CN108975759B - Internal-modification external-fixation graphene functional self-repairing microcapsule with cellular structure and preparation method thereof - Google Patents
Internal-modification external-fixation graphene functional self-repairing microcapsule with cellular structure and preparation method thereof Download PDFInfo
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Abstract
Aiming at the problems of a self-repairing system in the prior art, the invention provides a graphene functional self-repairing microcapsule with a cellular structure and a preparation method thereof. The internal-modification external-fixation graphene functional self-repairing microcapsule with a cellular structure comprises a capsule wall and a curing agent coated on the capsule wall, wherein graphene is dispersed in the capsule wall; a series of micro-nano microcapsules are dispersed in the curing agent, so that a cellular structure is formed; the micro-nano microcapsule is coated with a repairing agent. The self-repairing microcapsule system has a micro-nano multi-core coating structure, so that the stability of the microcapsule is improved, the probability of contact of a repairing agent and a curing agent is increased, and the repairing efficiency is improved. In addition, the capsule wall of the self-repairing microcapsule system is modified by silane, the unhydrolyzed silane emulsion after the microcapsule is broken can form a hydrophobic film in concrete capillary holes to prevent further diffusion of water, and the hydrolyzed silane emulsion can participate in the synthesis of the wall material to improve the performance of the microcapsule.
Description
Technical Field
The invention belongs to the field of organic composite materials, relates to a self-repairing material, and particularly relates to a graphene functional self-repairing microcapsule with a cellular structure and a preparation method thereof.
Background
With the continuous development of society, the building industry is also rapidly developed, and various high-rise buildings, bridges and roads are dug successively. Concrete is widely used in the construction field due to its excellent properties such as wide source, high compressive strength, easy construction, and high durability. However, due to inherent defects of low tensile strength, large brittleness and the like of concrete, micro cracks are easily generated to reduce the mechanical property of the concrete and influence the durability of the structure under the changes of external load and environmental temperature and humidity in the process of construction and later service. With the change of the load and the passage of time, the cracks gradually expand into cracks and even extend to the surface to cause the cracking of the concrete material. After the through cracks are formed, the concrete is easily corroded and damaged by the external environment and various harmful factors, such as steel bar corrosion, carbonization, chloride ion corrosion, sulfate corrosion and the like, and finally the concrete material is cracked and damaged, so that the durability of the concrete material is seriously influenced, and even the irrecoverable loss of people and property caused by sudden building damage can be caused.
Therefore, the effect of micro-cracks on durability has received increasing attention and importance. In order to prolong the service life of the concrete structure, the cracks need to be repaired in time. The traditional repair methods mainly have two types: surface treatment and grouting. The former is mainly to brush anti-seepage and anti-corrosion organic paint on the surface of the concrete structure, but the organic paint is easy to age, and the coating can be peeled off after a period of time; and the latter can not accurately judge the grouting point and the grouting amount. In addition, the traditional repairing methods not only need a large amount of manpower and material resources, but also have the defects of addressing symptoms and not addressing causes, the crack propagation cannot be inhibited, and tiny cracks existing in the structure cannot be repaired, so that potential safety hazards are left for the construction engineering.
Since 1925 Abrams discovered that the concrete test piece can be self-repaired, the self-repairing concrete technology begins to develop. In recent years, self-repairing technology based on bionics becomes a hot spot of research in the field of concrete self-repairing. The bionic self-repairing method of concrete is developed according to the principle that organisms in the nature secrete certain substances after being injured so as to enable the injured parts to heal in time, is an intelligent repairing method, and does not need to depend on manual assistance. In order to form an intelligent self-healing system in concrete, a carrier containing a repairing agent needs to be embedded into a concrete matrix in advance, when a micro crack is generated on the matrix, the carrier is broken under the action of the tip of the crack, the repairing agent flows out, and the carrier penetrates into the crack to repair the crack in time. The technology carries out targeted repair on concrete cracks, is pre-embedded in the concrete in advance, does not need secondary maintenance, and can greatly reduce the engineering maintenance cost.
Currently, microcapsule self-repair systems mainly include single-wall microcapsule repair systems, single-wall double-microcapsule repair systems, and double-wall microcapsule systems. Single wall microcapsule repair systems suffer from the following problems: (1) the thermochemical stability of the microcapsule is poor; (2) the reaction curing film forming speed is slow, and cracks cannot be effectively filled; (3) the catalyst is expensive and easy to deactivate; (4) the self-repairing system has a narrow application range and can only be limited in a certain base material. The single-wall double-microcapsule system comprises two microcapsules, namely a coating repairing agent and a coating curing agent. The single-wall double-microcapsule system solves the problem of the single-wall microcapsule system to a certain extent, but still has the problems that the repairing agent and the curing agent cannot be contacted simultaneously, the repairing cannot be carried out quickly, the response mechanism to cracks is complex and the like. The double-wall microcapsule system has better stability, and reduces the probability of inactivation of the repairing agent and the curing agent; greatly increasing the contact probability of the repairing agent and the catalyst and avoiding the adverse effect of excessive adding of the repairing agent and the catalyst on the concrete performance.
The invention patent application 201711236671.8 discloses an internal-repair external-fixation polyurea-based double-wall self-repairing microcapsule and a preparation method thereof. The internal repair and external fixation type polyurea-based double-wall self-repairing microcapsule is a double-wall microcapsule system which takes aliphatic isocyanate-amino-terminated polyether polymer as a repairing agent and takes an amino chain extender as a curing agent. The repairing agent and the curing agent are respectively stored in the inner capsule core and the outer capsule core, so that the problem that the contact rate of the repairing agent and the curing agent is low is solved, the repairing agent and the curing agent react quickly, and the cracks are repaired quickly. However, the self-repairing microcapsules with micron-sized structures are easy to break in the process of stirring and vibrating the concrete test block, so that the quantity of the remaining microcapsules in the concrete is small, and the timely response to cracks cannot be realized.
The invention patent application 201710331413.1 discloses a surface modified self-repairing microcapsule and a preparation method thereof. The surface modified self-repairing microcapsule selects a silane coupling agent as a surface treating agent of the microcapsule, and carbon nano tubes are grafted on the surface of the microcapsule through amidation reaction of amino and carboxyl, so that the surface modified self-repairing microcapsule has an antistatic function while the interface performance of the microcapsule and a resin matrix is improved. However, the function of the silane coupling agent is different from that of the silane emulsion, the silane coupling agent is mainly used for bonding organic and inorganic interfaces, and the silane coupling agent emphasizes the function of preventing water molecules from diffusing to form protection on a substrate.
In addition, modifying the wall material of microcapsules to improve their performance has also become a focus of recent attention of researchers; among them, graphene is favored as a functional material having excellent thermodynamic properties. The invention patent application 2017100094514.1 discloses a modified graphene phase change microcapsule and a preparation method thereof, wherein the surface of the modified graphene phase change microcapsule is modified by amino grafting through reduction of graphene by ethylenediamine, so that the capsule wall of the microcapsule is more uniform, and the heat conductivity coefficient of the microcapsule is effectively improved. The invention patent application 201510274641.0 discloses a preparation method of a phase change microcapsule with a graphene modified wall material, which is characterized in that graphene oxide is dispersed mainly through ultrasonic oscillation and is mixed with a wall material prepolymer, so that the thermal conductivity and the mechanical property of the wall material of the phase change microcapsule are modified, and the permeability of the wall material is reduced. However, the graphene oxide used in the above invention is relatively expensive, and the industrial production of the technology is limited to some extent.
