CN103613318A - Microencapsulation method of concrete water-based repair agent - Google Patents
Microencapsulation method of concrete water-based repair agent Download PDFInfo
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- CN103613318A CN103613318A CN201310603676.5A CN201310603676A CN103613318A CN 103613318 A CN103613318 A CN 103613318A CN 201310603676 A CN201310603676 A CN 201310603676A CN 103613318 A CN103613318 A CN 103613318A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/18—In situ polymerisation with all reactants being present in the same phase
- B01J13/185—In situ polymerisation with all reactants being present in the same phase in an organic phase
-
- 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
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/72—Repairing or restoring existing buildings or building materials
Abstract
The invention relates to the technical field of self-repair materials, and provides a microencapsulation method of a concrete water-based repair agent. The method comprises the following steps: preparing an inner water phase, wherein the inner water phase is 0.5-3mol/L of inorganic water-based concrete repair agent and 0.01-2wt% of gelling agent water solution; preparing an oil phase, wherein the oil phase is a styrene organic solution of which the volume concentration is 50-100%; preparing an outer water phase, wherein the outer water phase contains 0.01-3wt% of water-soluble styrene polymerization initiator; adding 3-15wt% of water-in-oil surfactant to the oil phase, agitating and mixing with the inner water phase after dissolving, so as to obtain colostrum; preparing double emulsions; adding 3-5wt% of oil-in-water surfactant to the outer water phase, agitating and mixing with the colostrum after dissolving; and warming the double emulsions to 35-70 DEG C, and agitating, so as to obtain a microcapsule of the concrete water-based repair agent. The preparation method of the microcapsule of the concrete water-based repair agent is low in cost and applicable to industrial production.
Description
Technical field
The invention belongs to self-repair material technical field, be specifically related to a kind of Microencapsulation Method of concrete water-based renovation agent.
Background technology
Concrete is a kind of porous gelling artificial stone material of the hydraulicity, and because its unit elongation is small, tensile strength is low, so very easily produce shrinkage crack and load Crack.The existence of crackle has greatly affected the weather resistance of concrete works, and a method of solution is repaired crackle exactly.But artificial reparation is only applicable to outside crackle, due to the unpredictability of crackle generation and the limitation of flaw detection technology, a large amount of internal fissures that exist are difficult to be found and repair, and need exploitation to have " intelligent " concrete of autonomous repairing effect for this reason.
A kind of implementation method of self-repair concrete is embedding renovation agent in advance in concrete substrate, and when crack propagation, the renovation agent of embedding is triggered and is released by certain physics or chemical factor, and crackle is repaired automatically.In the prior art, renovation agent is generally embedded in small fibre pipe or in microcapsule.Comparatively speaking, in both, microcapsule-type self-repair concrete has certain technical superiority: the one, easily in concrete, disperse, and the 2nd, isotropy, can repair the crackle of any direction expansion.
In microcapsule-type self-repair concrete, the most frequently used epoxy resin is as renovation agent, yet this organic polymer class renovation agent and the inorganic concrete substrate poor problem of Presence of an interface bonding force not only also exists problem of aging.Because its weather resistance is well below concrete substrate, the crackle of therefore being repaired by organic renovation agent, after the several years, can lose the ability of making crackle up gradually, and former crackle is ftractureed again, becomes potential safety hazard.
Some inorganic adhesive, as water glass, aluminium dihydrogen phosphate etc., is also good concrete renovation agent.They and concrete interface bonding force are strong, and equally durable with concrete, do not have problem of aging.But they are water miscible silicate, phosphoric acid salt, borate, vitriol, molybdate mostly, need to take the method for water-in-oil (W/O) to make its micro encapsulation, that is to say, their aqueous solution is dispersed in continuous oil phase, this is contrary with the preparation method of general epoxy microcapsule.The particle diameter of W/O microcapsule is smaller, conventionally below 10 microns.In order to obtain the tens W/O microcapsule to hundreds of micron grain size, and the size of microcapsule and wall thickness are controlled, can be adopted two emulsion process of water-in-oil-in-water (W/O/W) to prepare O/W microcapsule.
