically includes following steps：
(1) preparation of self-dissolving microballoon
Organic solvent and deionized water are uniformly mixed by (1-1), add in surfactant, ultrasonic mixing；
(1-2) adds in alkaline solution, at 25 DEG C, stirs evenly；
(1-3) disposably injects organic esters of silicon acis, and is sufficiently stirred；
(1-4) stands 36 hours in 25 DEG C, and filtering retains solid, washs, dry, by calcination process, obtains
SiO2Microballoon；
In actual fabrication process, the time of the ultrasonic mixing in step (1-1) is controllable to 20 minutes, step (1-2)
In mixing time be controllable to 10 minutes, and after adding in organosilicon acid esters, control mixing time is 30 seconds；
(2) reaming of self-dissolving microballoon
(2-1) prepares complex salt solution；
(2-2) is by SiO2Microballoon is placed in crucible, adds in complex salt solution, uniform through ultrasonic mixing, is impregnated, drying, then into
Row calcination process；
After (2-3) treats calcination process, product is washed, and drying obtains the SiO after reaming2Microballoon；
In actual fabrication process, the dip time in step (2-2) may be controlled to 45 minutes, and the temperature of drying can be with
It is 85 DEG C to control, and drying time is 2 hours；
(3) load of renovation agent
(3-1), which is prepared, repairs agent solution；
(3-2) is by the SiO after reaming2Microballoon, which is added to, to be repaired in agent solution, is impregnated in 25 DEG C or mechanical agitation 24 hours；
(3-3) is centrifuged, and removes supernatant liquor, and bottom microsphere solid is washed, after vacuum drying, and obtaining load has
The SiO of renovation agent2Microballoon；
In actual fabrication process, the vacuum drying temperature in step (3-3) may be controlled to 110 DEG C, and the time is small for 2
When；
(4) loading of protective film
(4-1) prepares protection coating solution；
(4-2) has the SiO of renovation agent by loading2Microballoon is immersed in protection coating solution, and in 120 DEG C, is impregnated 2 hours,
So that protective film is fully loaded into load and has the SiO of renovation agent2On microsphere surface.
In step (1-1), organic solvent is isopropanol, and surfactant is cetylamine, in step (1-2), alkaline solution
The ammonia spirit for being 25% for mass fraction, in step (1-3), organosilicon acid esters is ethyl orthosilicate, and isopropanol is with going
Ionized water, ammonia spirit, ethyl orthosilicate volume ratio be 15:9:0.15:0.7, the mass ratio of cetylamine and ethyl orthosilicate
It is 1:6.
In step (1-4), the condition of calcination process is：Under air atmosphere, controlled at 700 DEG C, roasting time 4
Hour.
In step (2-1), complex salt solution is contains NaCl, LiCl and KNO3Aqueous solution, and NaCl, LiCl, KNO3With
The mass ratio of water is 20:6:6:80.
In step (2-2), SiO2Microballoon is 2g/mL in the mass concentration of complex salt solution, and the condition of calcination process is：In sky
Under atmosphere is enclosed, controlled at 400 DEG C, roasting time is 5 hours.
In step (3-1), it is sodium silicate solution that mass fraction is 20% to repair agent solution, in step (3-2), after reaming
SiO2Microballoon is 1 with the mass ratio for repairing agent solution:60, in step (3-3), the condition of centrifugation is：Centrifugal rotational speed is
9000r/min, centrifugation time 10min.
In step (4-1), protection coating solution is PVP solution, and in step (4-2), load has the SiO of renovation agent2Microballoon with
The molar ratio of PVP is 1 in PVP solution:12.Wherein, the relative molecular mass of PVP is 60000 in PVP solution.