Disclosure of Invention
Aiming at the problems of a self-repairing system in the prior art, the invention provides a graphene functional self-repairing microcapsule with a cellular structure and a preparation method thereof. The self-repairing microcapsule system has a micro-nano multi-core coating structure, so that the stability of the microcapsule is improved, the probability of contact of a repairing agent and a curing agent is increased, and the repairing efficiency is improved. In addition, the capsule wall of the self-repairing microcapsule system is modified by silane, the unhydrolyzed silane emulsion after the microcapsule is broken can form a hydrophobic film in concrete capillary holes to prevent further diffusion of water, and the hydrolyzed silane emulsion can participate in the synthesis of the wall material to improve the performance of the microcapsule.
The technical scheme of the invention is as follows:
the internal-repair external-fixation graphene functionalized self-repair microcapsule with a cellular structure comprises a capsule wall and a curing agent coated on the capsule wall, wherein graphene is dispersed in the capsule wall; a series of micro-nano microcapsules are dispersed in the curing agent, so that a cellular structure is formed; the micro-nano microcapsule is coated with a repairing agent. The curing agent is hydroxyl compound emulsion or amino compound emulsion, and the repairing agent is isocyanate emulsion.
The capsule wall of the self-repairing microcapsule is a silane modified capsule wall obtained by reacting a curing agent coated by the self-repairing microcapsule and dispersed with graphene with isocyanate emulsion and silane emulsion outside the self-repairing microcapsule; the capsule wall of the micro-nano microcapsule is obtained by reacting a repairing agent coated by the micro-nano microcapsule with a curing agent outside the micro-nano microcapsule, and the graphene is oxygen plasma modified graphene.
The preparation method of the internal-modification external-fixation graphene functionalized self-repairing microcapsule with the cellular structure comprises the following steps:
(1) preparation of oil-in-water silane emulsion 1:
(1a) weighing a proper amount of silane, an emulsifying agent and a dispersing agent, wherein the weight ratio of the silane to the emulsifying agent to the dispersing agent is 80:1:1-120:5:1, and stirring at the normal temperature at the rotation speed of 2000-4000rpm for 15-30min to obtain an oil phase with uniform dispersion; (1b) weighing a proper amount of emulsifier and water, wherein the weight ratio of the emulsifier to the water is 1:80-1:120, and stirring for 15-30min at the normal temperature under the conditions of 1000-3000rpm to obtain a composite water phase; (1c) gradually dripping the oil phase into the water phase, wherein the weight ratio of the oil phase to the water phase is 1:0.8-1:1.5, and stirring at 5000-10000rpm for 4-5h at 40-60 ℃ to obtain the uniform and stable oil-in-water type composite emulsion, namely the silane emulsion 1.
(2) Preparing micro-nano microcapsule emulsion:
(2a) weighing a proper amount of isocyanate repairing agent, solvent and emulsifier, and stirring at the normal temperature of 3000-7000rpm for 60-100min to obtain isocyanate repairing agent emulsion 2a 1; the weight ratio of the isocyanate repairing agent to the solvent to the emulsifier is 1 (15-20) to 0.08-0.15. (2b) Weighing a proper amount of curing agent, solvent and emulsifier, and stirring for 80-120min at normal temperature under 5000-9000rpm to obtain curing agent emulsion 2b 1; the weight ratio of the curing agent, the solvent and the emulsifier is 1 (10-15) to 0.08-0.18. (2c) Dropwise adding the curing agent emulsion 2b1 into the isocyanate repairing agent emulsion 2a1, stirring at the normal temperature of 2000-6000rpm for 1-2h, and carrying out interface reaction on the isocyanate repairing agent emulsion 2a1 and the curing agent in the curing agent emulsion 2b1 to generate a capsule wall, so as to obtain the repair agent coated micro-nano microcapsule emulsion 2; the weight ratio of the isocyanate repair agent emulsion 2a1 to the curing agent emulsion 2b1 is 1:1-1: 5. In the step, the micro-nano microcapsule emulsion can be obtained only by adopting high-speed rotation; and the droplets of the isocyanate are relatively larger than those of the curing agent emulsion, so that the droplets of the curing agent emulsion are dispersed on the surfaces of the droplets of the isocyanate emulsion to generate an interfacial reaction to form the capsule wall.
(3) Preparing oxygen plasma modified graphene emulsion: placing a proper amount of graphene powder in an oxygen plasma instrument, carrying out vacuum treatment for 3-5min under the condition of 200mTorr-400Torr, and then introducing 3-5ml/min of oxygen for 3-5min to connect carbonyl, hydroxyl or carboxyl functional groups on the surface of the graphene to obtain modified graphene powder; and dissolving the modified graphene powder in a proper amount of solvent, and uniformly stirring at 1000-2000rpm to obtain the modified graphene emulsion 3.
(4) Preparing an internal-repairing external-fixing type graphene functionalized self-repairing microcapsule with a cellular structure:
(4a) weighing a proper amount of isocyanate reagent, emulsifier and solvent, and uniformly stirring at the normal temperature of 3000-6000rpm for 70-100min to obtain isocyanate emulsion 4a 2; the weight ratio of the isocyanate reagent to the emulsifier to the solvent is 1 (15-20) to (0.06-0.12).
(4b) Weighing a proper amount of curing agent, modified graphene emulsion 3, dispersing agent and solvent, and stirring at the normal temperature of 2000-5000rpm for 50-70min to obtain curing agent-graphene dispersion liquid 4b 2; the weight ratio of the curing agent to the modified graphene emulsion 3 to the solvent to the dispersant is 1 (0.4-0.8) to 10-15 (0.06-0.15).
(4c) Firstly, adding a proper amount of silane emulsion 1, micro-nano microcapsule emulsion 2 and an emulsifier into curing agent-graphene dispersion liquid 4b2, and then emulsifying at the normal temperature and the rotation speed of 1500-3500rpm for 1-2h to form a composite solution containing a plurality of micro-nano microcapsule emulsion droplets; then dripping isocyanate emulsion 4a2 into the composite solution, stirring for 2-3h under the temperature condition of 50-70 ℃ and the rotating speed of 1000-2500rpm, and carrying out interface reaction on the isocyanate emulsion 4a2 and curing agent emulsion liquid drops containing a plurality of micro-nano microcapsules to generate a capsule wall; obtaining an internal-modification external-fixation graphene functionalized self-repairing microcapsule emulsion with a cellular structure; the weight ratio of the curing agent-graphene dispersion liquid 4b2 to the silane emulsion 1 to the nano-microcapsule emulsion 2 to the emulsifier to the isocyanate emulsion 4a2 is 1 (0.5-0.8) to (0.15-0.25) to (1-3). The key steps of the application are as follows: firstly, micro-nano microcapsules are dripped, and then a curing agent is emulsified to obtain a composite system, so that emulsified liquid drops containing a plurality of micro-nano microcapsules can be formed.
(4d) And (4) centrifuging, washing and drying the emulsion obtained in the step (4c) to obtain the internal-modification external-fixation graphene functional self-repairing microcapsule with a cellular structure. According to the graphene functional self-repairing microcapsule disclosed by the invention, when the microcapsule is broken, crack repair is completed, and a hydrophobic film can be formed in concrete pores, so that further permeation of water is effectively prevented.