Two emulsion methods are that a kind of milk sap (be commonly referred to elementary milk sap, be called for short colostrum) is dispersed in to the double-deck milk sap forming in other external phase, have two types of W/O/W and O/W/O, but all have many cell structure of " two film three-phases ".The two emulsions of W/O/W type are in oil phase drop, to contain one or more water drops, and this oil phase drop that contains water drop is dispersed in again in continuous water and the milk sap forming.Adopt two emulsion process of W/O/W to prepare W/O microcapsule, be exactly to using the polymers soln of oiliness or the polymer monomer of oiliness as middle oil phase, then make the solvent evaporation in polymers soln or extract, make polymer deposition form cyst wall, or in water (or interior water), add initiator or catalyzer outside, make monomer polymerization become polymer and in oil phase deposition and form cyst wall.This method of preparing microcapsule is without regulating pH value, and without significantly changing temperature, solvent residual amount is low, method is simple, easy to operate, applicable being coated has bioactive water-soluble substances as polypeptide, protein etc., thereby obtains a wide range of applications in fields such as medicine, foods and cosmetics.But two emulsions are a non-thermodynamic stable system in essence,, there is the phenomenons such as Ostwald ripening (Ostwald ripening), flocculation, coalescent and layering in unstability very easily.
Summary of the invention
In view of this, the invention provides a kind of Microencapsulation Method of concrete water-based renovation agent.
A Microencapsulation Method for concrete water-based renovation agent, it comprises the steps:
Water in preparation, the inorganic aqueous concrete renovation agent that described interior water is 0.5～3mol/L and the jelling agent aqueous solution of 0.01～2wt%;
Preparation oil phase, described oil phase is the vinylbenzene organic solution of volumetric concentration 50～100%;
Prepare outer water, the water-soluble phenylethene polymerization starter that described outer water comprises 0.01～3wt%;
To the water-in-oil tensio-active agent that adds 3～15wt% in described oil phase, after dissolving, is uniformly mixed with described interior water, obtain colostrum;
The two emulsions of preparation; The oil-in-water tensio-active agent that adds 3～5wt% in described outer water, is uniformly mixed with described colostrum after dissolving;
Described pair of emulsion is warming up to 35～70 ℃, stirs, obtain the microcapsule of concrete water-based renovation agent.
The Microencapsulation Method cost of concrete water-based renovation agent provided by the invention is low, process stabilizing, simple, is applicable to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the optical microscope photograph of microcapsule of the concrete water-based renovation agent of embodiment mono-preparation;
Fig. 2 is the scanning electron microscope picture of microcapsule of the concrete water-based renovation agent of embodiment mono-preparation;
Fig. 3 is the scanning electron microscope picture of microcapsule of the concrete water-based renovation agent of embodiment bis-preparation.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the present invention provides a kind of Microencapsulation Method of concrete water-based renovation agent, and it comprises the steps:
S01: water in preparation, the inorganic aqueous concrete renovation agent that described interior water is 0.5～3mol/L and the jelling agent aqueous solution of 0.01～2wt%;
S02: preparation oil phase, described oil phase is the vinylbenzene organic solution of volumetric concentration 50～100%;
S03: prepare outer water, the water-soluble phenylethene polymerization starter that described outer water comprises 0.01～3wt%;
S04: to the water-in-oil tensio-active agent that adds 3～15wt% in described oil phase, is uniformly mixed with described interior water after dissolving, obtains colostrum;
S05: the two emulsions of preparation; The oil-in-water tensio-active agent that adds 3～5wt% in described outer water, is uniformly mixed with described colostrum after dissolving;
S06: described pair of emulsion is warming up to 35～70 ℃, stirs, obtain the microcapsule of concrete water-based renovation agent.
