CN115417618A - Anion curing expansion microcapsule and preparation method and application thereof - Google Patents
Anion curing expansion microcapsule and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- 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
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention belongs to the technical field of material science and engineering, and particularly relates to an anion curing expansion microcapsule as well as a preparation method and application thereof. The anion curing expansion microcapsule comprises a wall material and a core material; wherein the wall material is calcium alginate, and the core material is an anionic curing agent. The anion curing expansion microcapsule has high mechanical property and high anion curing efficiency, and can rapidly expand and stop leakage to play a repairing role when a salt solution invades; the microcapsule shell can be used as a concrete self-curing material, can reduce the shrinkage of a matrix, improve the freeze-thaw resistance and the cracking resistance, and effectively improve the strength of the cement-stone matrix; the three-dimensional network structure of the microcapsule shell greatly increases the contact area between the microcapsule shell and an anion curing agent, increases the anion curing efficiency, prolongs the curing period, improves the sulfate corrosion resistance and the chloride ion permeability resistance of the concrete, and improves the durability of the concrete.
Description
Technical Field
The invention belongs to the technical field of material science and engineering, and particularly relates to an anion curing expansion microcapsule as well as a preparation method and application thereof.
Background
The concrete structure is widely applied to various civil engineering, and is usually obtained by taking cement as a cementing material and sandstone as an aggregate, adding water and other additives, and then stirring. The embedding of the reinforcing steel bars can further enhance the mechanical properties of the concrete, such as tensile strength, ductility, crack resistance and the like. However, with the rise of marine industry and the development of marine engineering in China, the demand of high-performance reinforced concrete structures is greatly increased. The steel bar has serious corrosion problem in marine environment, which causes the safety and durability of concrete structure to be reduced, and causes serious economic loss, environmental pollution, resource waste and the like.
The pore solution in the unpolluted concrete environment keeps high alkalinity, the surface of the steel bar is provided with a layer of stable passive film, the corrosion rate is lower than 0.1 mu Acm -2 . However, the concentration of corrosive chloride ions in the marine environment is increased, and the chloride ions permeate into the concrete through multiple actions such as capillary action, diffusion, electrochemical migration and the like, so that the resistivity of the concrete is reduced, the pH value of a local environment is influenced, the property of a passivation film semiconductor is changed, the steel bar is passivated, the corrosion rate is increased, and finally the whole reinforced concrete structure is degraded.
The concrete sulfate erosion is an aggressive medium damage with great harmfulness, is one of important factors influencing the durability of concrete, and is an environmental water erosion with the most complex influencing factors and the greatest harmfulness. The production of ettringite, gypsum and wollastonite during sulfate attack produces expansive destructive effects on concrete, which is the primary cause of corrosive damage to concrete. The salt minerals generated by the reaction can dissolve or decompose components such as CH, C-S-H and the like in the hardened set cement, so that the strength and the bonding property of the set cement are lost. The attack forms can be divided into chemical attacks (ettringite, gypsum, cristobalite crystals), physical attacks (alkali metal sulfate crystals) and physical and chemical attacks (magnesium sulfate attack-crystallization). This results in destruction of the internal mechanism, eventually leading to a reduction in the durability of the concrete.
The corrosion inhibitor is specially used for preventing or delaying the corrosion of reinforced concrete so as to improve the durability of the structure. The corrosion inhibitor mainly has the following basic properties: 1. can inhibit the generation and the development of rust; 2. the basic performance of the concrete is not changed; 3. can be effective for a long time under alkaline or neutral conditions; 4. is basically harmless to human. The inorganic steel bar rust inhibitor mainly comprises nitrite, nitrate, chromate, dichromate, phosphate, polyphosphate, silicate, molybdate, borate and the like. The protective film acts on the surface of the steel bar to form a precipitative protective film, and the corrosion of the steel bar caused by chloride ions is inhibited. The organic rust inhibitor mainly takes amines, aldehydes, alkynols, organic phosphorus compounds, organic sulfur compounds, carboxylic acid and salts thereof, sulfonic acid and salts thereof, heterocyclic compounds and the like as main components, and has the functions of preventing harmful substances from entering the interior of concrete, prolonging the time for the concentration of chloride ions on the surface of a reinforcing steel bar to reach a critical value and prolonging the service life of the concrete. However, the existing corrosion inhibitor has slow reaction with anions, can not realize quick plugging on an anion transfer medium, and is difficult to fundamentally solve the problem of corrosion of the steel bar.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an anion curing expansion microcapsule and a preparation method and application thereof. When the anion curing expansion microcapsule is used in concrete, the sulfate erosion resistance and chloride ion permeation resistance of the concrete can be obviously improved, the corrosion problem of reinforcing steel bars is fundamentally solved or relieved, and the structural durability of the concrete is greatly prolonged.
