CN107840592B - Concrete self-repairing functional additive and preparation method thereof - Google Patents
Concrete self-repairing functional additive and preparation method thereof Download PDFInfo
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- 239000013538 functional additive Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000008139 complexing agent Substances 0.000 claims abstract description 38
- 239000002250 absorbent Substances 0.000 claims abstract description 28
- 239000011347 resin Substances 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 27
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims abstract description 22
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims abstract description 21
- 150000002500 ions Chemical class 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- RNIHAPSVIGPAFF-UHFFFAOYSA-N Acrylamide-acrylic acid resin Chemical compound NC(=O)C=C.OC(=O)C=C RNIHAPSVIGPAFF-UHFFFAOYSA-N 0.000 claims description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 238000005507 spraying Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 239000004566 building material Substances 0.000 abstract description 3
- 230000015271 coagulation Effects 0.000 abstract description 2
- 238000005345 coagulation Methods 0.000 abstract description 2
- 230000003111 delayed effect Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 17
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 15
- 229910001424 calcium ion Inorganic materials 0.000 description 15
- 238000012360 testing method Methods 0.000 description 12
- 239000004568 cement Substances 0.000 description 10
- 239000011148 porous material Substances 0.000 description 7
- 239000001509 sodium citrate Substances 0.000 description 7
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000008014 freezing Effects 0.000 description 6
- 238000007710 freezing Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- -1 silicate ions Chemical class 0.000 description 5
- 239000000176 sodium gluconate Substances 0.000 description 5
- 229940005574 sodium gluconate Drugs 0.000 description 5
- 235000012207 sodium gluconate Nutrition 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003094 microcapsule Substances 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 229910052918 calcium silicate Inorganic materials 0.000 description 3
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 3
- 229960001231 choline Drugs 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009435 building construction Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004083 survival effect Effects 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
- 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
-
- 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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/10—Acids or salts thereof containing carbon in the anion
- C04B22/106—Bicarbonates
-
- 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
- C04B28/02—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 containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F122/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F122/04—Anhydrides, e.g. cyclic anhydrides
- C08F122/06—Maleic anhydride
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Working Measures On Existing Buildindgs (AREA)
Abstract
The invention belongs to the field of building materials, and particularly relates to a concrete self-repairing functional additive and a preparation method thereof. The functional additive is prepared by mixing a multi-element ion complexing agent, calcium bicarbonate and water-absorbent resin, and the functional additive comprises the following raw materials in parts by weight: 40-60 parts of a multi-ion complexing agent, 40-50 parts of calcium bicarbonate and 1-5 parts of a water-absorbent resin. The functional admixture has the advantages of strong self-repairing capability, good wide crack self-repairing effect, high repairing speed and the like, has no delayed coagulation effect, has stronger practicability, and has stronger application and popularization values in the field of concrete self-repairing.
Description
Technical Field
The invention belongs to the field of building materials, and particularly relates to a concrete self-repairing functional additive and a preparation method thereof.
Background
Cement concrete has been widely used as an important basic building material in the fields of building construction, road construction, subway tunnels, bridges, reservoir dams, hydropower stations, wharfs and the like. However, concrete is a porous brittle material, and internal damage and cracks are easily generated under the action of external environmental factors. The damage and cracks can reduce the strength of the concrete, aggravate the occurrence of chemical erosion, freeze-thaw damage, steel bar corrosion and alkali-aggregate reaction of the concrete, and seriously reduce the durability of the concrete structure.
In order to improve the durability of concrete structures, the self-repairing technology of concrete damage and cracks is increasingly emphasized. The existing concrete self-repairing technology mainly comprises the following steps: the functional admixture is added to excite the self-repairing reaction of the components of the concrete at the internal damage and crack; the microcapsule containing the binder is added, and the binder can self-repair cracks after the microcapsule is broken; microorganism and nutrient solution are added into concrete, and calcite prepared by the reaction of the microorganism and the nutrient solution can be used for self-repairing damage and cracks. Among these self-repairing techniques, the microcapsule method has a problem that the capsule is difficult to break and the binder cannot flow out when damage or crack is generated, and the microbial method has a problem that the survival time of the microorganism is short and the strength of the concrete is reduced, and thus it is not practical.