Embodiment 6：
The present embodiment is used for the preparation method of the self-dissolving type porous microsphere of self-repairing of concrete cracks, and this method passes sequentially through
The preparation of self-dissolving microballoon, the reaming of self-dissolving microballoon, the load of renovation agent and the loading of protective film, the self-dissolving type for being made described are more
Hole microballoon, specifically includes following steps：
(1) preparation of self-dissolving microballoon
Organic solvent and deionized water are uniformly mixed by (1-1), add in surfactant, ultrasonic mixing；
(1-2) adds in alkaline solution, at 20 DEG C, stirs evenly；
(1-3) disposably injects organic esters of silicon acis, and is sufficiently stirred；
(1-4) stands 12 hours in 20 DEG C, and filtering retains solid, washs, dry, by calcination process, obtains
SiO2Microballoon；
In actual fabrication process, the time of the ultrasonic mixing in step (1-1) is controllable to 10 minutes, step (1-2)
In mixing time be controllable to 5 minutes, and after adding in organosilicon acid esters, control mixing time is 45 seconds；
(2) reaming of self-dissolving microballoon
(2-1) prepares complex salt solution；
(2-2) is by SiO2Microballoon is placed in crucible, adds in complex salt solution, uniform through ultrasonic mixing, is impregnated, drying, then into
Row calcination process；
After (2-3) treats calcination process, product is washed, and drying obtains the SiO after reaming2Microballoon；
In actual fabrication process, the dip time in step (2-2) may be controlled to 30 minutes, and the temperature of drying can be with
It is 75 DEG C to control, and drying time is 3 hours；
(3) load of renovation agent
(3-1), which is prepared, repairs agent solution；
(3-2) is by the SiO after reaming2Microballoon, which is added to, to be repaired in agent solution, is impregnated in 20 DEG C or mechanical agitation 48 hours；
(3-3) is centrifuged, and removes supernatant liquor, and bottom microsphere solid is washed, after vacuum drying, and obtaining load has
The SiO of renovation agent2Microballoon；
In actual fabrication process, the vacuum drying temperature in step (3-3) may be controlled to 100 DEG C, and the time is small for 3
When；
(4) loading of protective film
(4-1) prepares protection coating solution；
(4-2) has the SiO of renovation agent by loading2Microballoon is immersed in protection coating solution, and in 90 DEG C, is impregnated 5 hours, is made
It obtains protective film and is fully loaded into the SiO for loading and having renovation agent2On microsphere surface.
In step (1-1), organic solvent is isopropanol, and surfactant is cetylamine, in step (1-2), alkaline solution
The ammonia spirit for being 28% for mass fraction, in step (1-3), organosilicon acid esters is ethyl orthosilicate, and isopropanol is with going
Ionized water, ammonia spirit, ethyl orthosilicate volume ratio be 10:7:0.1:0.5, the mass ratio of cetylamine and ethyl orthosilicate is
1:5。
In step (1-4), the condition of calcination process is：Under air atmosphere, controlled at 500 DEG C, roasting time 8
Hour.
In step (2-1), complex salt solution is contains NaCl, LiCl and KNO3Aqueous solution, and NaCl, LiCl, KNO3With
The mass ratio of water is 15:4:4:65.
In step (2-2), SiO2Microballoon is 1g/mL in the mass concentration of complex salt solution, and the condition of calcination process is：In sky
Under atmosphere is enclosed, controlled at 300 DEG C, roasting time is 3 hours.
In step (3-1), it is sodium silicate solution that mass fraction is 10% to repair agent solution, in step (3-2), after reaming
SiO2Microballoon is 1 with the mass ratio for repairing agent solution:40, in step (3-3), the condition of centrifugation is：Centrifugal rotational speed is
8000r/min, centrifugation time 20min.
In step (4-1), protection coating solution is PVP solution, and in step (4-2), load has the SiO of renovation agent2Microballoon with
The molar ratio of PVP is 1 in PVP solution:8.Wherein, the relative molecular mass of PVP is 40000 in PVP solution.