In order to achieve the purpose, the invention adopts the technical scheme that:
an anion-curable swelling microcapsule comprising a wall material and a core material;
wherein the wall material is calcium alginate, and the core material is an anionic curing agent.
In the present invention, the anion curing agent is a material having a strong adsorption ability to corrosive ions such as chloride ions and sulfate ions, and examples thereof include barium carbonate and layered hydrotalcite.
The solidification expansion microcapsule takes the water-absorbing polymer calcium alginate as a wall material and the anion curing agent as a core material, is applied to concrete, quickly absorbs water and expands when harmful fluid such as seawater invades along a fine crack to realize short-time leak repairing, and inhibits the harmful fluid from continuously invading into the concrete. When the calcium alginate releases water, the anion curing agent embedded in the calcium alginate three-dimensional network structure starts to absorb harmful anions in an environmental solution, the contact area is large, the water releasing speed is slow, the sufficient reaction of the anion curing agent and the anions is ensured, the 'blocking and absorbing' of the concrete to the anions and a transmission medium thereof under a special application scene is realized, the corrosion problem of a reinforcing steel bar is fundamentally solved or relieved, and the structural durability of the concrete is greatly prolonged.
The invention also discovers that calcium alginate is used as a wall material, the obtained anion curing expansion microcapsule has the mechanical strength of more than 1N, has elasticity after water absorption, and is rarely broken in the stirring process of concrete or mortar, and if urea formaldehyde, styrene or phenolic resin or the like is used as the wall material, the obtained microcapsule has high brittleness and is easy to break in the stirring process, so that the core material is released in advance, and the microcapsule is invalid.
In addition, calcium alginate is used as a wall material and can also be used as a concrete internal curing material, so that the shrinkage of a matrix can be reduced, the freeze-thaw resistance and the cracking resistance can be improved in the natural curing process of the concrete, and the strength of the cement stone matrix can be effectively improved.
Preferably, the content of the core material is 30-55% by weight of the anion cured expansion microcapsule. The invention discovers that the content of the core material is controlled to be in the range, and the core material locks the water-absorbing resin, namely the calcium alginate, so that the water-absorbing resin cannot be freely expanded, and the phenomenon that the mechanical strength of the concrete is reduced due to the fact that the anion curing expansion microcapsule excessively absorbs water and swells to form pores can be avoided.
Preferably, the anionic curing agent is one or two selected from barium carbonate and corrosion-inhibiting hydrotalcite. Compared with other anion curing agents, the invention discovers that the anion curing expansion microcapsule prepared by adopting barium carbonate and corrosion-inhibiting hydrotalcite has better anion curing performance and lower production cost. The hydrotalcite is an interlayer compound formed by metal hydroxide with positive charges and anions with negative charges filled between layers, and the anions with anti-corrosion capacity are inserted into the hydrotalcite layers through chemical synthesis by utilizing the interlayer ion exchangeability to prepare the corrosion-inhibiting hydrotalcite.
Further preferably, the corrosion-inhibiting hydrotalcite is one or two selected from aluminum magnesium barium hydrotalcite and aluminum zinc molybdenum hydrotalcite.