Preferably, in the step (4c), when the isocyanate emulsion 4a2 is added dropwise into the mixed solution, an appropriate amount of acid is added dropwise to adjust the pH value of the system to 4-6; aims to accelerate the hydrolysis of the silane emulsion to generate silicon dioxide to participate in the preparation of the wall material. SiO 22The nano particles participate in the synthesis process of the capsule wall, and the mechanical property and the response capability of the capsule wall and the adhesive force of the microcapsule and the concrete base material are improved to a certain extent.
Wherein the silane is one or more of vinyl triethoxysilane, vinyl trimethoxysilane, ethyl orthosilicate, isobutyl triethoxysilane, trimethylsiloxy silane and octyl triethoxysilane.
The emulsifier is one or more of Op-10, polyvinyl alcohol, span 80, Arabic gum, sodium dodecyl benzene sulfonate and stearyl alcohol polyoxyethylene ether.
The dispersing agent is one or more of polyethylene glycol, potassium citrate, sodium silicate, sodium linoleate and sodium ethylene oxide orthophosphate.
The isocyanate repairing agent is one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, 2, 5-trimethylhexane diisocyanate and tetramethylm-xylylene diisocyanate. The solvent is one or more of ethyl acetate, ethylene glycol dimethyl ether, cyclohexane, cyclopentane, cyclohexanol, toluene, xylene and chlorobenzene.
The curing agent is a hydroxyl compound or an amino compound; the hydroxyl compound is one or more of 1, 4-butanediol, n-butanol, pentanediol, 1, 6-hexanediol, cyclohexanedimethanol, pentaerythritol, polyoxypropylene polyol and polytetrahydrofuran polyol; the amino compound is diethyl toluene diamine, dimethyl sulfur toluene diamine, N ' -dialkyl methyl diphenylamine, cyclohexane diamine, chlorinated MDH, ethylene diamine, 1, 3-diaminopropane, 1, 4-diaminobutane, diethylene amine, pentaethylene hexamine, hexaethylene diamine, tetraethylene pentamine, pentaethylene hexamine, polyether amine D400, polyether amine D230, ethylene diamine or 3,3' -4,4' -diamino-diphenylmethane MOCA.
The self-repairing system of the internal-repairing external-fixing type graphene functional self-repairing microcapsule with the cellular structure is adopted, and the mass fraction of the internal-repairing external-fixing type graphene functional self-repairing microcapsule with the cellular structure in the self-repairing system is 5% -18%; the self-repairing system is self-repairing concrete or a self-repairing coating.
The invention has the beneficial effects that:
(1) according to the internal-repair external-fixation graphene functional self-repairing microcapsule with the cellular structure, a series of micro-nano microcapsules are dispersed in a curing agent coated on the capsule wall, namely the size of the multi-core microcapsule is nano, so that the probability of breakage of the microcapsules in the concrete manufacturing process can be greatly reduced, and the self-repairing efficiency is greatly improved; and the plasma modified graphene is dispersed in the capsule wall, so that the performance of the capsule wall is further enhanced, the adopted modification method is simple and easy to operate, the production cost is greatly reduced, and the industrial production is facilitated.
(2) The internal-repair external-fixation graphene functionalized self-repairing microcapsule is a silane modified microcapsule; therefore, when the microcapsules are broken, the unhydrolyzed silane emulsion can form a hydrophobic film in concrete pores while crack repair is completed, further penetration of water is effectively prevented, and the problem that the corrosion of the concrete is accelerated due to water vapor intrusion in the service process of marine concrete is effectively solved.
(3) In the preparation process of the internally-repaired and externally-fixed graphene functionalized self-repairing microcapsule, SiO generated by hydrolysis of silane emulsion2The nano particles participate in the synthesis process of the capsule wall, and the mechanical property and the response capability of the capsule wall and the adhesive force of the microcapsule and the concrete base material are improved to a certain extent.
(4) Compared with the existing double-wall microcapsule, the internal repair and external fixation type graphene functional self-repair microcapsule with the cellular structure has the advantages that the curing agent and the repair agent react more quickly, so that the repair effect is accelerated, the timely repair of cracks is realized, and more serious consequences and higher repair cost are avoided.
Drawings
FIG. 1 is a schematic structural diagram of an internal-modification external-fixation graphene functionalized self-repairing microcapsule with a cellular structure; wherein A is a curing agent microcapsule, and B is a repairing agent microcapsule.
Fig. 2 is a light mirror image of the internally-modified externally-fixed graphene functionalized self-repairing microcapsule with a cellular structure prepared in example 6.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1:
the preparation method of the internal-modification external-fixation graphene functionalized self-repairing microcapsule with the cellular structure comprises the following steps:
(1) preparation of oil-in-water silane emulsion 1:
(1a) weighing a proper amount of silane, an emulsifying agent and a dispersing agent, wherein the weight ratio of the silane to the emulsifying agent to the dispersing agent is 80:1:1, and stirring at the normal temperature at the rotating speed of 2000rpm for 30min to obtain an oil phase with uniform dispersion; the silane is vinyl triethoxysilane, the emulsifier is Op-10, and the dispersant is polyethylene glycol.
(1b) Weighing a proper amount of emulsifier Op-10 and water, wherein the weight ratio of the emulsifier to the water is 1:110, and stirring at the normal temperature at 1400rpm for 26min to obtain a composite water phase;
(1c) gradually dripping the oil phase into the water phase, wherein the weight ratio of the oil phase to the water phase is 1:1.2, and stirring at 7000rpm at 44 ℃ for 4h to obtain uniform and stable oil-in-water type composite emulsion, namely silane emulsion 1.
(2) Preparing micro-nano microcapsule emulsion:
(2a) weighing a proper amount of isocyanate repairing agent, solvent and emulsifier, and stirring for 80min at 5400rpm at normal temperature to obtain isocyanate repairing agent emulsion 2a 1; the weight ratio of the isocyanate repairing agent to the solvent to the emulsifier is 1:15: 0.08. The isocyanate repairing agent is diphenylmethane diisocyanate, the solvent is ethyl acetate, and the emulsifier is Op-10.
(2b) Weighing a proper amount of curing agent, solvent and emulsifier, and stirring for 80min at the normal temperature at 6600rpm to obtain curing agent emulsion 2b 1; the weight ratio of the curing agent, the solvent and the emulsifier is 1:10: 0.12. The curing agent is a hydroxyl compound, and the hydroxyl compound is 1, 4-butanediol; the solvent is ethyl acetate; the emulsifier is Op-10.
(2c) Dropwise adding the curing agent emulsion 2b1 into the isocyanate repairing agent emulsion 2a1, stirring at 6000rpm at normal temperature for 1h, and carrying out interface reaction on the isocyanate repairing agent emulsion 2a1 and the curing agent in the curing agent emulsion 2b1 to generate a capsule wall, so as to obtain the repair agent-coated micro-nano microcapsule emulsion 2; the weight ratio of the isocyanate repair agent emulsion 2a1 to the curing agent emulsion 2b1 is 1:2. The step must adopt high-speed rotation to obtain micro-nano microcapsule emulsion; and the droplets of isocyanate are relatively larger than the droplets of the curing agent emulsion.