Embodiment 7：
The present embodiment is used for the preparation method of the self-dissolving type porous microsphere of self-repairing of concrete cracks, and this method passes sequentially through
The preparation of self-dissolving microballoon, the reaming of self-dissolving microballoon, the load of renovation agent and the loading of protective film, the self-dissolving type for being made described are more
Hole microballoon, specifically includes following steps：
(1) preparation of self-dissolving microballoon
Organic solvent and deionized water are uniformly mixed by (1-1), add in surfactant, ultrasonic mixing；
(1-2) adds in alkaline solution, at 24 DEG C, stirs evenly；
(1-3) disposably injects organic esters of silicon acis, and is sufficiently stirred；
(1-4) stands 24 hours in 24 DEG C, and filtering retains solid, washs, dry, by calcination process, obtains
SiO2Microballoon；
In actual fabrication process, the time of the ultrasonic mixing in step (1-1) is controllable to 15 minutes, step (1-2)
In mixing time be controllable to 8 minutes, and after adding in organosilicon acid esters, control mixing time is 40 seconds；
(2) reaming of self-dissolving microballoon
(2-1) prepares complex salt solution；
(2-2) is by SiO2Microballoon is placed in crucible, adds in complex salt solution, uniform through ultrasonic mixing, is impregnated, drying, then into
Row calcination process；
After (2-3) treats calcination process, product is washed, and drying obtains the SiO after reaming2Microballoon；
In actual fabrication process, the dip time in step (2-2) may be controlled to 40 minutes, and the temperature of drying can be with
It is 82 DEG C to control, and drying time is 2.5 hours；
(3) load of renovation agent
(3-1), which is prepared, repairs agent solution；
(3-2) is by the SiO after reaming2Microballoon, which is added to, to be repaired in agent solution, is impregnated 36 hours in 24 DEG C；
(3-3) is centrifuged, and removes supernatant liquor, and bottom microsphere solid is washed, after vacuum drying, and obtaining load has
The SiO of renovation agent2Microballoon；
In actual fabrication process, the vacuum drying temperature in step (3-3) may be controlled to 105 DEG C, the time 2.5
Hour；
(4) loading of protective film
(4-1) prepares protection coating solution；
(4-2) has the SiO of renovation agent by loading2Microballoon is immersed in protection coating solution, and in 110 DEG C, is impregnated 3 hours,
So that protective film is fully loaded into load and has the SiO of renovation agent2On microsphere surface.
In step (1-1), organic solvent is isopropanol, and surfactant is cetylamine, in step (1-2), alkaline solution
The ammonia spirit for being 27% for mass fraction, in step (1-3), organosilicon acid esters is ethyl orthosilicate, and isopropanol is with going
Ionized water, ammonia spirit, ethyl orthosilicate volume ratio be 12:8:0.13:0.6, the mass ratio of cetylamine and ethyl orthosilicate
It is 1:5.6.
In step (1-4), the condition of calcination process is：Under air atmosphere, controlled at 600 DEG C, roasting time 6
Hour.
In step (2-1), complex salt solution is contains NaCl, LiCl and KNO3Aqueous solution, and NaCl, LiCl, KNO3With
The mass ratio of water is 17:5:5:73.
In step (2-2), SiO2Microballoon is 1.5g/mL in the mass concentration of complex salt solution, and the condition of calcination process is：
Under air atmosphere, controlled at 360 DEG C, roasting time is 4 hours.
In step (3-1), it is sodium silicate solution that mass fraction is 15% to repair agent solution, in step (3-2), after reaming
SiO2Microballoon is 1 with the mass ratio for repairing agent solution:48, in step (3-3), the condition of centrifugation is：Centrifugal rotational speed is
8500r/min, centrifugation time 15min.
In step (4-1), protection coating solution is PVP solution, and in step (4-2), load has the SiO of renovation agent2Microballoon with
The molar ratio of PVP is 1 in PVP solution:10.Wherein, the relative molecular mass of PVP is 50000 in PVP solution.
Embodiment 8：
The present embodiment is used for the preparation method of the self-dissolving type porous microsphere of self-repairing of concrete cracks, and this method passes sequentially through
The preparation of self-dissolving microballoon, the reaming of self-dissolving microballoon, the load of renovation agent and the loading of protective film, the self-dissolving type for being made described are more
Hole microballoon, specifically includes following steps：
(1) preparation of self-dissolving microballoon
Organic solvent and deionized water are uniformly mixed by (1-1), add in surfactant, ultrasonic mixing；
(1-2) adds in alkaline solution, at 22 DEG C, stirs evenly；
(1-3) disposably injects organic esters of silicon acis, and is sufficiently stirred；
(1-4) stands 18 hours in 22 DEG C, and filtering retains solid, washs, dry, by calcination process, obtains
SiO2Microballoon；
In actual fabrication process, the time of the ultrasonic mixing in step (1-1) is controllable to 18 minutes, step (1-2)
In mixing time be controllable to 6 minutes, and after adding in organosilicon acid esters, control mixing time is 38 seconds；
(2) reaming of self-dissolving microballoon
(2-1) prepares complex salt solution；
(2-2) is by SiO2Microballoon is placed in crucible, adds in complex salt solution, uniform through ultrasonic mixing, is impregnated, drying, then into
Row calcination process；
After (2-3) treats calcination process, product is washed, and drying obtains the SiO after reaming2Microballoon；
In actual fabrication process, the dip time in step (2-2) may be controlled to 35 minutes, and the temperature of drying can be with
It is 78 DEG C to control, and drying time is 3 hours；
(3) load of renovation agent
(3-1), which is prepared, repairs agent solution；
(3-2) is by the SiO after reaming2Microballoon, which is added to, to be repaired in agent solution, is impregnated 30 hours in 22 DEG C；
(3-3) is centrifuged, and removes supernatant liquor, and bottom microsphere solid is washed, after vacuum drying, and obtaining load has
The SiO of renovation agent2Microballoon；
In actual fabrication process, the vacuum drying temperature in step (3-3) may be controlled to 108 DEG C, and the time is small for 2
When；
(4) loading of protective film
(4-1) prepares protection coating solution；
(4-2) has the SiO of renovation agent by loading2Microballoon is immersed in protection coating solution, and in 115 DEG C, is impregnated 4 hours,
So that protective film is fully loaded into load and has the SiO of renovation agent2On microsphere surface.
