CN108409178A - A kind of swelling type microcapsules/cement base self-healing system - Google Patents
A kind of swelling type microcapsules/cement base self-healing system Download PDFInfo
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- CN108409178A CN108409178A CN201810201290.4A CN201810201290A CN108409178A CN 108409178 A CN108409178 A CN 108409178A CN 201810201290 A CN201810201290 A CN 201810201290A CN 108409178 A CN108409178 A CN 108409178A
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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
- 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
- C04B20/1048—Polysaccharides, e.g. cellulose, or derivatives thereof
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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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/281—Polyepoxides
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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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
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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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The present invention relates to a kind of swelling type microcapsules/cement base self-healing systems.It is that capsule-core prepares swelling type microcapsules, and Microcapsules Size range is in 300 μm~2.5mm that the system, which includes using calcium alginate as cyst wall, epoxy resin,；A kind of self-repairing cement-base material, basis include cement, sand, microcapsules, water and epoxy curing agent, and the addition content of microcapsules is 0.5~10wt% of cement.Cement, sand and microcapsules are dispersed with stirring uniformly, water and epoxy curing agent are poured into the mixture of cement, sand and microcapsules, after stirring evenly, pouring molding, form removal conserves, that is, forms microcapsules/cement base self-healing system.The microcapsules of the present invention have the feature of water absorption and swelling, and moisture can be compensated in cement hydration process, realize interior care action；And synthesis technology is simple, mechanical property is preferable, non-breakable in cement admixture whipping process, can be dispersed in inside cement-based material, to realize crack autogenous healing.
Description
Technical field
The present invention relates to a kind of swelling type microcapsules/cement base self-healing system, belongs to concrete reducing and crack is repaired
Technical field.
Background technology
Cement products creeping, due to ambient humidity variation and differential settlement etc., will produce various during service
Crack, moisture and other harmful substances penetrate into cement intrinsic silicon by microcrack, can lead to strength reduction, carbonization, reinforcing bar rust
A series of problems, such as erosion, then seriously affects durability and the safety of cement products.For this critical issue, rehydration is reviewed one's lessons by oneself
Cement-based material can timely and effectively repair the damage in microscopic ranges, fundamentally inhibit the development of Crack Damage, it has also become
One of solution of forefront.
Currently, the research about cement-based material self-repair technology is more, wherein due to the micropore profit in cement matrix
In microcapsules dispersed filler, and resinae renovation agent is conducive to matrix strength recovery, microcapsules self-repairing cement-base material by
Great concern.
The research of microcapsules self-repairing cement-base material at present concentrates on preparing micro- glue as wall material using ureaformaldehyde or phenolic resin
Capsule, such as：Document one【Chinese invention patent, publication number CN101289298A, 2008】It is prepared for ureaformaldehyde tree by situ aggregation method
Fat wraps up epoxy resin micro-capsule, and is spiked into cement-based material, and self-healing system, when crackle generates, urea are formed
Urea formaldehyde microcapsules rupture under stress, discharge renovation agent.
But there are still some problems for above-mentioned cement-based material micro-capsule self-repair technology, for example, ureaformaldehyde or phenolic resin
Belong to fragile material, in cement admixture whipping process, cyst wall is broken, and renovation agent discharges in advance, and the mesh of reparation is not achieved
's；Secondly situ aggregation method preparation process is stringent, and production process is complicated, thus affects its popularization and application.
The present invention is that wall material prepares microcapsules using calcium alginate, and calcium alginate has chemical stability and excellent mechanics
Performance, can be subjected to damage influence caused by mechanical agitation, and covering property is good；And synthesis technology is relatively easy, is used as micro- glue
The wall material of capsule has more advantage than now widely used ureaformaldehyde or phenolic resin.
Existing report display, calcium alginate is good microcapsule wall material, using it as the microcapsule preparation process of wall material
Also relatively easy, such as：Document two【Chinese invention patent, publication number CN106117632A, 2016】It is related to a kind of hud typed pitch
Self repairing agent and preparation method thereof, including：Bitumen regenerant is added in polyethylene maleic anhydride aqueous copolymers solution to be stirred,
It after mixed solution and sodium alginate soln shear-mixed, is slowly added into calcium chloride solution, distillation water washing, drying
Obtain hud typed bitumen regenerant.The present invention prepares cement-based material and reviews one's lessons by oneself multiplexing microcapsules, using adhesives such as epoxy resin
Class is as renovation agent, and adhesive release generates the solidfied material of strong rubber stickiness, and pay the seam, repair process is more simple direct, more
Be conducive to industrial applications.