In step S01, described inorganic aqueous concrete renovation agent is water glass, potassium silicate, lithium silicate, aluminum phosphate (P
2o
5/ Al
2o
3mol ratio is 2.0～3.0), sodium tetraborate, potassium tetraborate, Sodium orthomolybdate, potassium molybdate, ammonium dimolybdate [(NH
4)
2mo
2o
74H
2o], Ammonium Heptamolybdate [(NH
4)
6mo
7o
244H
2o], potassium alum [KAl (SO
4)
212H
2o], tschermigite [NH
4al (SO
4)
212H
2o], aluminium sodium alum [NaAl (SO
4)
212H
2o], at least one in Tai-Ace S 150, zinc sulfate, manganous sulfate, magnesium sulfate, calcium sulfate.The jelling agent that described interior water contains 0.01～2wt%, described jelling agent is water-soluble polymer, be preferably at least one in gelatin (gelatin), carrageenin (Carrageenan), xanthan gum (Xanthan gum), sodium alginate (sodium alginate, NaAlg), Rhizoma amorphophalli powder (konjac flour), gum arabic (Acacia gum), pectin (pectin), agar (agar), carboxymethyl cellulose (CMC), hydroxypropyl modified starch (Hydroxypropyl starch), carboxymethyl starch (CMS).
In step S02, described styrene solution is not containing stopper, and the solvent of styrene solution is not miscible with water organic solvent, is preferably at least one in trichloromethane (chloroform), toluene, dimethylbenzene, hexalin, methyl ethyl ketone, ether.
In step S03, described water-soluble phenylethene polymerization starter refers to water-soluble azo class initiator or water soluble oxidized---reduction initiator.The preferred azo diisobutyl of water-soluble azo class initiator amidine hydrochloride (AIBA wherein, V-50 initiator), azo two isobutyl imidazoline salt hydrochlorate (AIBI, VA-044 initiator), azo dicyano valeric acid (ACVA, V-501 initiator), azo di-isopropyl tetrahydroglyoxaline (AIP, VA-061 initiator); In water soluble oxidized one reduction initiator, the preferred hydrogen peroxide (H of oxygenant
2o
2), ammonium persulphate [(NH
4)
2s
2o
8], Sodium Persulfate (Na
2s
2o
8), Potassium Persulphate (K
2s
2o
8), hydrogen phosphide cumene (CHP), tertbutyl peroxide (TBHP); Persulphate, hydroperoxide, the ferrous (FeSO of reductive agent preferably sulfuric acid
4), S-WAT (Na
2sO
3), glucose, oxalic acid, trolamine (TEA), percarbonic acid acid amides (urea).
In described step S04, described water-in-oil (W/O) tensio-active agent HLB value during room temperature in pure water is 4～6.Volume ratio (the interior water: be oil phase) 1:3～4, stir speed (S.S.) is greater than 5000r/min of water and oil phase in described in during mixing.
In step S05, described oil-in-water (O/W) tensio-active agent HLB value during room temperature in pure water is 8～12.(the colostrum: outer water) be 1:1.5～2.5, stir speed (S.S.) is 15～100r/min of the volume ratio of colostrum and outer water described in during mixing.
In described step S04 and S05, described W/O tensio-active agent and O/W tensio-active agent, preferably descend one or more composite in surfactant: sorbitan fatty acid ester Soxylat A 25-7, trade mark Tween20～Tween80; Sorbitan fatty acid ester, trade mark Span20～Span80; PEG-30 dimerization hydroxy stearic acid ester, trade mark Arlacel P135; Castor oil polyoxyethylene ether, trade mark EL35 and EL40; Alkylphenol polyoxyethylene, trade mark OP4～OP7; Fatty alcohol-polyoxyethylene ether, trade mark AEO3～AEO10.
In described step S06, temperature of reaction is 35～70 ℃, and the reaction times is 10～120 minutes, and stir speed (S.S.) is 15～100r/min.During reaction, pass into rare gas element.