In step (1-1), organic solvent is isopropanol, and surfactant is cetylamine, in step (1-2), alkaline solution
The ammonia spirit for being 27% for mass fraction, in step (1-3), organosilicon acid esters is ethyl orthosilicate, and isopropanol is with going
Ionized water, ammonia spirit, ethyl orthosilicate volume ratio be 14:8:0.14:0.5, the mass ratio of cetylamine and ethyl orthosilicate
It is 1:5.8.
In step (1-4), the condition of calcination process is：Under air atmosphere, controlled at 630 DEG C, roasting time 7
Hour.
In step (2-1), complex salt solution is contains LiCl, Na2CO3And NH3Aqueous solution, and LiCl, Na2CO3、NH3
Mass ratio with water is 20:5:5:70.
In step (2-2), SiO2Microballoon is 1.8g/mL in the mass concentration of complex salt solution, and the condition of calcination process is：
Under air atmosphere, controlled at 340 DEG C, roasting time is 5 hours.
In step (3-1), it is sodium silicate solution that mass fraction is 18% to repair agent solution, in step (3-2), after reaming
SiO2Microballoon is 1 with the mass ratio for repairing agent solution:56, in step (3-3), the condition of centrifugation is：Centrifugal rotational speed is
8600r/min, centrifugation time 18min.
In step (4-1), protection coating solution is PVP solution, and in step (4-2), load has the SiO of renovation agent2Microballoon with
The molar ratio of PVP is 1 in PVP solution:9.Wherein, the relative molecular mass of PVP is 10000 in PVP solution.
Embodiment 9：
The present embodiment specifically includes following step for the preparation method of the self-dissolving type porous microsphere of self-repairing of concrete cracks
Suddenly：
(1) preparation of self-dissolving microballoon
Organic solvent and deionized water are uniformly mixed by (1-1), add in surfactant, ultrasonic mixing；
(1-2) adds in alkaline solution, at 20 DEG C, stirs evenly；
(1-3) disposably injects organic esters of silicon acis, and is sufficiently stirred；
(1-4) stands 18 hours in 20 DEG C, and filtering retains solid, washs, dry, by calcination process, obtains
SiO2Microballoon；
In actual fabrication process, the time of the ultrasonic mixing in step (1-1) is controllable to 18 minutes, step (1-2)
In mixing time be controllable to 6 minutes, and after adding in organosilicon acid esters, control mixing time is 30 seconds；
(2) reaming of self-dissolving microballoon
(2-1) prepares complex salt solution；
(2-2) is by SiO2Microballoon is placed in crucible, adds in complex salt solution, uniform through ultrasonic mixing, is impregnated, drying, then into
Row calcination process；
After (2-3) treats calcination process, product is washed, and drying obtains the SiO after reaming2Microballoon；
In actual fabrication process, the dip time in step (2-2) may be controlled to 40 minutes, and the temperature of drying can be with
It is 80 DEG C to control, and drying time is 3 hours；
(3) load of renovation agent
(3-1), which is prepared, repairs agent solution；
(3-2) is by the SiO after reaming2Microballoon, which is added to, to be repaired in agent solution, is impregnated 30 hours in 20 DEG C；
(3-3) is centrifuged, and removes supernatant liquor, and bottom microsphere solid is washed, after vacuum drying, and obtaining load has
The SiO of renovation agent2Microballoon；
In actual fabrication process, the vacuum drying temperature in step (3-3) may be controlled to 106 DEG C, and the time is small for 2
When；
(4) loading of protective film
(4-1) prepares protection coating solution；
(4-2) has the SiO of renovation agent by loading2Microballoon is immersed in protection coating solution, and in 106 DEG C, is impregnated 5 hours,
So that protective film is fully loaded into load and has the SiO of renovation agent2On microsphere surface.