Invention content
The purpose of the present invention is exactly to provide a kind of swelling type microcapsules/cement to overcome defect of the existing technology
Base self-healing system, swellability microcapsules of the incorporation with reparation crack function, pass through suitable technique in cement-based material
Condition and component proportion form swelling type microcapsules/cement base self-healing system.
A kind of swelling type microcapsules/cement base self-healing system, including by cyst wall, epoxy resin of calcium alginate be capsule-core
Prepare swelling type microcapsules；Microcapsules Size range is in 300 μm~2.5mm, preferably 700 μm~1.3mm.Prepare calcium alginate packet
Epoxy resin micro-capsule is covered, the main each component that controls accounts for system percentage composition, specifically includes following steps：
(1) sodium alginate soln is uniformly mixed with emulsifier, epoxy resin is then added thereto, at 55 DEG C~65 DEG C
1.5h is stirred, mixing speed 300r/min~600r/min is controlled, obtains the mixed solution of epoxy resin and sodium alginate；Its
In, the mass ratio of calcium alginate and epoxy resin is 1:3~1:5；
(2) mixed solution that step 1 obtains is added drop-wise in calcium chloride solution, after being added dropwise to complete, 2.5h- is reacted in calcification
3.5h；
(3) after reaction, acetone or absolute ethyl alcohol washing are dried to obtain microcapsules for the calcification of step (2).
By said program, a concentration of 1wt%~4wt% of sodium alginate soln in step (1).
By said program, the emulsifier described in step (1) be selected from neopelex, lauryl sodium sulfate and
One kind of polyvinyl alcohol, preferably neopelex；The emulsifier ratio be sodium alginate soln 0.15wt%~
0.25wt%.
By said program, a concentration of 1.5wt%~3wt% of the calcium chloride solution described in step (2)；Calcium chloride solution with
The mass ratio of sodium alginate soln is 1.5:1~10:1..
A kind of swelling type microcapsules/cement base self-healing system, the system preparation method include the following steps：
(1) it weighs suitable microcapsules, cement, sand to be uniformly mixed, cement：Sand：Water=1:1.1-1.9:0.30-0.55；
Wherein microcapsule content is the 0.5wt%~10wt%, preferably 1.5wt%~5.5wt% of cement；
(2) water and curing agent mixed liquor are poured into the mixture of cement, sand and microcapsules, after stirring evenly, pours and build up
Type, form removal, maintenance form microcapsules/cement base self-healing system.
By said program, the curing agent described in step (2) is selected from ethylenediamine, diethylenetriamine, tetraethylenepentamine, 3N, N-
Dimethylamino propylamine and N, one kind of N- diethylaminopropylamines, preferably tetraethylenepentamine.
By said program, the curing agent content described in step (2) is 10wt%~15wt% of microcapsules.
The present invention uses the microcapsules with excellent mechanical performances and dispersibility, by cement mortar mechanical agitation process,
It is dispersed in uniform microcapsule in cement-based material matrix, when micro-crack generates, moisture enters intrinsic silicon by micro-crack,
Microcapsules water absorption and swelling, the renovation agent of release is cured with the curing agent in matrix to react, and then being formed has strong rubber stickiness
Solidfied material, pay the seam realizes the automatic reparation of fracture.
Beneficial effects of the present invention are：
A kind of swelling type microcapsules/cement base self-healing system, the cement-based material test specimen containing calcium alginate microcapsule
After maintenance processing, compared with corresponding cement-based material, contract with dry rate is decreased obviously, this is because the swellability microcapsules used
Moisture is absorbed in fresh concrete, compensates the moisture loss of hydrated cementitious, is alleviated self-desiccation phenomenon, be further reduced
The risk of cement-based material cracking.This illustrates that the swellability microcapsules of the present invention have interior care action in cement-based material.