The Microencapsulation Method of the concrete water-based renovation agent that the embodiment of the present invention provides, its technique is mainly manifested in the choosing and suitable consumption of tensio-active agent of choosing suitable oil-in-water (O/W) and water-in-oil (W/O); In interior water, add appropriate and suitable jelling agent, to block the mutual seepage of water in inside and outside water; When forming two emulsion, stir speed (S.S.) wants slow, and polyreaction is wanted rapidly.Conventionally, during water-in-oil, within the HLB value of tensio-active agent is controlled at 4～7 scopes; During oil-in-water, the HLB value of tensio-active agent is controlled in 8～18 scopes.But the HLB value of tensio-active agent becomes with the polarity of the salinity in temperature, pH value, water, oil phase solvent, thereby different tensio-active agent correspondences different processing condition.The two emulsion methods of W/O/W type are prepared microcapsule, if define the composition of core (interior water) and wall material (oil phase), Surfactant, organic solvent are chosen so, and the control of temperature, pH value, salinity and stir speed (S.S.) is all had to uniqueness.
By specific embodiment, illustrate below the Microencapsulation Method of above-mentioned concrete water-based renovation agent.
Embodiment mono-:
S11: water in preparation, the phosphate dihydrogen aluminum solution that preparation 30mL concentration is 1mol/L, splashes into 5 (approximately 0.25 milliliter) 5wt% aqueous gelatin solutions, water viscosity in regulating;
S12: preparation oil phase is that the 5wt%NaOH aqueous solution is made washing lotion toward pouring appropriate concentration in commercial styrene, vibrates, separatory, and Pi goes to wash rear reddish NaOH washing lotion, repeatedly, until NaOH washing lotion is colourless.Then add 5g anhydrous sodium sulphate, airtight, dry more than 3 days, to remove moisture in lucifuge place.Finally underpressure distillation again, by middle runnings lucifuge cryopreservation, this is not contain the vinylbenzene of stopper (Resorcinol).
Get 15mL through the vinylbenzene of above-mentioned processing, the toluene of processing through distillation with 15mL mixes, and makes cinnamic toluene solution, as oil phase.
S13: prepare outer water.Get in 70mL deionized water, add 0.20g Potassium Persulphate and 0.11g S-WAT as initiator.
S14: preparation colostrum.The mass ratio mixing that department class 80 and tween 80 press to 9:1, as W/O tensio-active agent, HLB value during room temperature is 5.4.
Get above-mentioned W/O tensio-active agent 4.4g, join in the made oil phase of step 2, be uniformly mixed, then mix with the made interior water of step 1, clarifixator high-speed stirring 2 minutes, rotating speed 10000r/min, obtains white milk shape colostrum.
S15: the two emulsions of preparation W/O/W type.The mass ratio mixing that department class 80 and tween 80 press to 6:4, as O/W tensio-active agent, HLB value during room temperature is 8.6.
Get above-mentioned O/W tensio-active agent 10g, join in the made outer water of step S13, be uniformly mixed, pour in 500mL there-necked flask, more carefully add the made colostrum of step S14, logical nitrogen, stirring at low speed, rotating speed 20r/min, obtains the two emulsions of W/O/W type.
S16: lead to nitrogen in the two emulsions of the made W/O/W type of step 5, be warming up to 70 ℃, react after 40 minutes and stop, filtering, obtain the polystyrene microcapsule of phosphate dihydrogen aluminum solution.Opticmicroscope and sem observation, the pattern of microcapsule respectively as depicted in figs. 1 and 2.
Embodiment bis-:
S21: water in preparation, the sodium silicate solution that preparation 30mL concentration is 1mol/L, splashes into 2 (approximately 0.1 milliliter) 5wt% xanthan gum solutions, water viscosity in regulating;
S22: preparation oil phase is that the 5wt%NaOH aqueous solution is made washing lotion toward pouring appropriate concentration in commercial styrene, vibrates, separatory, and Pi goes to wash rear reddish NaOH washing lotion, repeatedly, until NaOH washing lotion is colourless.Then add 5g anhydrous sodium sulphate, airtight, dry more than 3 days, to remove moisture in lucifuge place.Finally underpressure distillation again, by middle runnings lucifuge cryopreservation, this is not contain the vinylbenzene of stopper (Resorcinol).