In step (1-1), organic solvent is isopropanol, and surfactant is cetylamine, in step (1-2), alkaline solution
The ammonia spirit for being 28% for mass fraction, in step (1-3), organosilicon acid esters is ethyl orthosilicate, and isopropanol is with going
Ionized water, ammonia spirit, ethyl orthosilicate volume ratio be 11:9:0.1:0.6, the mass ratio of cetylamine and ethyl orthosilicate is
1:5。
In step (1-4), the condition of calcination process is：Under air atmosphere, controlled at 680 DEG C, roasting time 5
Hour.
In step (2-1), complex salt solution is contains LiCl and NH4HCO3Aqueous solution, and LiCl, NH4HCO3With water
Mass ratio is 18:5:68.
In step (2-2), SiO2Microballoon is 1.2g/mL in the mass concentration of complex salt solution, and the condition of calcination process is：
Under air atmosphere, controlled at 380 DEG C, roasting time is 4 hours.
In step (3-1), it is sodium silicate solution that mass fraction is 12% to repair agent solution, in step (3-2), after reaming
SiO2Microballoon is 1 with the mass ratio for repairing agent solution:48, in step (3-3), the condition of centrifugation is：Centrifugal rotational speed is
9000r/min, centrifugation time 12min.
In step (4-1), protection coating solution is PVP solution, and in step (4-2), load has the SiO of renovation agent2Microballoon with
The molar ratio of PVP is 1 in PVP solution:10.Wherein, the relative molecular mass of PVP is 42000 in PVP solution.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (8)
1. the preparation method of the self-dissolving type porous microsphere for self-repairing of concrete cracks, which is characterized in that this method is led to successively
The preparation of self-dissolving microballoon, the reaming of self-dissolving microballoon, the load of renovation agent and the loading of protective film are crossed, the self-dissolving type is made
Porous microsphere specifically includes following steps：
(1) preparation of self-dissolving microballoon
Organic solvent and deionized water are uniformly mixed by (1-1), add in surfactant, ultrasonic mixing；
(1-2) adds in alkaline solution, at 20-25 DEG C, stirs evenly；
(1-3) disposably injects organic esters of silicon acis, and is sufficiently stirred；
(1-4) stands 12-36 hours in 20-25 DEG C, and filtering retains solid, washs, dry, by calcination process, obtains
SiO2Microballoon；
(2) reaming of self-dissolving microballoon
(2-1) prepares complex salt solution；
(2-2) is by SiO2Microballoon is placed in crucible, adds in complex salt solution, uniform through ultrasonic mixing, is impregnated, drying, then roasted
Processing；
After (2-3) treats calcination process, product is washed, and drying obtains the SiO after reaming2Microballoon；
(3) load of renovation agent
(3-1), which is prepared, repairs agent solution；
(3-2) is by the SiO after reaming2Microballoon, which is added to, to be repaired in agent solution, is impregnated in 20-25 DEG C or mechanical agitation 24-48 is small
When；
(3-3) is centrifuged, and removes supernatant liquor, and bottom microsphere solid is washed, after vacuum drying, and obtaining load has reparation
The SiO of agent2Microballoon；
(4) loading of protective film
(4-1) prepares protection coating solution；
(4-2) has the SiO of renovation agent by loading2Microballoon is immersed in protection coating solution, and in 90-120 DEG C, is impregnated 2-5 hours,
So that protective film is fully loaded into load and has the SiO of renovation agent2On microsphere surface；
Reparation agent solution described in step (3-1) is the sodium silicate solution that mass fraction is 10-20%, institute in step (3-2)
SiO after the reaming stated2Microballoon is 1 with the mass ratio for repairing agent solution:40-60, centrifugation described in step (3-3)
Condition is：Centrifugal rotational speed is 8000-9000r/min, centrifugation time 10-20min；
Protection coating solution described in step (4-1) is PVP solution, and the load described in step (4-2) has the SiO of renovation agent2It is micro-
The molar ratio of ball and PVP in PVP solution are 1:8-12.
2. the preparation method of the self-dissolving type porous microsphere according to claim 1 for self-repairing of concrete cracks, special
Sign is, the organic solvent described in step (1-1) is isopropanol, and the surfactant is cetylamine, in step (1-2)
The alkaline solution is the ammonia spirit that mass fraction is 25-28%, and the organosilicon acid esters described in step (1-3) is positive silicon
Acetoacetic ester, and the volume ratio of the isopropanol and deionized water, ammonia spirit, ethyl orthosilicate is 10-15:7-9:0.1-
0.15:The mass ratio of 0.5-0.7, the cetylamine and ethyl orthosilicate is 1:5-6.