Self-repairing microcapsule wall material mechanical property of the present invention is good, the failure by rupture load born be 10.53N~
11.84N, be ureaformaldehyde or phenolic resin class is capsule wall material 26~31 times；It is not fragile in cement admixture whipping process
It is broken.
Self-repairing microcapsule core material clad ratio of the present invention is up to 72%, is capable of providing enough renovation agents for cement matrix
Expect selfreparing.
A kind of swelling type microcapsules/cement base self-healing system, the cement-based material test specimen containing calcium alginate microcapsule
After maintenance processing, compared with corresponding cement-based material, compression strength declines less or even is basically unchanged, and illustrates calcium alginate
Microcapsules damage cement matrix mechanical property smaller.
A kind of swelling type microcapsules/cement base self-healing system, the cement-based material test specimen containing calcium alginate microcapsule
After it experienced the pre- destructions of 30%~75%F (F=72N) and maintenance processing, compared with corresponding cement-based material, water penetration
Coefficient is decreased obviously, and impermeability enhancing, these data illustrate microcapsules during crackle generates, and water absorption and swelling discharges ring
Oxygen resin is cured with the curing agent in matrix and reacts, and crack is blocked, to realize the function of selfreparing.
Description of the drawings
Fig. 1：The 7d compression strength of microcapsules described in embodiment 1/cement base self-repair material
Fig. 2：The water permeability coefficient of 7d is repaired after microcapsules described in embodiment 1/cement base self-repair material precompressed
Fig. 3：The 7d shrinking percentages of microcapsules described in embodiment 1/cement base self-repair material
Fig. 4：The 7d compression strength of microcapsules described in embodiment 2/cement base self-repair material
Fig. 5：The water permeability coefficient of 7d is repaired after microcapsules described in embodiment 2/cement base self-repair material precompressed
Fig. 6：The 7d shrinking percentages of microcapsules described in embodiment 2/cement base self-repair material
Fig. 7：The 7d compression strength of microcapsules described in embodiment 3/cement base self-repair material
Fig. 8：The water permeability coefficient of 7d is repaired after microcapsules described in embodiment 3/cement base self-repair material precompressed
Fig. 9：The 7d shrinking percentages of microcapsules described in embodiment 3/cement base self-repair material
Figure 10：The diameter characterization for the microcapsules that the present invention prepares
Figure 11：The microcapsules displacement-load curves of different-grain diameter
Specific implementation mode
With reference to example, the present invention will be further described, but not as limiting the scope of the invention.
Embodiment 1
(1) 4.0g sodium alginate solids are weighed, is added in 250mL deionized waters, blender is used in combination to be stirred, wait for sea
After mosanom solid is completely dissolved, the sodium alginate soln of 1.6wt% is obtained；
In 55 DEG C of water-baths, above-mentioned sodium alginate soln and 0.63g detergent alkylates is added into four-hole boiling flask respectively
Sodium sulfonate, starts mechanical stirring device, and emulsifier is matched according to the 0.25wt% of sodium alginate soln；
20.0gE-51 bisphenol A type epoxy resins are added under stirring thereto, low whipping speed is to be stirred under 600r/min
1.5h is mixed, epoxy resin-mixed solution of sodium alginate is obtained after cooling.The mass ratio of calcium alginate and epoxy resin is 1:5.
(2) mixed solution that step (1) obtains is added in disposable syringe, uses medical 25G syringe needles；
9.0g calcium chloride solids are weighed, are added in 300mL deionized waters, after calcium solid to be chlorinated is completely dissolved, are obtained
The calcium chloride solution of 3.0wt%；
The mixed solution for being loaded in syringe is added drop-wise in above-mentioned calcium chloride solution, after being added dropwise to complete, continues calcification
2.5h。
(3) calcification of step (2) after reaction, pours out calcium chloride solution, then by the good microcapsules of calcification with anhydrous
Ethyl alcohol flushes three times, and is put into 60 DEG C of air dry ovens after dry 6h and takes out to get to epoxy resin-calcium alginate microcapsule.
Gained microcapsules average grain diameter is 1.28mm.