Compared with the microcapsule method and the microbial method, the self-repairing technology of the functional additive method has certain practicability. The patent CN 101386508A discloses a formula and a preparation process of a crack self-repairing material, and the formula of the crack self-repairing material disclosed by the invention is as follows: 62 to 77 percent of Portland cement, 0.2 to 1 percent of sodium citrate, 3 to 8 percent of choline, 1 to 3 percent of calcium oxide and 22 to 35 percent of 80 to 120 meshes. When concrete cracks, sodium citrate and choline respectively form water-soluble unstable complexes with calcium ions and silicate ions in the concrete under the condition of moisture or humidity, and the sodium citrate and the choline are crystallized to form precipitates at pores and cracks of the concrete, so that self-repairing is realized. Patent CN 105884299A discloses a super self-healing scale cracking concrete high-permeability crystallization repair material, which comprises the following components: 30-45% of ordinary portland cement, 40-60% of quartz sand, 3-15% of fly ash, 1-8% of silica fume, 1-10% of aluminate cement, 1-10% of gypsum, 0.1-4% of sodium hydroxide, 0.1-4% of water glass, 0.1-2% of redispersible rubber powder, 0.05-1.5% of polycarboxylic acid water reducing agent, 0.01-1% of sodium gluconate and 0.1-2.5% of polypropylene fiber. However, the existing concrete self-repairing functional additives all have the following characteristics: (1) the used sodium citrate and sodium gluconate have strong inhibiting effect on the hydration of cement, belong to typical cement concrete retarders, and can greatly prolong the setting time of the concrete when a small amount of the retarder is added; (2) the chelating products formed after the sodium citrate, the sodium gluconate and the like react with calcium ions are of an annular structure, the molecular size is large, the migration speed to the crack of concrete is slow, and even the chelating products cannot migrate through some tiny pores; (3) free calcium ions and silicate ions in the concrete are less, the quantity of chelated calcium ions such as sodium citrate and sodium gluconate is less, the capacity of carrying calcium ions to cracks is weak, and the cracks cannot be self-repaired for wider cracks; (4) sodium citrate, sodium gluconate and the like have chelation reaction with calcium ions and migrate into cracks, and functional additives and silicate ions have reactions which can only occur under the condition of moisture or humidity, and the crack self-repairing needs a long time, but the moisture retention capacity of concrete is very weak, the volatilization of internal moisture is very fast, once no moisture or humidity exists in the concrete, the self-repairing reaction is stopped, and the good repairing is difficult to realize. The existence of these problems severely limits the application of functional admixtures to self-repair of concrete.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a concrete self-repairing functional additive and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
the admixture with the self-repairing function for the concrete is prepared by mixing a multi-element ion complexing agent, calcium bicarbonate and water-absorbent resin, and comprises the following raw materials in parts by weight: 40-60 parts of a multi-ion complexing agent, 40-50 parts of calcium bicarbonate and 1-5 parts of a water-absorbent resin.
In the above scheme, the molecular structural formula of the multi-element ion complexing agent is:
wherein n is 2 or 3, and the molecular weight is 280-430 Da.
In the scheme, the multi-element ion complexing agent is prepared by the following method: adding maleic anhydride and deionized water into a reactor with a condensation reflux device, heating while stirring, heating to 90-95 ℃ after the maleic anhydride is completely dissolved, adding aqueous hydrogen peroxide, reacting at constant temperature for a period of time, adding sodium hydroxide solution, continuing to react, and after the reaction is finished, spray-drying the product to obtain the multi-element ion complexing agent.
In the scheme, the preparation method comprises the following raw materials in parts by weight: 100 parts of maleic anhydride, 100 parts of deionized water, 30 parts of aqueous hydrogen peroxide and 100 parts of sodium hydroxide solution; the volume concentration of the hydrogen peroxide aqueous solution is 25-35%, and the molar concentration of the sodium hydroxide solution is 0.1-0.15 mol/L.