(3) Preparing oxygen plasma modified graphene emulsion: placing a proper amount of graphene powder in an oxygen plasma instrument, carrying out vacuum treatment for 3-5min under the condition of 200mTorr-400Torr, and then introducing 3-5ml/min of oxygen for 3-5min to connect carbonyl, hydroxyl or carboxyl functional groups on the surface of the graphene to obtain modified graphene powder; and dissolving the modified graphene powder in a proper amount of solvent, and uniformly stirring at 1600rpm to obtain the modified graphene emulsion 3.
(4) Preparing an internal-repairing external-fixing type graphene functionalized self-repairing microcapsule with a cellular structure:
(4a) weighing a proper amount of isocyanate reagent, emulsifier and solvent, and uniformly stirring at the normal temperature of 3000rpm for 100min to obtain isocyanate emulsion 4a 2; the weight ratio of the isocyanate reagent to the solvent to the emulsifier is 1:15: 0.06. The isocyanate repairing agent is diphenylmethane diisocyanate; the emulsifier is Op-10; the solvent is ethyl acetate.
(4b) Weighing a proper amount of curing agent, modified graphene emulsion 3, dispersant and solvent, and stirring at the normal temperature of 2200rpm for 60min to obtain curing agent-graphene dispersion liquid 4b 2; the weight ratio of the curing agent to the modified graphene emulsion 3 to the solvent to the dispersant is 1:0.4:10: 0.06. The curing agent is a hydroxyl compound, and the hydroxyl compound is 1, 4-butanediol; the dispersing agent is polyethylene glycol; the solvent is ethyl acetate.
(4c) Firstly, adding a certain amount of silane emulsion 1, micro-nano microcapsule emulsion 2 and an emulsifier into curing agent-graphene dispersion liquid 4b2, and then emulsifying at normal temperature and at the rotating speed of 2200rpm for 1.5h to form a composite solution containing a plurality of micro-nano microcapsule emulsion droplets; the outer layer of the emulsion liquid drop is a curing agent. The emulsifier is Op-10. Then, a proper amount of acid is dripped into the composite solution to ensure that the pH value of the system is 5; then dripping isocyanate emulsion 4a2, stirring for 2h under the temperature condition of 65 ℃ and the rotating speed of 2000rpm, and carrying out interface reaction on the isocyanate emulsion 4a2 and curing agent emulsion liquid drops containing a plurality of micro-nano microcapsules to generate a capsule wall. Obtaining an internal-modification external-fixation graphene functionalized self-repairing microcapsule emulsion with a cellular structure; the weight ratio of the curing agent-graphene dispersion liquid 4b2 to the silane emulsion 1 to the nano-microcapsule emulsion 2 to the emulsifier to the isocyanate emulsion 4a2 is 1:0.5:0.5:0.15: 1. The key steps of the application are as follows: firstly, micro-nano microcapsules are dripped, and then a curing agent is emulsified to obtainA composite system, so that emulsified liquid drops containing a plurality of micro-nano microcapsules can be formed. The purpose of dripping acid into the composite solution is to accelerate the hydrolysis of the silane emulsion to generate silicon dioxide so as to participate in the preparation of the wall material. Modified graphene and SiO2The nano particles participate in the synthesis process of the capsule wall, and the mechanical property and the response capability of the capsule wall and the adhesive force of the microcapsule and the concrete base material are improved to a certain extent.
(4d) And (4) centrifuging, washing and drying the emulsion obtained in the step (4c) to obtain the internal-modification external-fixation graphene functional self-repairing microcapsule with a cellular structure. When the microcapsule is broken, the crack can be repaired, and a hydrophobic film can be formed in concrete pores, so that the further permeation of water is effectively prevented.
The self-repairing concrete adopting the internal-repairing external-fixing type graphene functional self-repairing microcapsule with the cellular structure has the advantages that the mass fraction of the self-repairing microcapsule in the self-repairing concrete is 10%.
Example 2:
different from the embodiment 1, the preparation method of the internally-modified externally-fixed graphene functionalized self-repairing microcapsule with the cellular structure comprises the following steps:
(1) preparation of oil-in-water silane emulsion 1:
(1a) weighing a proper amount of silane, an emulsifying agent and a dispersing agent, wherein the weight ratio of the silane to the emulsifying agent to the dispersing agent is 100:2:1, and stirring at the normal temperature at the rotating speed of 2400rpm for 26min to obtain an oil phase which is uniformly dispersed; the silane is vinyl trimethoxy silane, the emulsifier is polyvinyl alcohol, and the dispersing agent is potassium citrate.
(1b) Weighing appropriate amount of emulsifier polyvinyl alcohol and water, wherein the weight ratio of the emulsifier to the water is 1:120, and stirring at 1800rpm for 22min at normal temperature to obtain a composite water phase;
(1c) gradually dripping the oil phase into the water phase, wherein the weight ratio of the oil phase to the water phase is 1:1.4, and stirring at 8000rpm at 48 ℃ for 4h to obtain uniform and stable oil-in-water type composite emulsion, namely silane emulsion 1.
(2) Preparing micro-nano microcapsule emulsion:
(2a) weighing a proper amount of isocyanate repairing agent, solvent and emulsifier, and stirring for 90min at 6200rpm at normal temperature to obtain isocyanate repairing agent emulsion 2a 1; the weight ratio of the isocyanate repairing agent to the solvent to the emulsifier is 1:16: 0.08. The isocyanate repairing agent is toluene diisocyanate, the solvent is ethylene glycol dimethyl ether, and the emulsifier is polyvinyl alcohol.
(2b) Weighing a proper amount of curing agent, solvent and emulsifier, and stirring at 9000rpm for 85min at normal temperature to obtain curing agent emulsion 2b 1; the weight ratio of the curing agent to the solvent to the emulsifier is 1:10: 0.15. The curing agent is a hydroxyl compound, and the hydroxyl compound is a mixture of n-butyl alcohol and pentanediol; the solvent is ethylene glycol dimethyl ether, and the emulsifier is span 80.
(2c) Dropwise adding the curing agent emulsion 2b1 into the isocyanate repairing agent emulsion 2a1, stirring at the normal temperature of 2000rpm for 2h, and carrying out interface reaction on the isocyanate repairing agent emulsion 2a1 and the curing agent in the curing agent emulsion 2b1 to generate a capsule wall, so as to obtain the repair agent-coated micro-nano microcapsule emulsion 2; the weight ratio of the isocyanate repair agent emulsion 2a1 to the curing agent emulsion 2b1 is 1: 3.
(3) Preparing oxygen plasma modified graphene emulsion: and (3) dissolving the modified graphene powder in a proper amount of solvent, and uniformly stirring at 1800rpm to obtain a modified graphene emulsion 3.
(4) Preparing an internal-repairing external-fixing type graphene functionalized self-repairing microcapsule with a cellular structure:
(4a) weighing a proper amount of isocyanate reagent, emulsifier and solvent, and uniformly stirring at 3600rpm at normal temperature for 95min to obtain isocyanate emulsion 4a 2; the weight ratio of the isocyanate reagent, the solvent and the emulsifier is 1:18: 0.06. The isocyanate repairing agent is isophorone diisocyanate, the emulsifier is polyvinyl alcohol, and the solvent is cyclohexane.
(4b) Weighing a proper amount of curing agent, modified graphene emulsion 3, dispersant and solvent, and stirring at 2800rpm for 65min at normal temperature to obtain curing agent-graphene dispersion liquid 4b 2; the weight ratio of the curing agent to the modified graphene emulsion 3 to the solvent to the dispersant is 1:0.5:10: 0.09. The curing agent is a hydroxyl compound, and the hydroxyl compound is n-butyl alcohol; the dispersing agent is sodium silicate, and the solvent is cyclohexane and cyclopentane.