By the 600g cement of precise, 240g water (ratio of mud 0.40) under low speed (60rpm) agitating paddle mechanical agitation
120s；Then 9g, 21g, 33g calcium alginate microcapsule is added with the 1.5% of cement quality, 3.5%, 5.5% respectively, presses simultaneously
Curing agent tetraethylenepentamine 1.35g, 3.15g, 4.95g is accordingly added according to the 15% of microcapsules quality, continues low speed (60rpm) and stirs
120s is mixed, is turned to uniform.Mix cement by new and pour into mold (40mm × 40mm × 40mm), test specimen pour after in standard curing
It is conserved for 24 hours under condition (95% or more relative humidity, 20 ± 2 DEG C of temperature).After the completion of first maintenance, form removal is carried out to mold,
And sample is continued to be put into progress 7d standard curings in fog room, its compression strength is then tested, sees Fig. 1.Add calcium alginate
For the cement base sample of microcapsules compared with blank sample, compression strength declines unobvious, and microcapsules volume is 5.5% (cement
Quality) when, intensity only declines 11.3%, and it is smaller to illustrate that 1 calcium alginate microcapsule of embodiment damages cement matrix mechanical property.
By the 600g cement of precise, 240g water (ratio of mud 0.40) under low speed (60rpm) agitating paddle mechanical agitation
120s；9g calcium alginate microcapsules and 1.35g curing agent tetraethylenepentamine (the 15% of microcapsules quality) is added, continues low speed
(60rpm) stirs 120s, turns to uniform.It is poured into newly cement is mixed in mold (diameter 7.5cm, high 3.5cm cylinders), test specimen
It is conserved for 24 hours under standard curing condition (95% or more relative humidity, 20 ± 2 DEG C of temperature) after pouring.After the completion of first maintenance,
Form removal is carried out to mold, and continues to be put into fog room sample and carry out standard curing, after conserving 7d, respectively with 0%, 30%,
45%, 60%, 75%F (F=72N) precompressions carry out precompressed to test specimen, unload after pressurize 120s, are repaiied under the conditions of standard curing
Multiple 7d, tests its water permeability coefficient, sees Fig. 2.Cement base sample containing calcium alginate microcapsule experienced 30%~75%F
(F=72N) after destruction and maintenance are handled in advance, compared with blank sample, water permeability coefficient is decreased obviously, in experience 60%F (F
=72N) pre- destruction and maintenance processing after, add microcapsules sample water permeability coefficient be 3.1410-7·cm·s-1, and
The water permeability coefficient for not adding microcapsules sample is 12.3110-7·cm·s-1, impermeability significantly increases, these data are said
1 microcapsules of bright embodiment are during crackle generates, water absorption and swelling, and the curing agent in release epoxy resin, with matrix occurs solid
Change reaction, crack is blocked, to realize the function of selfreparing.
By the 600g cement of precise, 240g water (ratio of mud 0.40) under low speed (60rpm) agitating paddle mechanical agitation
120s；Then 9g, 21g, 33g calcium alginate microcapsule is added with the 1.5% of cement quality, 3.5%, 5.5% respectively, presses simultaneously
Curing agent tetraethylenepentamine 1.35g, 3.15g, 4.95g is accordingly added according to the 15% of microcapsules quality, continues low speed (60rpm) and stirs
120s is mixed, is turned to uniform.It is poured into newly cement is mixed in mold (25mm × 25mm × 280mm), test specimen is supported after pouring in standard
It is conserved for 24 hours under guard strip part (95% or more relative humidity, 20 ± 2 DEG C of temperature).After the completion of first maintenance, form removal is carried out to mold
Afterwards, it is sealed with polyethylene film all surface, is put into constant temperature and moisture test room (65 ± 5% or more relative humidity, temperature 20
± 2 DEG C), it conserves to certain age, measures its rate of self-contraction, see Fig. 3.It is compared with blank sample, adds calcium alginate microcapsule
Cement base sample its contract with dry rate be decreased obviously, or even expand, this is because the 1 swellability microcapsules of embodiment used exist
Moisture is absorbed in fresh concrete, compensates the moisture loss of hydrated cementitious, alleviates self-desiccation phenomenon, and then realizes interior support
Protective function.