In the scheme, the constant-temperature reaction time in the preparation method is 3-5 h, and the sodium hydroxide solution is added for continuous reaction for 1-2 h.
In the scheme, the water-absorbent resin is acrylic acid-acrylamide copolymerized water-absorbent resin, and the water absorption multiplying power is 100-300.
The preparation method of the concrete self-repairing functional additive comprises the following steps: 1) weighing 40-60 parts of a multi-element ion complexing agent, 30-50 parts of calcium bicarbonate and 1-5 parts of water-absorbent resin according to the weight parts of the raw materials; 2) and adding 40-60 parts of the weighed multi-element ion complexing agent, 30-50 parts of calcium bicarbonate and 1-5 parts of water-absorbent resin into a mixer for mechanical mixing for 5min to obtain the concrete self-repairing functional admixture.
The multi-element ion complexing agent synthesized by the invention is prepared by reacting 2 or 3 maleic anhydrides, and the molecular structural formula is as follows:
The invention has the following beneficial effects:
(1) the concrete self-repairing functional additive is prepared from a multi-ion complexing agent, calcium bicarbonate and water-absorbent resin, wherein the multi-ion complexing agent contains a plurality of complexing units and can complex a large number of calcium ions; the calcium bicarbonate can provide calcium ions and carbonate ions by hydrolysis; the multi-ion complexing agent, free calcium ions in the concrete and calcium ions generated by hydrolysis of calcium bicarbonate form soluble complexes which can migrate to pores, microcracks and cracks along with water, and the soluble complexes containing the calcium ions react with silicate ions and carbonate ions in the concrete (carbonate ions generated by hydrolysis of calcium bicarbonate and carbonate ions generated by hydrolysis of carbon dioxide in air permeating into the concrete) to generate calcium silicate and calcium carbonate precipitates so as to repair damage and cracks; the quantity of ions which can be complexed by the multi-element ion complexing agent is large, the source of calcium ions in the functional admixture is sufficient, and meanwhile, the super-absorbent capacity of the water-absorbent resin is utilized, so that the concrete can be in a wet state for a long time, the continuous self-repairing process is ensured, the self-repairing capacity of the functional admixture on internal damage and wider cracks of the concrete is greatly improved, and the functional admixture has the advantages of strong self-repairing capacity, good wide crack self-repairing effect and the like;
(2) the multi-element ion complexing agent is of a linear molecular structure, and a complex formed by the multi-element ion complexing agent and calcium ions has a high migration speed in pores or cracks of concrete, and is easy to pass through tiny pores, so that the complex is favorable for the migration speed of the complex to microcracks and cracks of the concrete, and the multi-element ion complexing agent has the advantage of high repair speed;
(3) the multi-element ion complexing agent does not contain hydroxyl, has no inhibiting effect on the hydration process of cement, does not influence the setting time of concrete, has no delayed coagulation effect, has stronger practicability and has stronger application and popularization values in the field of self-repairing of concrete.
Drawings
FIG. 1 is a photograph of a crack self-healing of ordinary concrete (control) without the addition of the self-healing admixture of the present invention, wherein the left image is an initial crack; the right panel shows the cracks after standard cure 28 d.
FIG. 2 is a photo of self-repairing of a concrete crack with the addition of the self-repairing additive of the present invention, wherein the left image is an initial crack; the right panel shows the cracks after standard cure 28 d.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
In the following examples, the multi-ionic complexing agent was prepared by the following method: adding 200 parts of deionized water and 200 parts of maleic anhydride into a 1000ml three-neck flask with condensation reflux, stirring to completely dissolve the maleic anhydride, heating to 90-95 ℃, adding 30 parts of 30 vt% hydrogen peroxide aqueous solution, reacting at constant temperature for 4 hours, adding 100 parts of 0.12mol/L sodium hydroxide solution, reacting for 1.5 hours, and then spray drying to obtain the multi-element ion complexing agent.