Most preferably, the anion curing agent is a mixture of barium carbonate and corrosion inhibition hydrotalcite with the mass ratio of 2:1-5:1. Experiments show that the sulfate erosion resistance and the chloride ion permeation resistance of the obtained microcapsule are optimal by compounding the two.
The corrosion inhibition hydrotalcite is preferably prepared by a coprecipitation method.
The invention also provides a method for preparing the anion curing expansion microcapsule, which comprises the following steps:
(1) Mixing an anionic curing agent, a dispersing agent and deionized water, and uniformly mixing by adopting a ball milling method to obtain a mixed solution;
(2) Dissolving sodium alginate in deionized water to obtain a wall material aqueous solution;
(3) Mixing the mixed solution with the wall material aqueous solution to obtain a mixture;
(4) And (4) mixing the mixture obtained in the step (3) with a calcium salt solution, filtering, washing and drying to obtain the anion curing expansion microcapsule.
Preferably, in the step (1), the mass ratio of the anionic curing agent to the deionized water is 1:1-1:2.
Preferably, in the step (1), the dispersant is used in an amount of 2wt% based on the amount of the anionic curing agent.
Preferably, in step (1), the dispersant is ammonium polyacrylate and/or sodium hexametaphosphate, and the invention finds that the anion-cured microcapsule prepared by using the dispersant has the most uniform shape.
Preferably, in the step (1), the ball milling method is roller ball milling, the ball-to-material ratio is 2:1, and the ball milling time is 12 to 36 hours.
Preferably, the step (2) is specifically: and heating the deionized water to 55-70 ℃, slowly adding sodium alginate powder while stirring, and continuously stirring to obtain the wall material aqueous solution.
Further preferably, in the step (2), the mass ratio of the sodium alginate powder to the deionized water is 1.
Preferably, the step (3) is specifically: and carrying out ultrasonic dispersion on the mixed solution for a period of time, then slowly adding the mixed solution after ultrasonic treatment into the wall material aqueous solution, and continuously stirring for a period of time.
Further preferably, in the step (3), the power of the ultrasonic dispersion is 250W, and the time of the ultrasonic dispersion is 5 to 10 minutes.
More preferably, in the step (3), the mass ratio of the anion curing agent in the mixed solution to the sodium alginate in the wall material aqueous solution is 3.0 to 6.0:1, the continuous stirring time is 30-90 minutes.
Preferably, the step (4) is specifically: and (4) dripping the mixture obtained in the step (3) into a calcium salt solution, and filtering, washing and drying to obtain the anion cured expansion microcapsule.
Preferably, in the step (4), the calcium salt solution is one or two of a calcium nitrate solution and a calcium lactate solution, the concentration of the calcium salt solution is 1-2%, and the drying temperature is 30-40 ℃.
In summary, the invention preferably prepares the mixed solution by ball milling-ultrasonic technology, uniformly mixes the mixed solution with the wall material aqueous solution, and prepares the anion curing expansion microcapsule by an orifice forming coagulation bath method. The microcapsule prepared by the method has high core material content, high mechanical strength and simple preparation process.
The invention also provides the application of the anion curing expansion microcapsule or the anion curing expansion microcapsule prepared by the preparation method in the field of concrete, in particular the application in a reinforced concrete structure for preventing seawater corrosion.
The invention has the beneficial effects that:
1) According to the anion curing expansion microcapsule provided by the invention, the anion curing agent is coated in the water-absorbent polymer calcium alginate, so that the effect of blocking before absorbing is exerted, the sulfate corrosion resistance and chloride ion permeation resistance of concrete are improved, and a powerful technical support is provided for the application in special environments such as ocean engineering and the like.
2) The anion curing expansion microcapsule provided by the invention has the mechanical strength of more than 1N, has elasticity after absorbing water, and reduces breakage in the stirring process of concrete or mortar;
3) The anion curing expansion microcapsule provided by the invention can be used as an internal curing material in concrete, and plays a certain role in cracking resistance and shrinkage resistance, so that the durability of the concrete is improved;
4) The anion curing expansion microcapsule provided by the invention has the water absorption rate controlled at 40-90%, and avoids the reduction of concrete mechanical strength caused by pores formed by excessive water absorption and swelling.