Embodiment 2
(1) 2.5g sodium alginate solids are weighed, is added in 250mL deionized waters, blender is used in combination to be stirred, wait for sea
After mosanom solid is completely dissolved, the sodium alginate soln of 1.0wt% is obtained；
In 65 DEG C of water-baths, above-mentioned sodium alginate soln and 0.38g detergent alkylates is added into four-hole boiling flask respectively
Sodium sulfonate, starts mechanical stirring device, and emulsifier is matched according to the 0.15wt% of sodium alginate soln；
7.5gE-51 bisphenol A type epoxy resins are added under stirring thereto, low whipping speed is to be stirred under 600r/min
1.5h is mixed, epoxy resin-mixed solution of sodium alginate is obtained after cooling.The mass ratio of calcium alginate and epoxy resin is 1:3.
(2) mixed solution that step (1) obtains is added to 50mL disposable syringes, uses medical 21G syringe needles；
4.5g calcium chloride solids are weighed, are added in 300mL deionized waters, after calcium solid to be chlorinated is completely dissolved, are obtained
The calcium chloride solution of 1.5wt%；
The mixed solution for being loaded in syringe is added drop-wise in above-mentioned calcium chloride solution, after being added dropwise to complete, continues calcification
3.5h。
Gained microcapsules average grain diameter is 2.5mm.
By the 600g cement of precise, 180g water (ratio of mud 0.30) under low speed (60rpm) agitating paddle mechanical agitation
120s；Then respectively with the 0.5% of cement quality, 1.0%, 1.5% addition 3g, 6g, 9g calcium alginate microcapsule, while according to
The 15% of microcapsules quality is corresponding to be added curing agent tetraethylenepentamine 0.45g, 0.90g, 1.35g, continues low speed (60rpm) and stirs
120s is turned to uniform.Mix cement by new and pour into mold (40mm × 40mm × 40mm), test specimen pour after in standard curing item
It is conserved for 24 hours under part (95% or more relative humidity, 20 ± 2 DEG C of temperature).After the completion of first maintenance, form removal is carried out to mold, and
Continue sample to be put into progress 7d standard curings in fog room, then tests its compression strength, see Fig. 4.It is micro- to add calcium alginate
For the cement base sample of capsule compared with blank sample, compression strength decline is less, illustrates 2 calcium alginate microcapsule pair of embodiment
The damage of cement matrix mechanical property is smaller.
By the 600g cement of precise, 180g water (ratio of mud 0.30) under low speed (60rpm) agitating paddle mechanical agitation
120s；9g calcium alginate microcapsules and 1.35g curing agent tetraethylenepentamine (the 15% of microcapsules quality) is added, continues low speed
(60rpm) stirs 120s, turns to uniform.It is poured into newly cement is mixed in mold (diameter 7.5cm, high 3.5cm cylinders), test specimen
It is conserved for 24 hours under standard curing condition (95% or more relative humidity, 20 ± 2 DEG C of temperature) after pouring.After the completion of first maintenance,
Form removal is carried out to mold, and continues to be put into fog room sample and carry out standard curing, after conserving 7d, respectively with 0%, 30%,
45%, 60%, 75%F (F=72N) precompressions carry out precompressed to test specimen, unload after pressurize 120s, are repaiied under the conditions of standard curing
Multiple 7d, tests its water permeability coefficient, sees Fig. 5.Cement base sample containing calcium alginate microcapsule experienced pre- destruction and support
After shield processing, compared with blank sample, water permeability coefficient is decreased obviously, and impermeability significantly increases, and illustrates 2 micro- glue of embodiment
Capsule is during crackle generates, water absorption and swelling, discharges epoxy resin, blocks crack, realizes the function of selfreparing.