(4c) Firstly, adding a certain amount of silane emulsion 1, micro-nano microcapsule emulsion 2 and an emulsifier into curing agent-graphene dispersion liquid 4b2, and then emulsifying for 1.5h at the normal temperature and the rotation speed of 2600rpm to form a composite solution containing a plurality of micro-nano microcapsule emulsion droplets; the outer layer of the emulsion liquid drop is a curing agent. The emulsifier is span 80. Then, a proper amount of acid is dripped into the composite solution to ensure that the pH value of the system is 5.5; dripping isocyanate emulsion 4a2, stirring for 2.5h at the temperature of 70 ℃ and the rotating speed of 2300rpm, and carrying out interfacial reaction on the isocyanate emulsion 4a2 and curing agent emulsion droplets containing a plurality of micro-nano microcapsules to generate capsule walls. Obtaining an internal-modification external-fixation graphene functionalized self-repairing microcapsule emulsion with a cellular structure; the weight ratio of the curing agent-graphene dispersion liquid 4b2 to the silane emulsion 1 to the nano-microcapsule emulsion 2 to the emulsifier to the isocyanate emulsion 4a2 is 1:0.65:0.5:0.18: 1.
(4d) And (4) centrifuging, washing and drying the emulsion obtained in the step (4c) to obtain the internal-modification external-fixation graphene functional self-repairing microcapsule with a cellular structure.
The self-repairing coating of the internal-repairing external-fixing type graphene functionalized self-repairing microcapsule with the cellular structure is adopted, and the mass percentage of the self-repairing microcapsule in the self-repairing coating is 15%.
Example 3:
different from the embodiment 1, the preparation method of the internally-modified externally-fixed graphene functionalized self-repairing microcapsule with the cellular structure comprises the following steps:
(1) preparation of oil-in-water silane emulsion 1:
(1a) weighing a proper amount of silane, an emulsifier and a dispersant, wherein the weight ratio of the silane to the emulsifier to the dispersant is 120:2.5:1, and stirring at the normal temperature at the rotating speed of 2800rpm for 22min to obtain an oil phase with uniform dispersion; the silane is isobutyl triethoxy silane, the emulsifier is sodium dodecyl benzene sulfonate, and the dispersant is sodium linoleate. .
(1b) Weighing a proper amount of emulsifier sodium dodecyl benzene sulfonate and water, wherein the weight ratio of the emulsifier to the water is 1:105, and stirring for 20min at the normal temperature under 2200rpm to obtain a composite water phase;
(1c) gradually dripping the oil phase into the water phase, wherein the weight ratio of the oil phase to the water phase is 1:1.5, and stirring at 9000rpm at 52 ℃ for 4.5h to obtain uniform and stable oil-in-water type composite emulsion, namely silane emulsion 1.
(2) Preparing micro-nano microcapsule emulsion:
(2a) weighing a proper amount of isocyanate repairing agent, solvent and emulsifier, and stirring at 7000rpm at normal temperature for 100min to obtain isocyanate repairing agent emulsion 2a 1; the weight ratio of the isocyanate repairing agent to the solvent to the emulsifier is 1:18: 0.08. The isocyanate repairing agent is 1, 6-hexamethylene diisocyanate, the solvent is cyclohexanol, and the emulsifier is sodium dodecyl benzene sulfonate.
(2b) Weighing a proper amount of curing agent, solvent and emulsifier, and stirring at the normal temperature at 8500rpm for 120min to obtain curing agent emulsion 2b 1; the weight ratio of the curing agent, the solvent and the emulsifier is 1:15: 0.18. The curing agent is a hydroxyl compound, and the hydroxyl compound is pentaerythritol; the amino compound is cyclohexane diamine, the solvent is cyclopentane, and the emulsifier is Arabic gum.
(2c) Dropwise adding the curing agent emulsion 2b1 into the isocyanate repairing agent emulsion 2a1, stirring at 2800rpm at normal temperature for 2h, and carrying out interface reaction on the isocyanate repairing agent emulsion 2a1 and the curing agent in the curing agent emulsion 2b1 to generate a capsule wall, so as to obtain the repair agent-coated micro-nano microcapsule emulsion 2; the weight ratio of the isocyanate repair agent emulsion 2a1 to the curing agent emulsion 2b1 is 1: 4.
(3) Preparing oxygen plasma modified graphene emulsion: and dissolving the modified graphene powder in a proper amount of solvent, and uniformly stirring at 2000rpm to obtain a modified graphene emulsion 3.
(4) Preparing an internal-repairing external-fixing type graphene functionalized self-repairing microcapsule with a cellular structure:
(4a) weighing a proper amount of isocyanate reagent, emulsifier and solvent, and uniformly stirring for 90min at the normal temperature of 4200rpm to obtain isocyanate emulsion 4a 2; the weight ratio of the isocyanate reagent, the solvent and the emulsifier is 1:20: 0.06. The isocyanate repairing agent is 1, 6-hexamethylene diisocyanate, the emulsifying agent is Arabic gum, and the solvent is cyclohexane.
(4b) Weighing a proper amount of curing agent, modified graphene emulsion 3, dispersant and solvent, and stirring at 3400rpm for 70min at normal temperature to obtain curing agent-graphene dispersion liquid 4b 2; the weight ratio of the curing agent to the modified graphene emulsion 3 to the solvent to the dispersant is 1:0.6:10: 0.12. The amino compound of the curing agent is diethyl toluene diamine; the dispersing agent is sodium linoleate, and the solvent is cyclohexane.
(4c) Firstly, adding a certain amount of silane emulsion 1, micro-nano microcapsule emulsion 2 and an emulsifier into curing agent-graphene dispersion liquid 4b2, and then emulsifying for 1h at the normal temperature and at the rotating speed of 3000rpm to form a composite solution containing a plurality of emulsified liquid drops of micro-nano microcapsules; the outer layer of the emulsion liquid drop is a curing agent. The emulsifier is sodium dodecyl benzene sulfonate. Then, a proper amount of acid is dripped into the composite solution to ensure that the pH value of the system is 6; then, the isocyanate emulsion 4a2 is added dropwise, and the mixture is stirred for 2.5 hours under the temperature condition of 50 ℃ and the rotating speed of 2500rpm, so that the isocyanate emulsion 4a2 and the curing agent emulsion liquid drop containing a plurality of micro-nano microcapsules are subjected to interfacial reaction to generate the capsule wall. Obtaining an internal-modification external-fixation graphene functionalized self-repairing microcapsule emulsion with a cellular structure; the weight ratio of the curing agent-graphene dispersion liquid 4b2 to the silane emulsion 1 to the nano-microcapsule emulsion 2 to the emulsifier to the isocyanate emulsion 4a2 is 1:0.8:0.5:0.18: 1.
(4d) And (4) centrifuging, washing and drying the emulsion obtained in the step (4c) to obtain the internal-modification external-fixation graphene functional self-repairing microcapsule with a cellular structure.
The self-repairing concrete adopting the internal-repairing external-fixing type graphene functional self-repairing microcapsule with the cellular structure has the advantages that the mass fraction of the self-repairing microcapsule in the self-repairing concrete is 18%.