Drawings
FIG. 1 is an anion cured microcapsule (single particle) prepared in example 1;
FIG. 2 is an anionically cured microcapsule (multiparticulates) prepared in example 1;
FIG. 3 shows the screening results of the anionically solidified microcapsules prepared in example 1;
figure 4 is an anionic cured microcapsule (single particle) prepared in comparative example 1.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. Modifications or substitutions to methods, steps or conditions of the present invention may be made without departing from the spirit and scope of the invention.
The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. All reagents or instruments are conventional products available from regular vendors, not indicated by the manufacturer.
In the following examples of the present invention,
the preparation method of the magnesium-aluminum-barium hydrotalcite comprises the following steps: mixing the following components in a mass ratio of 20:5:3, dissolving the aluminum material, the barium material and the magnesium material in water, adjusting the pH to 9, reacting at 65 ℃, and then roasting at high temperature of 250 ℃ to obtain aluminum-magnesium-barium hydrotalcite; the aluminum material is aluminum nitrate, the magnesium material is magnesium nitrate, and the barium material is barium nitrate.
The preparation method of the aluminum-zinc-molybdenum hydrotalcite comprises the following steps: mixing the following components in a mass ratio of 20:4.5:6, dissolving the aluminum material, the zinc material and the molybdenum material in water, adjusting the pH to 9, reacting at 65 ℃, and then roasting at high temperature of 250 ℃ to obtain aluminum-zinc-molybdenum hydrotalcite; the aluminum material is aluminum nitrate, the zinc material is zinc nitrate, and the molybdenum material is molybdenum nitrate.
The dispersant is sodium hexametaphosphate.
Example 1
60 parts of barium carbonate, 90 parts of magnesium, aluminum, barium, water, talcum powder, 1.2 parts of dispersing agent and 120 parts of agate balls are respectively weighed according to the mass ratio of 2:1, and put into a ball milling tank to be ball milled and mixed for 36 hours in a rolling drum to obtain the anion curing agent mixed solution. Weighing 500 parts of deionized water in a reaction kettle, heating the reaction kettle to 60 ℃ and keeping the temperature constant, slowly adding 8 parts of sodium alginate powder at a stirring speed of 670r/min, and continuously stirring for 90 minutes to obtain a sodium alginate solution. And pouring the anion curing agent solution into a beaker, and keeping the beaker for 10min under 250W ultrasonic oscillation to obtain the evenly dispersed anion curing agent mixed solution. According to the mass ratio of the anion curing agent to the sodium alginate of 5.5, 110 parts of anion curing agent mixed solution is added and continuously stirred for 60 minutes to obtain milk white mixed solution. Preparing a sufficient amount of 2% calcium nitrate solution, dripping the milky mixed solution into the calcium nitrate solution, filtering, washing with water, washing with alcohol, and drying at 30 ℃ to obtain the anion curing expansion microcapsule ACM-50. The content of the anionic curing agent is 52.37wt%, and the strength is 2.3N (micro mechanical testing machine).
FIG. 1 shows the anion-cured microcapsules prepared in example 1 (single particles), which are uniformly milky white in shape and spherical in shape.
Figure 2 shows the anionically cured microcapsules (multiparticulates) prepared in example 1.
FIG. 3 shows the screening results of the anionically solidified microcapsules prepared in example 1, from which it can be seen that the microcapsules having a size of 0 to 1.18mm account for 1.4% by mass of the total, the microcapsules having a size of 1.18 to 2.36mm account for 69.7% by mass of the total, and the microcapsules having a size of 2.36 to 4mm account for 28.9% by mass of the total.