By the 600g cement of precise, 180g water (ratio of mud 0.30) under low speed (60rpm) agitating paddle mechanical agitation
120s；Then respectively with the 0.5% of cement quality, 1.0%, 1.5% addition 3g, 6g, 9g calcium alginate microcapsule, while according to
The 15% of microcapsules quality is corresponding to be added curing agent tetraethylenepentamine 0.45g, 0.90g, 1.35g, continues low speed (60rpm) and stirs
120s is turned to uniform.Mix cement by new and pour into mold (25mm × 25mm × 280mm), test specimen pour after in standard curing
It is conserved for 24 hours under condition (95% or more relative humidity, 20 ± 2 DEG C of temperature).After the completion of first maintenance, form removal is carried out to mold
Afterwards, it is sealed with polyethylene film all surface, is put into constant temperature and moisture test room (65 ± 5% or more relative humidity, temperature 20
± 2 DEG C), it conserves to certain age, measures its rate of self-contraction, see Fig. 6.It is compared with blank sample, adds calcium alginate microcapsule
Cement base sample its contract with dry rate be decreased obviously, illustrate that 2 microcapsules of embodiment alleviate self-desiccation phenomenon, realize interior maintenance work(
Energy.
Embodiment 3
(1) 10.0g sodium alginate solids are weighed, is added in 250mL deionized waters, blender is used in combination to be stirred, wait for
After sodium alginate solid is completely dissolved, the sodium alginate soln of 4.0wt% is obtained；
In 55 DEG C of water-baths, above-mentioned sodium alginate soln and 0.65g detergent alkylates is added into four-hole boiling flask respectively
Sodium sulfonate, starts mechanical stirring device, and emulsifier is matched according to the 0.25wt% of sodium alginate soln；
40.0gE-51 bisphenol A type epoxy resins are added under stirring thereto, low whipping speed is to be stirred under 300r/min
1.5h is mixed, epoxy resin-mixed solution of sodium alginate is obtained after cooling.The mass ratio of calcium alginate and epoxy resin is 1:4.
(2) mixed solution that step (1) obtains is added to 50mL disposable syringes, uses medical 30G syringe needles；
9.0g calcium chloride solids are weighed, are added in 300mL deionized waters, after calcium solid to be chlorinated is completely dissolved, are obtained
The calcium chloride solution of 3.0wt%；
The mixed solution for being loaded in syringe is added drop-wise in above-mentioned calcium chloride solution, after being added dropwise to complete, continues calcification
3.5h。
(3) calcification of step (2) after reaction, pours out calcium chloride solution, then by the good microcapsules of calcification with anhydrous
Ethyl alcohol flushes three times, and is put into 60 DEG C of air dry ovens after dry 6h and takes out to get to epoxy resin-calcium alginate microcapsule.
Gained microcapsules average grain diameter is 300 μm.
By the 600g cement of precise, 330g water (ratio of mud 0.55) under low speed (60rpm) agitating paddle mechanical agitation
120s；Then 9g, 21g, 33g, 45g, 57g is added with the 1.5% of cement quality, 3.5%, 5.5%, 7.5%, 9.5% respectively
Calcium alginate microcapsule, at the same according to the 15% of microcapsules quality be accordingly added curing agent tetraethylenepentamine 1.35g, 3.15g,
4.95g, 6.75g, 8.55g continue low speed (60rpm) and stir 120s, turn to uniform.By newly mixing cement pours into mold (40mm
× 40mm × 40mm) in, test specimen conserves after pouring under standard curing condition (95% or more relative humidity, 20 ± 2 DEG C of temperature)
24h.After the completion of first maintenance, form removal is carried out to mold, and sample is continued to be put into progress 7d standard curings in fog room, so
After test its compression strength, see Fig. 7.The cement base sample of calcium alginate microcapsule is added compared with blank sample, pressure resistance
Degree decline is less, and it is smaller to illustrate that 3 calcium alginate microcapsule of embodiment damages cement matrix mechanical property.