Example 1
A self-repairing functional concrete admixture is prepared by the following method: weighing 53 parts of a multi-ion complexing agent, 45 parts of calcium bicarbonate and 2 parts of acrylic acid-acrylamide copolymerized water-absorbent resin, adding into a mixer, and mechanically stirring for 5min to obtain the concrete self-repairing functional additive.
Example 2
A self-repairing functional concrete admixture is prepared by the following method: weighing 53 parts of multi-ion complexing agent, 43 parts of calcium bicarbonate and 4 parts of acrylic acid-acrylamide copolymerized water-absorbent resin, adding into a mixer, and mechanically stirring for 5min to obtain the concrete self-repairing functional additive.
Weighing cement, crushed stone, mineral powder, sand, water, a water reducing agent and the concrete self-repairing functional admixture prepared in the embodiment 1 or the embodiment 2 according to the mass ratio in the table 1. Firstly adding broken stone, sand, mineral powder, cement and the additive with the self-repairing function into a concrete mixer to be mixed for 30s, and then adding a water reducing agent and water into the mixer to be mixed for 120s to obtain concrete with the crack self-repairing function; the concrete self-repairing functional additive is not added in a control group, and other conditions are the same.
The prepared self-repairing concrete and the control group concrete are respectively subjected to freeze-thaw damage self-repairing and crack self-repairing tests, and the concrete operation is as follows:
(1) taking parts of the self-repairing concrete and the control group concrete, respectively adding the parts into a 100mm multiplied by 100mm mould, demoulding after 1 day, putting the parts into a curing room for curing for 28 days, taking out the test piece, carrying out 200 times of slow quick freezing and melting cycles according to the national standard GB/T50082-2009, taking out the test piece after the freezing and melting cycles are finished, watering and curing for 28 days (watering once every 4 days), and testing the compressive strength of the test piece before and after the freezing and melting cycles and after the watering and curing. Example 1 the compressive strength of the self-repairing concrete before freeze-thaw cycle is 43.2MPa, the compressive strength after freeze-thaw cycle is 35.8MPa, and the compressive strength after watering and curing is 39.8 MPa; example 2 the compressive strength of the self-repairing concrete before freeze-thaw cycle is 42.5MPa, the compressive strength after freeze-thaw cycle is 35.2MPa, and the compressive strength after watering and curing is 40.6 MPa; the compressive strength of the concrete of the control group before freeze-thaw cycle is 41.8MPa, the compressive strength after freeze-thaw cycle is 31.7MPa, and the compressive strength after watering and curing is 32.6 MPa. Test results show that the internal damage of common concrete (a control group) generated by freeze-thaw cycling can not be healed after 28 days of curing, while the internal damage of the concrete doped with the self-repairing admixture can be well repaired after curing (the recovery rate of the compressive strength of the embodiment 1 is 92.1 percent, and the recovery rate of the compressive strength of the embodiment 2 is 95.5 percent); compared with the example 1, the self-repairing functional admixture used in the example 2 has more water-absorbent resin, and the damage self-repairing capability of the concrete is further improved.
(2) And respectively pouring parts of the self-repairing concrete and the concrete of the control group into a concrete flat anti-cracking mould, immediately blowing for 4 hours by using a fan after vibrating and leveling, keeping the central air speed of the concrete sample to be not less than 5m/s, enabling the concrete to generate cracks, measuring the initial cracks, then carrying out watering maintenance (watering once every 4 days), and respectively measuring the width of the cracks when the concrete is maintained for 7 days, 14 days, 21 days and 28 days. The crack width measurements are listed in table 2. As can be seen from the table 2, the crack self-healing capability of the common concrete of the control group is very weak, and the crack width basically has no change along with the extension of the curing time, while the concrete doped with the admixture with the self-healing function has good self-healing effect on small cracks (less than 0.2mm) and also has very strong crack self-healing capability on wider cracks (more than 0.3 mm); compared with the example 1, the self-repairing functional admixture used in the example 2 has more water-absorbent resin, and the crack self-repairing capability of the concrete is further enhanced.