Get 30mL through the vinylbenzene of above-mentioned processing, the chloroform of processing through distillation with 15mL mixes, and makes cinnamic chloroformic solution, as oil phase.
S23: prepare outer water, get in 70mL deionized water, add the methanol solution of 20mL20wt%V-50 initiator.
S24: preparation colostrum, using 0.15g Arlacel P135 as W/O tensio-active agent (HLB value during room temperature is 5.5), join in the made oil phase of step 2, be uniformly mixed, mix with the made interior water of step 1 again, clarifixator high-speed stirring 5 minutes, rotating speed 10000r/min, obtains white milk shape colostrum.
S25: the two emulsions of preparation W/O/W type.The mass ratio mixing that department class 80 and tween 80 press to 1:1, as O/W tensio-active agent, HLB value during room temperature is 9.9.
Get above-mentioned O/W tensio-active agent 10g, join in the made outer water of step S23, be uniformly mixed, pour in 500mL there-necked flask, more carefully add the made colostrum of step S24, logical nitrogen, stirring at low speed, rotating speed 20r/min, obtains the two emulsions of W/O/W type.
S26: lead to nitrogen in the two emulsions of the made W/O/W type of step S25, be warming up to 70 ℃, react after 60 minutes and stop, filtering, obtain the polystyrene microcapsule of sodium silicate solution.Sem observation, the pattern of microcapsule as shown in Figure 3.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. a Microencapsulation Method for concrete water-based renovation agent, is characterized in that, comprises the steps:
Water in preparation, the inorganic aqueous concrete renovation agent that described interior water is 0.5～3mol/L and the jelling agent aqueous solution of 0.01～2wt%;
Preparation oil phase, described oil phase is the vinylbenzene organic solution of volumetric concentration 50～100%;
Prepare outer water, the water-soluble phenylethene polymerization starter that described outer water comprises 0.01～3wt%;
To the water-in-oil tensio-active agent that adds 3～15wt% in described oil phase, after dissolving, is uniformly mixed with described interior water, obtain colostrum;
The two emulsions of preparation; The oil-in-water tensio-active agent that adds 3～5wt% in described outer water, is uniformly mixed with described colostrum after dissolving;
Described pair of emulsion is warming up to 35～70 ℃, stirs, obtain the microcapsule of concrete water-based renovation agent.
2. the Microencapsulation Method of concrete water-based renovation agent as claimed in claim 1, it is characterized in that, described inorganic aqueous concrete renovation agent is water glass, potassium silicate, lithium silicate, aluminum phosphate, sodium tetraborate, potassium tetraborate, Sodium orthomolybdate, potassium molybdate, ammonium dimolybdate, Ammonium Heptamolybdate, at least one in potassium alum, tschermigite, aluminium sodium alum, Tai-Ace S 150, zinc sulfate, manganous sulfate, magnesium sulfate, calcium sulfate.
3. the Microencapsulation Method of concrete water-based renovation agent as claimed in claim 1, it is characterized in that, described jelling agent is at least one in gelatin, carrageenin, xanthan gum, sodium alginate, Rhizoma amorphophalli powder, gum arabic, pectin, agar, carboxymethyl cellulose, hydroxypropyl modified starch, carboxymethyl starch.
4. the Microencapsulation Method of concrete water-based renovation agent as claimed in claim 1, is characterized in that, the solvent of described vinylbenzene organic solution is at least one in trichloromethane, toluene, dimethylbenzene, hexalin, methyl ethyl ketone, ether.
5. the Microencapsulation Method of concrete water-based renovation agent as claimed in claim 1, is characterized in that, described water-soluble phenylethene polymerization starter is water-soluble azo class initiator or water soluble oxidized-reduction initiator.
6. the Microencapsulation Method of concrete water-based renovation agent as claimed in claim 1, is characterized in that, described water-in-oil tensio-active agent HLB value under room temperature in pure water is 4～6.
7. the Microencapsulation Method of concrete water-based renovation agent as claimed in claim 1, is characterized in that, during the outer water of described preparation, the volume ratio of described interior water and oil phase is 1:3～4.