Example 4:
different from the embodiment 1, the preparation method of the internally-modified externally-fixed graphene functionalized self-repairing microcapsule with the cellular structure comprises the following steps:
(1) preparation of oil-in-water silane emulsion 1:
(1a) weighing a proper amount of silane, an emulsifying agent and a dispersing agent, wherein the weight ratio of the silane to the emulsifying agent to the dispersing agent is 90:3:1, and stirring for 20min at the normal temperature at the rotating speed of 3200rpm to obtain an oil phase with uniform dispersion; the silane is trimethylsiloxy silane, the emulsifier is octadecyl alcohol polyoxyethylene ether, and the dispersant is sodium silicate.
(1b) Weighing a proper amount of emulsifier octadecanol-based polyoxyethylene ether and water, wherein the weight ratio of the emulsifier to the water is 1:80, and stirring for 18min at the normal temperature and 2600rpm to obtain a composite water phase;
(1c) gradually dripping the oil phase into the water phase, wherein the weight ratio of the oil phase to the water phase is 1:1.1, stirring at 56 ℃ and 10000rpm for 4.5h to obtain uniform and stable oil-in-water type composite emulsion, namely silane emulsion 1.
(2) Preparing micro-nano microcapsule emulsion:
(2a) weighing a proper amount of isocyanate repairing agent, solvent and emulsifier, and stirring at the normal temperature of 3000rpm for 60min to obtain isocyanate repairing agent emulsion 2a 1; the weight ratio of the isocyanate repairing agent to the solvent to the emulsifier is 1:20: 0.15. The isocyanate repairing agent is 1, 6-hexamethylene diisocyanate, the solvent is toluene, and the emulsifier is octadecyl alcohol polyoxyethylene ether.
(2b) Weighing a proper amount of curing agent, solvent and emulsifier, and stirring at the normal temperature of 5800rpm for 110min to obtain curing agent emulsion 2b 1; the weight ratio of the curing agent, the solvent and the emulsifier is 1:10: 0.08. The curing agent is an amino compound, and the amino compound is ethylenediamine; the solvent is dimethylbenzene, and the emulsifier is octadecyl alcohol polyoxyethylene ether.
(2c) Dropwise adding the curing agent emulsion 2b1 into the isocyanate repairing agent emulsion 2a1, stirring at 3600rpm at normal temperature for 1.5h, and carrying out interface reaction on the isocyanate repairing agent emulsion 2a1 and the curing agent in the curing agent emulsion 2b1 to generate a capsule wall, so as to obtain the repair agent-coated micro-nano microcapsule emulsion 2; the weight ratio of the isocyanate repair agent emulsion 2a1 to the curing agent emulsion 2b1 is 1: 5.
(3) Preparing oxygen plasma modified graphene emulsion: and dissolving the modified graphene powder in a proper amount of solvent, and uniformly stirring at 1000rpm to obtain a modified graphene emulsion 3.
(4) Preparing an internal-repairing external-fixing type graphene functionalized self-repairing microcapsule with a cellular structure:
(4a) weighing a proper amount of isocyanate reagent, emulsifier and solvent, and uniformly stirring for 85min at the normal temperature of 4800rpm to obtain isocyanate emulsion 4a 2; the weight ratio of the isocyanate reagent, the solvent and the emulsifier is 1:15: 0.08. The isocyanate repairing agent is 1, 6-hexamethylene diisocyanate, the emulsifying agent is Arabic gum, and the solvent is cyclohexanol.
(4b) Weighing a proper amount of curing agent, modified graphene emulsion 3, dispersant and solvent, and stirring at the normal temperature at 4000rpm for 60min to obtain curing agent-graphene dispersion liquid 4b 2; the weight ratio of the curing agent to the modified graphene emulsion 3 to the solvent to the dispersant is 1:0.7:10: 0.15. The curing agent is an amino compound, the amino compound is cyclohexane diamine, the dispersing agent is sodium silicate, and the solvent is chlorobenzene.
(4c) Firstly, adding a certain amount of silane emulsion 1, micro-nano microcapsule emulsion 2 and an emulsifier into curing agent-graphene dispersion liquid 4b2, and then emulsifying for 1h at the normal temperature and the rotation speed of 3500rpm to form a composite solution containing a plurality of emulsified liquid drops of micro-nano microcapsules; the outer layer of the emulsion liquid drop is a curing agent. The emulsifier is span 80. Then, a proper amount of acid is dripped into the composite solution to ensure that the pH value of the system is 4; then dripping isocyanate emulsion 4a2, stirring for 3h under the temperature condition of 55 ℃ and the rotating speed of 1000rpm, and carrying out interface reaction on the isocyanate emulsion 4a2 and curing agent emulsion liquid drops containing a plurality of micro-nano microcapsules to generate a capsule wall. Obtaining an internal-modification external-fixation graphene functionalized self-repairing microcapsule emulsion with a cellular structure; the weight ratio of the curing agent-graphene dispersion liquid 4b2 to the silane emulsion 1 to the nano-microcapsule emulsion 2 to the emulsifier to the isocyanate emulsion 4a2 is 1:0.5:0.65:0.25: 2.
(4d) And (4) centrifuging, washing and drying the emulsion obtained in the step (4c) to obtain the internal-modification external-fixation graphene functional self-repairing microcapsule with a cellular structure.
The self-repairing coating of the internal-repairing external-fixing type graphene functionalized self-repairing microcapsule with the cellular structure is adopted, and the mass percentage of the self-repairing microcapsule in the self-repairing coating is 10%.
Example 5:
different from the embodiment 1, the preparation method of the internally-modified externally-fixed graphene functionalized self-repairing microcapsule with the cellular structure comprises the following steps:
(1) preparation of oil-in-water silane emulsion 1:
(1a) weighing a proper amount of silane, an emulsifier and a dispersant, wherein the weight ratio of the silane to the emulsifier to the dispersant is 110:4:1, and stirring at the normal temperature at the rotating speed of 3600rpm for 18min to obtain an oil phase with uniform dispersion; the silane is trimethylsiloxy silane, the emulsifier is octadecyl alcohol polyoxyethylene ether, and the dispersant is sodium silicate.
(1b) Weighing a proper amount of emulsifier octadecanol-based polyoxyethylene ether and water, wherein the weight ratio of the emulsifier to the water is 1:90, and stirring at the normal temperature at 3000rpm for 15min to obtain a composite water phase;
(1c) gradually dripping the oil phase into the water phase, wherein the weight ratio of the oil phase to the water phase is 1:0.8, and stirring at 5000rpm at 60 ℃ for 5h to obtain uniform and stable oil-in-water type composite emulsion, namely silane emulsion 1.
(2) Preparing micro-nano microcapsule emulsion:
(2a) weighing a proper amount of isocyanate repairing agent, solvent and emulsifier, and stirring at 3800rpm for 70min at normal temperature to obtain isocyanate repairing agent emulsion 2a 1; the weight ratio of the isocyanate repairing agent to the solvent to the emulsifier is 1:20: 0.12. The isocyanate repairing agent is tetramethylm-xylylene diisocyanate, the solvent is chlorobenzene, and the emulsifier is octadecyl alcohol polyoxyethylene ether.
(2b) Weighing a proper amount of curing agent, solvent and emulsifier, and stirring at the normal temperature of 5000rpm for 100min to obtain curing agent emulsion 2b 1; the weight ratio of the curing agent, the solvent and the emulsifier is 1:12: 0.18. The curing agent is an amino compound, the amino compound is tetraethylenepentamine, the solvent is cyclohexane, and the emulsifier is Arabic gum.