By the 600g cement of precise, 330g water (ratio of mud 0.55) under low speed (60rpm) agitating paddle mechanical agitation
120s；9g calcium alginate microcapsules and 1.35g curing agent tetraethylenepentamine (the 15% of microcapsules quality) is added, continues low speed
(60rpm) stirs 120s, turns to uniform.It is poured into newly cement is mixed in mold (diameter 7.5cm, high 3.5cm cylinders), test specimen
It is conserved for 24 hours under standard curing condition (95% or more relative humidity, 20 ± 2 DEG C of temperature) after pouring.After the completion of first maintenance,
Form removal is carried out to mold, and continues to be put into fog room sample and carry out standard curing, after conserving 7d, respectively with 0%, 30%,
45%, 60%, 75%F (F=72N) precompressions carry out precompressed to test specimen, unload after pressurize 120s, are repaiied under the conditions of standard curing
Multiple 7d, tests its water permeability coefficient, sees Fig. 8.Cement base sample containing calcium alginate microcapsule experienced pre- destruction and support
After shield processing, compared with blank sample, water permeability coefficient is decreased obviously, and impermeability significantly increases, and illustrates 3 micro- glue of embodiment
Capsule is during crackle generates, water absorption and swelling, discharges epoxy resin, blocks crack, realizes the function of selfreparing.
By the 600g cement of precise, 330g water (ratio of mud 0.55) under low speed (60rpm) agitating paddle mechanical agitation
120s；Then 9g, 21g, 33g calcium alginate microcapsule is added with the 1.5% of cement quality, 3.5%, 5.5% respectively, presses simultaneously
Curing agent tetraethylenepentamine 1.35g, 3.15g, 4.95g is accordingly added according to the 15% of microcapsules quality, continues low speed (60rpm) and stirs
120s is mixed, is turned to uniform.It is poured into newly cement is mixed in mold (25mm × 25mm × 280mm), test specimen is supported after pouring in standard
It is conserved for 24 hours under guard strip part (95% or more relative humidity, 20 ± 2 DEG C of temperature).After the completion of first maintenance, form removal is carried out to mold
Afterwards, it is sealed with polyethylene film all surface, is put into constant temperature and moisture test room (65 ± 5% or more relative humidity, temperature 20
± 2 DEG C), it conserves to certain age, measures its rate of self-contraction, see Fig. 9.It is compared with blank sample, adds calcium alginate microcapsule
Cement base sample its contract with dry rate be decreased obviously, illustrate that 3 microcapsules of embodiment alleviate self-desiccation phenomenon, realize interior maintenance work(
Energy.
The microcapsules of 1,2,3 gained of above-described embodiment are placed in optical microphotograph under the microscope, as shown in Figure 10, the results showed that
Microcapsules prepared by the present invention are spherical in shape in appearance, and property uniform in size is preferable, this enables microcapsules preferably evenly dispersed
In cement-based material；Single microcapsules mechanical test is carried out to the microcapsules of 1,2,3 gained of above-described embodiment, such as Figure 11 institutes
Show, the results showed that since microcapsule wall material-calcium alginate prepared by the present invention is representative network supporting structure, have good
Mechanical property, the failure by rupture load born be 10.53N~11.84N, be ureaformaldehyde or phenolic resin class microcapsule wall material
26~31 times, the influence that cement mortar mechanical agitation is brought can be born.
Claims (6)
1. a kind of cement-based material reviews one's lessons by oneself multiplexing swelling type microcapsules, which is characterized in that microcapsules are using calcium alginate as cyst wall, ring
Oxygen resin is capsule-core；Microcapsules Size range is in 300 μm~2.5mm.
2. preparing a kind of method that cement-based material reviews one's lessons by oneself multiplexing swelling type microcapsules as described in claim 1, which is characterized in that
The microcapsules are prepared in accordance with the following steps：
(1) sodium alginate soln is uniformly mixed with emulsifier, epoxy resin is then added thereto, stirred at 55 DEG C~65 DEG C
1.5h controls mixing speed 300r/min~600r/min, obtains the mixed solution of epoxy resin and sodium alginate；Wherein, extra large
The mass ratio of calcium alginate and epoxy resin is 1:3~1:5；Emulsifier addition be sodium alginate soln 0.15wt%~
0.25wt%；A concentration of 1wt%~4wt% of sodium alginate soln；
(2) mixed solution that step 1 obtains is added drop-wise in calcium chloride solution, after being added dropwise to complete, 2.5h-3.5h is reacted in calcification；
(3) after reaction, acetone or absolute ethyl alcohol washing are dried to obtain microcapsules for the calcification of step (2).
3. according to the method for claim 2, it is characterised in that emulsifier described in step (1) be selected from neopelex,
One kind of lauryl sodium sulfate and polyvinyl alcohol.