8. the Microencapsulation Method of concrete water-based renovation agent as claimed in claim 1, is characterized in that, described oil-in-water tensio-active agent HLB value under room temperature in pure water is 8～12.
9. the Microencapsulation Method of concrete water-based renovation agent as claimed in claim 1, is characterized in that, during the two emulsion of described preparation, the volume ratio of described colostrum and outer water is 1:1.5～2.5.
10. the Microencapsulation Method of concrete water-based renovation agent as claimed in claim 1, is characterized in that, described pair of emulsion is warming up to 35～70 ℃, and stir speed (S.S.) is 15～100r/min, and the time is 10～120 minutes.
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| CN201310603676.5A CN103613318B (en) | 2013-11-25 | 2013-11-25 | Microencapsulation method of concrete water-based repair agent |
| PCT/CN2014/071293 WO2015074343A1 (en) | 2013-11-25 | 2014-01-23 | Microencapsulation method for concrete water-based repair agent |
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| CN201310603676.5A CN103613318B (en) | 2013-11-25 | 2013-11-25 | Microencapsulation method of concrete water-based repair agent |
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| CN103011667A (en) * | 2012-12-03 | 2013-04-03 | 深圳大学 | Method for preparing polystyrene/sodium monofluorophosphate microcapsule corrosion inhibitor |
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| 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 |
| US9598313B2 (en) | 2014-05-29 | 2017-03-21 | Nano And Advanced Materials Institute Limited | Self-healing material and preparation process thereof |
| CN105174770B (en) * | 2014-05-29 | 2017-04-12 | 纳米及先进材料研发院有限公司 | Self-healing material and preparation process thereof |
| CN104909656A (en) * | 2015-05-29 | 2015-09-16 | 合肥瑞鹤装饰工程有限公司 | High temperature resistant vegetable fiber cement composite strip plate and producing method thereof |
| CN105565689A (en) * | 2016-01-05 | 2016-05-11 | 同济大学 | Autolysis enhanced self-repairing system, concrete comprising same, and preparation method thereof |
| CN105565689B (en) * | 2016-01-05 | 2018-07-03 | 同济大学 | The enhanced self-repairing system of self-dissolving and the concrete with the system and preparation method thereof |
| CN107129182B (en) * | 2017-05-18 | 2019-03-15 | 济南大学 | A kind of modified gel powder and its production method and application |
| CN107129182A (en) * | 2017-05-18 | 2017-09-05 | 济南大学 | A kind of modified gel powder and its production method and application |
| CN108193770A (en) * | 2017-12-29 | 2018-06-22 | 华南理工大学 | A kind of concrete structure of selfreparing |
| CN108383411A (en) * | 2018-02-02 | 2018-08-10 | 华南理工大学 | A kind of microcapsules and preparation method thereof for cement base microcrack selfreparing |
| CN108439905A (en) * | 2018-04-25 | 2018-08-24 | 北京鸿锐嘉科技发展有限公司 | Slip casting binder and its performance parameter detection method |
| CN110584176A (en) * | 2018-06-12 | 2019-12-20 | 中国农业大学 | Water-in-oil particles, composite emulsion, preparation method and application thereof |
| CN108751869A (en) * | 2018-07-24 | 2018-11-06 | 华南理工大学 | A kind of permeable crystallization type self-repair concrete structure and preparation method thereof |
| CN109928656A (en) * | 2019-03-05 | 2019-06-25 | 武汉源锦建材科技有限公司 | A kind of heat of hydration suppressive concrete corrosion-prevention rust-resistance agent and its preparation method and application |
| CN109928656B (en) * | 2019-03-05 | 2021-06-11 | 武汉源锦建材科技有限公司 | Hydration heat inhibition type concrete corrosion and rust inhibitor and preparation method and application thereof |
| CN116214683A (en) * | 2023-05-05 | 2023-06-06 | 石家庄市长安育才建材有限公司 | Concrete surface beautifying agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015074343A1 (en) | 2015-05-28 |
| CN103613318B (en) | 2015-06-24 |
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