Example 2
Respectively weighing 60 parts of barium carbonate, 60 parts of aluminum-zinc-molybdenum hydrotalcite powder, 60 parts of deionized water, 1.2 parts of dispersing agent and 120 parts of agate balls according to the mass ratio of 5:1, and putting the materials into a ball milling tank to perform roller ball milling and mixing for 12 hours to obtain the anion curing agent mixed solution. Weighing 400 parts of deionized water in a reaction kettle, heating the reaction kettle to 70 ℃ and keeping the temperature constant, slowly adding 8 parts of sodium alginate powder at a stirring speed of 670r/min, and continuously stirring for 90 minutes to obtain a sodium alginate solution. And pouring the anion curing agent solution into a beaker, and keeping for 5min under 250W ultrasonic oscillation to obtain the uniformly dispersed anion curing agent mixed solution. And adding 52 parts of the mixed solution of the anionic curing agent according to the mass ratio of the anionic curing agent to the sodium alginate of 3.2, and continuously stirring for 90 minutes to obtain a milky mixed solution. Preparing a sufficient amount of 1% calcium nitrate solution, dripping the milky mixed solution into the calcium nitrate solution, filtering, washing with water, washing with alcohol, and drying at 30 ℃ to obtain the anion curing expansion microcapsule ACZ-30. The content of the anionic curing agent was 30.4wt%, and the strength was 1.9N.
Example 3
Respectively weighing 60 parts of barium carbonate, magnesium-aluminum-barium hydrotalcite and aluminum-zinc-molybdenum hydrotalcite, 120 parts of deionized water, 1.2 parts of dispersing agent and 120 parts of agate balls according to the mass ratio of 2.5. Weighing 1000 parts of deionized water in a reaction kettle, heating the reaction kettle to 55 ℃, keeping the temperature constant, slowly adding 8 parts of sodium alginate powder at the stirring speed of 670r/min, and continuously stirring for 90 minutes to obtain a sodium alginate solution. And pouring the anion curing agent solution into a beaker, and keeping for 5min under 250W ultrasonic oscillation to obtain the uniformly dispersed anion curing agent mixed solution. And adding 108 parts of the mixed solution of the anionic curing agent according to the mass ratio of the anionic curing agent to the sodium alginate of 4.5, and continuously stirring for 30 minutes to obtain a milky mixed solution. Preparing a sufficient calcium lactate solution with the concentration of 1%, dripping the milky mixed solution into the calcium nitrate solution, filtering, washing with water, washing with alcohol, and drying at 30 ℃ to obtain the anion-cured expanded microcapsule ACC-40. The content of the anionic curing agent is 42.55wt%, and the strength is 2.9N.
Example 4
The only difference from example 1 is: the raw material of the anion curing agent is 60 parts of barium carbonate.
And processing to obtain the anion curing expansion microcapsule AB-50. The barium carbonate content was 52.87wt%.
Example 5
The only difference from example 1 is: the anion curing agent is prepared from 60 parts of magnesium-aluminum-barium hydrotalcite powder.
And processing to obtain the anion curing expansion microcapsule AM-50. The content of the magnesium-aluminum-barium hydrotalcite is 51.36wt%.
Comparative example 1
Respectively weighing 60 parts of barium carbonate, 90 parts of magnesium-aluminum-barium water talcum powder, 90 parts of deionized water, 120 parts of agate balls and 120 parts of dispersant-free water talcum powder according to the mass ratio of 2:1, and putting the materials into a ball milling tank to perform roller ball milling and mixing for 36 hours to obtain the anion curing agent mixed solution. Weighing 500 parts of deionized water in a reaction kettle, heating the reaction kettle to 60 ℃ and keeping the temperature constant, slowly adding 8 parts of sodium alginate powder at a stirring speed of 670r/min, and continuously stirring for 90 minutes to obtain a sodium alginate solution. And pouring the anion curing agent solution into a beaker, and keeping the beaker for 10min under 250W ultrasonic oscillation to obtain the uniformly dispersed anion curing agent mixed solution. Adding 108 parts of anion curing agent mixed solution according to the mass ratio of 4.5 of anion curing agent to sodium alginate, and continuously stirring for 30 minutes to obtain mixed solution. Preparing a sufficient amount of 2% calcium chloride solution, dripping the mixed solution into the calcium chloride solution, filtering, washing with water, washing with alcohol and drying at 30 ℃ to obtain the anion curing expansion microcapsule DBL-50.