TABLE 1 concrete proportions
Table 2 crack width variation during curing of concrete prepared in examples 1 and 2 and control
Example 3
A self-repairing functional concrete admixture is prepared by the following method: weighing 53 parts of a multi-ion complexing agent, 45 parts of calcium bicarbonate and 3 parts of acrylic acid-acrylamide copolymerized water-absorbent resin, adding into a mixer, and mechanically stirring for 5min to obtain the concrete self-repairing functional additive.
Example 4
A self-repairing functional concrete admixture is prepared by the following method: weighing 57 parts of a multi-ion complexing agent, 40 parts of calcium bicarbonate and 3 parts of acrylic acid-acrylamide copolymerized water-absorbent resin, adding into a mixer, and mechanically stirring for 5min to obtain the concrete self-repairing functional additive.
And weighing cement, crushed stone, mineral powder, sand, water, a water reducing agent and the concrete self-repairing functional admixture prepared in the embodiment 3 or the embodiment 4 according to the mass ratio in the table 3. Firstly adding broken stone, sand, mineral powder, cement and the additive with the self-repairing function into a concrete mixer to be mixed for 30s, and then adding a water reducing agent and water into the mixer to be mixed for 120s to obtain concrete with the crack self-repairing function; the concrete self-repairing functional additive is not added in a control group, and other conditions are the same.
Performing freeze-thaw damage self-repairing and crack self-repairing tests on the prepared self-repairing concrete and the control group concrete respectively:
(1) taking parts of the self-repairing concrete and the control group concrete, respectively adding the parts into a 100mm multiplied by 100mm mould, demoulding after 1 day, putting the parts into a curing room for curing for 28 days, taking out the test piece, carrying out 300 times of slow quick freezing and melting cycles according to the national standard GB/T50082-2009, taking out the test piece after the freezing and melting cycles are finished, watering and curing for 28 days (watering once every 4 days), and testing the compressive strength of the test piece before and after the freezing and melting cycles and after the watering and curing. Example 3 compressive strength of self-repairing concrete before freeze-thaw cycle is 59.3MPa, compressive strength after freeze-thaw cycle is 50.4MPa, and compressive strength after watering and curing is 55.0 MPa; example 4 the compressive strength of the self-repairing concrete before freeze-thaw cycle is 61.1MPa, the compressive strength after freeze-thaw cycle is 51.2MPa, and the compressive strength after watering and curing is 57.6 MPa; the compressive strength of the concrete of the comparison group before freeze-thaw cycle is 57.5MPa, the compressive strength after freeze-thaw cycle is 42.7MPa, and the compressive strength after watering and curing is 44.2 MPa. The test results also show that: the internal damage of the common concrete (a control group) generated by freeze-thaw cycle is basically not healed after 28 days of curing, while the internal damage of the concrete doped with the self-repairing additive is well repaired after curing; compared with the embodiment 3, the content of the multi-ion complexing agent in the self-repairing functional additive used in the embodiment 4 is increased, and the internal damage self-repairing capability of the concrete is further improved.
(2) And respectively pouring parts of the self-repairing concrete and the concrete of the control group into a concrete flat anti-cracking mould, immediately blowing for 4 hours by using a fan after vibrating and leveling, keeping the central air speed of the concrete sample to be not less than 5m/s, enabling the concrete to generate cracks, measuring the initial cracks, then carrying out watering maintenance (watering once every 4 days), and respectively measuring the width of the cracks when the concrete is maintained for 7 days, 14 days, 21 days and 28 days. The crack width measurements are listed in table 4. As can be seen from Table 4, the crack width of the control group of the ordinary concrete is basically unchanged, while the crack repairing capability of the concrete doped with the functional admixture prepared in examples 3 and 4 is remarkably improved. Compared with the embodiment 3, the self-repairing functional additive used in the embodiment 4 has the advantages that the content of the multi-ion complexing agent is increased, the self-repairing capability of the concrete cracks is further improved, and the self-repairing capability of the concrete cracks with the thickness of more than 0.7mm is realized.