4. according to the method for claim 2, it is characterised in that a concentration of 1.5wt% of the calcium chloride solution described in step (2)~
3wt%；The mass ratio of calcium chloride solution and sodium alginate soln is 1.5:1~10:1.
5. a kind of swelling type microcapsules/cement base self-healing system, which is characterized in that the system preparation method includes following step
Suddenly：
(1) it weighs microcapsules, cement, sand to be uniformly mixed, wherein microcapsule content is 0.5wt%~10wt% of cement；
(2) water and curing agent mixed liquor are poured into the mixture of cement, sand and microcapsules, after stirring evenly, pouring molding is torn open
Mould, maintenance, that is, form microcapsules/cement base self-healing system；
Cement：Sand：Mass ratio=1 of water:1.1-1.9:0.30-0.55；Curing agent content be microcapsules 10wt%~
15wt%.
6. according to the system of claim 5, it is characterised in that curing agent described in step (2) be selected from ethylenediamine, diethylenetriamine,
One kind of tetraethylenepentamine, 3N, N- dimethylamino propylamines and N, N- diethylaminopropylamine.
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| CN110734243A (en) * | 2019-11-01 | 2020-01-31 | 北京工业大学 | SAPs microcapsule and cement-based self-repairing material |
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| CN112552761A (en) * | 2020-12-18 | 2021-03-26 | 杨华 | Concrete salt-resistant protective agent |
| CN113213806A (en) * | 2021-05-21 | 2021-08-06 | 武汉理工大学 | Delayed permeation type core-shell structure chloride ion curing agent and preparation method thereof |
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| CN109250940A (en) * | 2018-10-09 | 2019-01-22 | 北京工业大学 | A kind of calcium alginate microcapsule of high core material content |
| CN109250940B (en) * | 2018-10-09 | 2021-02-26 | 北京工业大学 | Calcium alginate microcapsule with high core material content |
| CN110240457A (en) * | 2019-06-24 | 2019-09-17 | 北京建工一建工程建设有限公司 | A kind of self-repair concrete and preparation method thereof |
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| CN112552761A (en) * | 2020-12-18 | 2021-03-26 | 杨华 | Concrete salt-resistant protective agent |
| CN113233815A (en) * | 2021-05-10 | 2021-08-10 | 北京工业大学 | Non-air-entraining type antifreeze agent suitable for cement-based material |
| CN113233850A (en) * | 2021-05-13 | 2021-08-10 | 南京茂汇盈科技有限公司 | Modified concrete and preparation method thereof |
| CN113213806A (en) * | 2021-05-21 | 2021-08-06 | 武汉理工大学 | Delayed permeation type core-shell structure chloride ion curing agent and preparation method thereof |
| CN113800828A (en) * | 2021-09-03 | 2021-12-17 | 山东省冶金产品质量监督检验站有限公司 | Microcapsule technology-based reinforcement anticorrosion system for concrete |
| CN114605133A (en) * | 2022-01-26 | 2022-06-10 | 苏州白鲨建材有限公司 | Gypsum-based dry-mixed moisture-proof anti-cracking mortar and preparation method thereof |
| CN114716178A (en) * | 2022-03-18 | 2022-07-08 | 天津大学 | Environment-friendly cement self-repairing system, preparation method and application |
| CN114716178B (en) * | 2022-03-18 | 2023-02-17 | 天津大学 | Environment-friendly cement self-repairing system, preparation method and application |
| US11820711B2 (en) | 2022-03-18 | 2023-11-21 | Tianjin University | Environment-friendly cement self-repairing system, its preparation method and application |
| CN115353334A (en) * | 2022-08-20 | 2022-11-18 | 温州华邦混凝土有限公司 | Environment-friendly concrete resistant to chloride ion permeation and preparation method thereof |
| CN115353334B (en) * | 2022-08-20 | 2023-10-03 | 温州华邦混凝土有限公司 | Environment-friendly concrete resistant to chloride ion permeation and preparation method thereof |
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| CN116063050A (en) * | 2023-03-07 | 2023-05-05 | 成都理工大学 | Carbon dioxide corrosion resistant self-healing cement system |
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