Fig. 4 shows that the anion-curing microcapsules (single particles) prepared in comparative example 1 are not uniform in color and unstable in shape, unlike the uniform milky white microcapsules prepared in example 1. The result shows that the dispersion of the anionic curing agent is not uniform, the anionic curing effect can be greatly influenced, and meanwhile, the adverse effect is caused on the performance of concrete. In addition, comparative example 1 using calcium chloride solution to cure the microcapsules also resulted in the deactivation of the anionic curing agent in the microcapsules.
Experimental example 1 (Marine concrete Performance test)
The raw materials of the marine concrete used for the tests are as follows:
the raw materials comprise P.I 42.5 cement, river sand fineness modulus 2.8, limestone aggregate (two-stage gradation of 5-10mm and 10-20mm, namely small stone and large stone), a polycarboxylic acid water reducing agent, and anion curing expanding agents ACM-50, ACZ-30, ACC-40, AB-50, AM-50 and DBL-50. The formula of the marine concrete is shown in the following table 1.
TABLE 1 Marine concrete mix proportion (kg/m) 3 )
| Cement | Sand | Small stone | Big stone | Water (W) | Water reducing agent | Anion curing microcapsules |
| 420 | 745 | 447 | 670 | 168 | 2.8 | 12.6 |
The formulation of the blank marine concrete is shown in table 2 below.
TABLE 2 Marine concrete blank mix proportion (kg/m) 3 )
| Cement | Sand | Small stone | Big stone | Water (I) | Water reducing agent |
| 420 | 745 | 447 | 670 | 168 | 2.8 |
The sulfate erosion resistance of the concrete after 120 times of dry and wet cycles and the chloride ion permeability resistance of the concrete after 120 times of dry and wet cycles were measured according to GB50082-2016, and the results are shown in Table 3.
TABLE 3 application effect of anion-curing microcapsules in marine concrete
As can be seen from table 3, the sulfuric acid corrosion resistance coefficients of examples 1 to 4 are all improved compared with the blank sample, which indicates that the content of the anionic curing agent in the microcapsule has a positive effect on the corrosion resistance of the concrete, and the sulfuric acid corrosion resistance coefficient of the concrete is greatly improved by the synergistic effect of the expansion and crack blocking of the microcapsule and the anionic curing function. The permeability coefficient of chloride ions of examples 1, 2, 3 and 5 is reduced, which shows that the microcapsules carrying the hydrotalcite anion curing agent have obvious adsorption effect on chloride ions. It can be known from comparison of examples 1, 4 and 5 that the sulfate curing ability of barium carbonate is superior to that of hydrotalcite, the chloride curing ability is inferior to that of hydrotalcite, and the corrosion resistance of concrete can be comprehensively improved by compounding the barium carbonate and the hydrotalcite into microcapsules. During the concrete mixing process, the microcapsules can absorb certain water and expand to reduce the actual water-cement ratio of the concrete to a certain extent, so that the slump is reduced, but the influence is not obvious. In addition, the self-curing effect of the microcapsules can improve the compressive strength of the concrete. However, the DBL-50 microcapsule of comparative example 1 has no dispersant added, resulting in non-standard shape and uneven distribution of the anionic curing agent, resulting in a certain decrease in both compressive strength and corrosion resistance of the concrete.
The above examples are only for describing the preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.
Claims (10)
1. An anion-curing expansion microcapsule is characterized by comprising a wall material and a core material;
wherein the wall material is calcium alginate, and the core material is an anion curing agent.
2. The anion-curable expanded microcapsule according to claim 1, wherein the content of the core material is 30 to 55% by weight based on the weight of the anion-curable expanded microcapsule.
3. The anion-curing expansion microcapsule according to claim 1 or 2, wherein the anion-curing agent is selected from one or two of barium carbonate and corrosion-inhibiting hydrotalcite;
preferably, the corrosion inhibition hydrotalcite is one or two of aluminum-magnesium-barium hydrotalcite and aluminum-zinc-molybdenum hydrotalcite;
more preferably, the anion curing agent is a mixture of barium carbonate and corrosion-inhibiting hydrotalcite with the mass ratio of 2:1-5:1.