(2c) Dropwise adding the curing agent emulsion 2b1 into the isocyanate repairing agent emulsion 2a1, stirring at the normal temperature of 4200rpm for 1.5h, and carrying out interface reaction on the isocyanate repairing agent emulsion 2a1 and the curing agent in the curing agent emulsion 2b1 to generate a capsule wall, so as to obtain the repair agent-coated micro-nano microcapsule emulsion 2; the weight ratio of the isocyanate repair agent emulsion 2a1 to the curing agent emulsion 2b1 is 1:1.
(3) Preparing oxygen plasma modified graphene emulsion: and dissolving the modified graphene powder in a proper amount of solvent, and uniformly stirring at 1200rpm to obtain a modified graphene emulsion 3.
(4) Preparing an internal-repairing external-fixing type graphene functionalized self-repairing microcapsule with a cellular structure:
(4a) weighing a proper amount of isocyanate reagent, emulsifier and solvent, and uniformly stirring for 80min at the normal temperature at 5400rpm to obtain isocyanate emulsion 4a 2; the weight ratio of the isocyanate reagent, the solvent and the emulsifier is 1:15: 0.10. The isocyanate repairing agent is isophorone diisocyanate, the emulsifier is sodium dodecyl benzene sulfonate, and the solvent is cyclohexane.
(4b) Weighing a proper amount of curing agent, modified graphene emulsion 3, dispersant and solvent, and stirring at the normal temperature and 5000rpm for 50min to obtain curing agent-graphene dispersion liquid 4b 2; the weight ratio of the curing agent to the modified graphene emulsion 3 to the solvent to the dispersant is 1:0.8:12: 0.10. The curing agent is an amino compound, the amino compound is diethyleneamine, the dispersing agent is sodium silicate, and the solvent is cyclohexanol.
(4c) Firstly, adding a certain amount of silane emulsion 1, micro-nano microcapsule emulsion 2 and an emulsifier into curing agent-graphene dispersion liquid 4b2, and then emulsifying for 2 hours at normal temperature and at the rotating speed of 1500rpm to form a composite solution containing a plurality of micro-nano microcapsule emulsion droplets; the outer layer of the emulsion liquid drop is a curing agent. The emulsifier is sodium dodecyl benzene sulfonate. Then, a proper amount of acid is dripped into the composite solution to ensure that the pH value of the system is 4.5; then dripping isocyanate emulsion 4a2, stirring for 3h under the temperature condition of 60 ℃ and the rotating speed of 1300rpm, and carrying out interface reaction on the isocyanate emulsion 4a2 and curing agent emulsion liquid drops containing a plurality of micro-nano microcapsules to generate a capsule wall. Obtaining an internal-modification external-fixation graphene functionalized self-repairing microcapsule emulsion with a cellular structure; the weight ratio of the curing agent-graphene dispersion liquid 4b2 to the silane emulsion 1 to the nano-microcapsule emulsion 2 to the emulsifier to the isocyanate emulsion 4a2 is 1:0.5:0.8:0.15: 1.
(4d) And (4) centrifuging, washing and drying the emulsion obtained in the step (4c) to obtain the internal-modification external-fixation graphene functional self-repairing microcapsule with a cellular structure.
The self-repairing concrete adopting the internal-repairing external-fixing type graphene functional self-repairing microcapsule with the cellular structure has the advantages that the mass fraction of the self-repairing microcapsule in the self-repairing concrete is 15%.
Example 6:
different from the embodiment 1, the preparation method of the internally-modified externally-fixed graphene functionalized self-repairing microcapsule with the cellular structure comprises the following steps:
(1) preparation of oil-in-water silane emulsion 1:
(1a) weighing a proper amount of silane, an emulsifier and a dispersant, wherein the weight ratio of the silane to the emulsifier to the dispersant is 100:5:1, and stirring at the normal temperature at the rotation speed of 4000rpm for 15min to obtain an oil phase with uniform dispersion; the silane is octyl triethoxysilane, the emulsifier is octadecyl alcohol polyoxyethylene ether, and the dispersant is sodium orthophosphate polyoxyethylene ether.
(1b) Weighing a proper amount of emulsifier octadecanol polyoxyethylene ether and water, wherein the weight ratio of the emulsifier to the water is 1:100, and stirring the mixture for 30min at the normal temperature and 1000rpm to obtain a composite water phase;
(1c) gradually dripping the oil phase into the water phase, wherein the weight ratio of the oil phase to the water phase is 1:0.8, and stirring at 6000rpm at 50 ℃ for 5h to obtain uniform and stable oil-in-water type composite emulsion, namely silane emulsion 1.
(2) Preparing micro-nano microcapsule emulsion:
(2a) weighing a proper amount of isocyanate repairing agent, solvent and emulsifier, and stirring for 75min at room temperature at 4600rpm to obtain isocyanate repairing agent emulsion 2a 1; the weight ratio of the isocyanate repairing agent to the solvent to the emulsifier is 1:15: 0.10. The isocyanate repairing agent is 2, 2, 5-trimethylhexane diisocyanate, the solvent is xylene, and the emulsifier is sodium dodecyl benzene sulfonate.
(2b) Weighing a proper amount of curing agent, solvent and emulsifier, and stirring for 90min at the normal temperature at 7200rpm to obtain curing agent emulsion 2b 1; the weight ratio of the curing agent, the solvent and the emulsifier is 1:15: 0.08. The curing agent is a hydroxyl compound, the hydroxyl compound is polyoxypropylene polyol, the solvent is toluene, and the emulsifying agent is Arabic gum.
(2c) Dropwise adding the curing agent emulsion 2b1 into the isocyanate repairing agent emulsion 2a1, stirring at the normal temperature and 5000rpm for 1h, and carrying out interface reaction on the isocyanate repairing agent emulsion 2a1 and the curing agent in the curing agent emulsion 2b1 to generate a capsule wall, so as to obtain the repair agent-coated micro-nano microcapsule emulsion 2; the weight ratio of the isocyanate repair agent emulsion 2a1 to the curing agent emulsion 2b1 is 1: 2.5. The step must adopt high-speed rotation to obtain micro-nano microcapsule emulsion; and the droplets of isocyanate are relatively larger than the droplets of the curing agent emulsion.
(3) Preparing oxygen plasma modified graphene emulsion: and dissolving the modified graphene powder in a proper amount of solvent, and uniformly stirring at 1400rpm to obtain a modified graphene emulsion 3.
(4) Preparing an internal-repairing external-fixing type graphene functionalized self-repairing microcapsule with a cellular structure:
(4a) weighing a proper amount of isocyanate reagent, emulsifier and solvent, and uniformly stirring at the normal temperature of 6000rpm for 70min to obtain isocyanate emulsion 4a 2; the weight ratio of the isocyanate reagent, the solvent and the emulsifier is 1:20: 0.12. The isocyanate repairing agent is toluene diisocyanate, the emulsifying agent is Arabic gum, and the solvent is cyclohexanol.
(4b) Weighing a proper amount of curing agent, modified graphene emulsion 3, dispersant and solvent, and stirring at the normal temperature of 2000rpm for 55min to obtain curing agent-graphene dispersion liquid 4b 2; the weight ratio of the curing agent to the modified graphene emulsion 3 to the solvent to the dispersant is 1:0.8:15: 0.15. The curing agent is a hydroxyl compound, the hydroxyl compound is polyoxypropylene polyol, the dispersing agent is sodium silicate, and the solvent is cyclohexane.