TABLE 3 concrete proportions
Table 4 crack width variation during curing of concrete prepared in examples 3 and 4 and control
Example 5
A self-repairing functional concrete admixture is prepared by the following method: weighing 40 parts of multi-element ion complexing agent, 50 parts of calcium bicarbonate and 5 parts of acrylic acid-acrylamide copolymerized water-absorbent resin; and adding the weighed multi-element ion complexing agent, calcium bicarbonate and water-absorbent resin into a mixer for mechanical mixing for 5min to obtain the concrete self-repairing functional additive.
Example 6
A self-repairing functional concrete admixture is prepared by the following method: weighing 60 parts of a multi-ion complexing agent, 30 parts of calcium bicarbonate and 1 part of acrylic acid-acrylamide copolymerized water-absorbent resin; and adding the weighed multi-element ion complexing agent, calcium bicarbonate and water-absorbent resin into a mixer for mechanical mixing for 5min to obtain the concrete self-repairing functional additive.
It is apparent that the above embodiments are only examples for clearly illustrating and do not limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are therefore intended to be included within the scope of the invention as claimed.
Claims (6)
1. The concrete self-repairing functional admixture is characterized by being prepared by mixing a multi-ion complexing agent, calcium bicarbonate and a water-absorbent resin, wherein the raw materials comprise, by weight, 40 ~ 60 parts of the multi-ion complexing agent, 40 ~ 50 parts of the calcium bicarbonate and 1 ~ 5 parts of the water-absorbent resin, and the molecular structural formula of the multi-ion complexing agent is as follows:
wherein n is 2, the molecular weight is 280 ~ 430, and the water-absorbent resin is acrylic acid-acrylamide copolymerized water-absorbent resin.
2. The admixture with the self-repairing function for the concrete of claim 1, wherein the multi-element ion complexing agent is prepared by adding maleic anhydride and deionized water into a reactor with a condensing reflux device, heating while stirring, heating to 90 ~ 95 ℃ after the maleic anhydride is completely dissolved, adding aqueous hydrogen peroxide, reacting for a period of time at constant temperature, adding sodium hydroxide solution, continuing to react, and after the reaction is finished, spraying and drying the product to obtain the multi-element ion complexing agent.
3. The self-repairing functional additive for concrete of claim 2, wherein the raw materials in the preparation method comprise, by weight, 100 parts of maleic anhydride, 100 parts of deionized water, 30 parts of aqueous hydrogen peroxide and 100 parts of sodium hydroxide solution, wherein the volume concentration of the aqueous hydrogen peroxide is 25% ~ 35%, and the molar concentration of the sodium hydroxide solution is 0.1mol/L ~ 0.15.15 mol/L.
4. The concrete self-repairing functional admixture according to claim 2, wherein the constant temperature reaction time in the preparation method is 3h ~ 5h, and the reaction is continued for 1h ~ 2h by adding sodium hydroxide solution.
5. The self-repairing functional concrete admixture of claim 1, wherein the water absorption capacity of the acrylic acid-acrylamide copolymerized water-absorbent resin is 100 ~ 300.
6. The preparation method of the concrete self-repairing functional admixture of claim 1 ~ 5 is characterized by comprising the steps of 1) weighing 40 ~ 60 parts of multi-ion complexing agent, 40 ~ 50 parts of calcium bicarbonate and 1 ~ 5 parts of water-absorbent resin according to the weight part ratio of the raw materials, and 2) adding 40 ~ 60 parts of the weighed multi-ion complexing agent, 40 ~ 50 parts of calcium bicarbonate and 1 ~ 5 parts of water-absorbent resin into a mixer for mechanical mixing for 5min to obtain the concrete self-repairing functional admixture.
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Application publication date: 20180327 Assignee: Shenzhen Liyichen Waterproof Technology Co.,Ltd. Assignor: WUHAN University OF TECHNOLOGY Contract record no.: X2024980000716 Denomination of invention: A self repairing functional admixture for concrete and its preparation method Granted publication date: 20200114 License type: Exclusive License Record date: 20240116 |