4. A process for the preparation of anionically cured expanded microcapsules according to any of claims 1 to 3, comprising the steps of:
(1) Mixing an anionic curing agent, a dispersing agent and deionized water, and uniformly mixing by adopting a ball milling method to obtain a mixed solution;
(2) Dissolving sodium alginate in deionized water to obtain a wall material aqueous solution;
(3) Mixing the mixed solution with the wall material aqueous solution to obtain a mixture;
(4) And (4) mixing the mixture obtained in the step (3) with a calcium salt solution, filtering, washing and drying to obtain the anion curing expansion microcapsule.
5. The preparation method according to claim 4, wherein in the step (1), the mass ratio of the anionic curing agent to the deionized water is 1:1-1:2;
and/or the dosage of the dispersant is 2wt% of that of the anionic curing agent;
and/or the ball milling method is roller ball milling, the ball-to-material ratio is 2:1, and the ball milling time is 12-36 hours.
6. The preparation method according to claim 4 or 5, wherein the step (2) is specifically: heating the deionized water to 55-70 ℃, slowly adding sodium alginate powder while stirring, and continuously stirring to obtain a wall material aqueous solution;
preferably, the mass ratio of the sodium alginate powder to the deionized water is 1.
7. The method according to any one of claims 4 to 6, wherein the step (3) is specifically: carrying out ultrasonic dispersion on the mixed solution for a period of time, slowly adding the mixed solution after ultrasonic treatment into the wall material aqueous solution, and continuously stirring for a period of time;
preferably, the power of ultrasonic dispersion is 250W, and the time of ultrasonic dispersion is 5-10 minutes;
and/or the mass ratio of the anion curing agent in the mixed solution to the sodium alginate in the wall material water solution is (3.0-6.0): 1, the continuous stirring time is 30-90 minutes.
8. The method according to any one of claims 4 to 7, wherein the step (4) is specifically: dripping the mixture obtained in the step (3) into a calcium salt solution, and filtering, washing and drying to obtain anion curing expansion microcapsules;
and/or in the step (4), the calcium salt solution is one or two of a calcium nitrate solution and a calcium lactate solution, the concentration of the calcium salt solution is 1-2%, and the drying temperature is 30-40 ℃.
9. Use of the anionically curing expanded microcapsules according to any one of claims 1 to 3 or of the anionically curing expanded microcapsules according to any one of claims 4 to 8 in the field of concrete.
10. Use of the anionically solidified expanded microcapsules of any one of claims 1 to 3 or of the anionically solidified expanded microcapsules of any one of claims 4 to 8 in reinforced concrete structures protected against seawater corrosion.
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| CN118063173A (en) * | 2024-04-24 | 2024-05-24 | 浙江大学 | Low-shrinkage seawater concrete with chloride ion curing capability and preparation method thereof |
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| US20020136840A1 (en) * | 2001-03-26 | 2002-09-26 | Hebeisen John C. | Corrosion resistant component and method for fabricating same |
| CN108409178A (en) * | 2018-03-12 | 2018-08-17 | 北京工业大学 | A kind of swelling type microcapsules/cement base self-healing system |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020136840A1 (en) * | 2001-03-26 | 2002-09-26 | Hebeisen John C. | Corrosion resistant component and method for fabricating same |
| CN108409178A (en) * | 2018-03-12 | 2018-08-17 | 北京工业大学 | A kind of swelling type microcapsules/cement base self-healing system |
| CN112777959A (en) * | 2021-01-06 | 2021-05-11 | 北京建筑材料科学研究总院有限公司 | Modified hydrotalcite and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118063173A (en) * | 2024-04-24 | 2024-05-24 | 浙江大学 | Low-shrinkage seawater concrete with chloride ion curing capability and preparation method thereof |
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| CN115417618B (en) | 2023-07-04 |
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