3. the preparation method of the self-dissolving type porous microsphere according to claim 1 for self-repairing of concrete cracks, special
Sign is that the condition of the calcination process described in step (1-4) is：Under air atmosphere, controlled at 500-700 DEG C, roasting
It is 4-8 hours to burn the time.
4. the preparation method of the self-dissolving type porous microsphere according to claim 1 for self-repairing of concrete cracks, special
Sign is that the complex salt solution described in step (2-1) is contains NaCl, LiCl, KNO3、Na2CO3、NH4HCO3Or NH3In two
The aqueous solution of kind or many kinds of substance.
5. the preparation method of the self-dissolving type porous microsphere according to claim 4 for self-repairing of concrete cracks, special
Sign is that the complex salt solution is contains NaCl, LiCl and KNO3Aqueous solution, and NaCl, LiCl, KNO3With the matter of water
Amount is than being 15-20:4-6:4-6:65-80.
6. the preparation method of the self-dissolving type porous microsphere according to claim 1 for self-repairing of concrete cracks, special
Sign is, the SiO described in step (2-2)2Microballoon complex salt solution mass concentration for 1-2g/mL, the calcination process
Condition be：Under air atmosphere, controlled at 300-400 DEG C, roasting time is 3-5 hours.
7. the preparation method of the self-dissolving type porous microsphere according to claim 1 for self-repairing of concrete cracks, special
Sign is that the relative molecular mass of PVP is 10000-60000 in the PVP solution.
8. method as described in any one of claim 1 to 7 is prepared more for the self-dissolving type of self-repairing of concrete cracks
Hole microballoon.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1715184A (en) * | 2004-06-28 | 2006-01-04 | 中国科学院理化技术研究所 | The preparation method of sphericity mesoporous silicon dioxide |
| EP2423265A1 (en) * | 2010-08-24 | 2012-02-29 | Omya Development AG | Process for the preparation of cement, motars, concrete compositions containing a calcium carbonate-based filler (pre)-treated with a superplasticizer, compositions and cement products obtained and their applications |
| CN102642843A (en) * | 2012-05-10 | 2012-08-22 | 北京理工大学 | Method for simultaneously preparing multilevel-structure mesoporous silicon dioxide and carbon nano material |
| CN102786061A (en) * | 2012-07-20 | 2012-11-21 | 东华大学 | Preparation method of hollow mesoporous silica nanoparticle |
| CN103102876A (en) * | 2012-12-31 | 2013-05-15 | 哈尔滨工业大学 | Preparation method for inorganic-organic composite type profile control agent |
| CN105174770A (en) * | 2014-05-29 | 2015-12-23 | 纳米及先进材料研发院有限公司 | Self-healing material and preparation process thereof |
-
2016
- 2016-01-05 CN CN201610005049.5A patent/CN105565326B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1715184A (en) * | 2004-06-28 | 2006-01-04 | 中国科学院理化技术研究所 | The preparation method of sphericity mesoporous silicon dioxide |
| EP2423265A1 (en) * | 2010-08-24 | 2012-02-29 | Omya Development AG | Process for the preparation of cement, motars, concrete compositions containing a calcium carbonate-based filler (pre)-treated with a superplasticizer, compositions and cement products obtained and their applications |
| CN102642843A (en) * | 2012-05-10 | 2012-08-22 | 北京理工大学 | Method for simultaneously preparing multilevel-structure mesoporous silicon dioxide and carbon nano material |
| CN102786061A (en) * | 2012-07-20 | 2012-11-21 | 东华大学 | Preparation method of hollow mesoporous silica nanoparticle |
| CN103102876A (en) * | 2012-12-31 | 2013-05-15 | 哈尔滨工业大学 | Preparation method for inorganic-organic composite type profile control agent |
| CN105174770A (en) * | 2014-05-29 | 2015-12-23 | 纳米及先进材料研发院有限公司 | Self-healing material and preparation process thereof |
Non-Patent Citations (1)
| Title |
|---|
| 介孔二氧化硅微球的扩孔及组装磁性纳米铁粒子;王平等;《过程工程学报》;20080229;第8卷(第1期);第2.1-2.4部分 * |
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