(4c) Firstly, adding a certain amount of silane emulsion 1, micro-nano microcapsule emulsion 2 and an emulsifier into curing agent-graphene dispersion liquid 4b2, and then emulsifying for 2 hours at normal temperature and at the rotating speed of 1800rpm to form a composite solution containing a plurality of emulsified liquid drops of micro-nano microcapsules; the outer layer of the emulsion liquid drop is a curing agent. The emulsifier is sodium dodecyl benzene sulfonate. Then, a proper amount of acid is dripped into the composite solution to ensure that the pH value of the system is 5; then dripping isocyanate emulsion 4a2, stirring for 2h under the temperature condition of 65 ℃ and the rotating speed of 1600rpm, and carrying out interface reaction on the isocyanate emulsion 4a2 and curing agent emulsion liquid drops containing a plurality of micro-nano microcapsules to generate a capsule wall. Obtaining an internal-modification external-fixation graphene functionalized self-repairing microcapsule emulsion with a cellular structure; the weight ratio of the curing agent-graphene dispersion liquid 4b2 to the silane emulsion 1 to the nano-microcapsule emulsion 2 to the emulsifier to the isocyanate emulsion 4a2 is 1:0.8:0.8:0.25: 3.
(4d) And (4) centrifuging, washing and drying the emulsion obtained in the step (4c) to obtain the internal-modification external-fixation graphene functional self-repairing microcapsule with a cellular structure.
The self-repairing coating of the internal-repairing external-fixing type graphene functionalized self-repairing microcapsule with the cellular structure is adopted, and the mass percentage of the self-repairing microcapsule in the self-repairing coating is 18%.
Table 1 micro-morphological characterization of the microcapsules prepared in examples 1-6
Table 2 characterization of mechanical properties of the microcapsules prepared in examples 1 to 6
As is apparent from the characterization results in tables 1 and 2, the microcapsules prepared in examples 1 to 6 had a particle size of 10 to 180 μm, a tensile strength of 9.24 to 10.93MPa, an elongation at break of 217.75 to 231.62%, and a Shore hardness (A) of 54 to 62.
As shown in FIG. 2, the microcapsules of the present invention have a cellular structure, i.e., a series of micro-nano microcapsules are dispersed in the curing agent coated on the capsule wall, such that the probability of the microcapsules breaking during the concrete manufacturing process can be substantially reduced, and the self-repairing efficiency can be substantially improved.
Example 7: strength performance detection after self-repairing system repair
The microcapsules prepared in examples 1,3 and 5 were incorporated into cement for the preparation of self-healing concrete. After 28 days of maintenance, taking a group of self-repairing concrete (each group contains 3 test blocks) to test the initial compressive strength; and (3) lightly pressing the self-repairing concrete by using a pressure testing machine to generate cracks in the self-repairing concrete by using another group (each group contains 3 test blocks), and testing the compressive strength of the self-repairing concrete after half a month. The microcapsules prepared in examples 2, 4 and 6 were incorporated into coatings for the preparation of self-healing coatings. And (3) taking one group (each group contains 3 coatings) of self-repairing coatings to test the initial tensile strength, taking the other group (each group contains 3 coatings) of self-repairing coatings to stretch the self-repairing soil layer by adopting a tensile testing machine to generate cracks in the self-repairing soil layer, and testing the tensile strength of the group of self-repairing coatings after half a month to obtain the data shown in the table 3.
Table 3 determination of strength after repair of self-healing systems of microcapsules prepared in examples 1-6
As can be seen from Table 3, the compressive strength of the repaired concrete is 45.97-46.73MPa, and the average value is 46.38 MPa; compared with the prior art, the repair efficiency is improved by 10.48 percent. The compressive strength of the repaired epoxy coating is 16.78-18.66MPa, and the average value is 17.76 MPa; compared with the prior art, the repair efficiency is improved by 13.72 percent.
Example 8: determination of Water absorption after repair of self-healing System
The microcapsules prepared in examples 1-6 were incorporated into cement to prepare self-healing concrete (microcapsule content 8%) while preparing a set of blank concrete test blocks. After curing for 28 days, the self-repairing concrete is lightly pressed by a pressure tester to generate cracks inside the self-repairing concrete, and after half a month, the self-repairing concrete is dried to constant weight by an oven, and then the water absorption of the group of self-repairing concrete is tested. The weight gain method is used for testing the water absorption increment of the sample at 2, 4, 8, 12 and 24 hours.
Table 4 examples 1-6 preparation of water absorption test after repair of microcapsule self-healing systems
As can be seen from Table 4, the water absorption capacity of the repaired concrete for 24 hours is 577.3-592.2g/m3Compared with a blank sample, the reduction is 5.3 to 7.7 percent.
In conclusion, the internal-repair external-fixation type self-repairing microcapsule with the cellular structure has good morphology in the aspect of microscopic morphology, and the particle size is mainly distributed between 30 and 200 mu m; mechanical tests show that the cured microcapsule is an elastic material (the elongation at break is 217.75-231.62%) with certain strength (the tensile strength is 9.24-10.93MPa) and hardness (Shore A54-62). This is due to the SiO produced by hydrolysis of the silane emulsion2The nano particles participate in the synthesis process of the capsule wall, and the mechanical property of the capsule wall is improved to a certain extent. In addition, plasma modified graphene is dispersed in the capsule wall, so that the performance of the capsule wall is further enhanced.
The internal repair and external fixation type self-repairing microcapsules with cell structures are doped into concrete and an epoxy coating, and a pre-pressing crack experiment shows that the microcapsules have a certain repairing effect on cracks, the compressive strength improvement rate of the repaired concrete is 10.48%, and the tensile strength improvement rate of the repaired epoxy coating is 13.72%. The multi-core microcapsule has the size of nanometer level, so that the probability of the microcapsule breaking in the concrete making process is greatly reduced, and the self-repairing efficiency is greatly improved.
The internal repair and external fixation type self-repairing microcapsules with cellular structures are doped into concrete, and a water absorption test shows that the microcapsules have a certain repairing effect on cracks, and the water absorption reduction rate of the repaired concrete is 5.3-7.7%. When the microcapsule is broken, the unhydrolyzed silane emulsion can form a hydrophobic film in concrete pores while the crack is repaired, so that the further permeation of water is effectively prevented.
Claims (8)
1. The preparation method of the internal-modification external-fixation graphene functionalized self-repairing microcapsule with the cellular structure is characterized by comprising the following steps of: the method comprises the following steps:
(1) preparation of oil-in-water silane emulsion 1: (1a) weighing a proper amount of silane, an emulsifying agent and a dispersing agent, wherein the weight ratio of the silane to the emulsifying agent to the dispersing agent is 80:1:1-120:5:1, and stirring at the normal temperature at the rotation speed of 2000-4000rpm for 15-30min to obtain an oil phase with uniform dispersion; (1b) weighing a proper amount of emulsifier and water, wherein the weight ratio of the emulsifier to the water is 1:80-1:120, and stirring for 15-30min at the normal temperature under the conditions of 1000-3000rpm to obtain a composite water phase; (1c) gradually dripping the oil phase into the water phase, wherein the weight ratio of the oil phase to the water phase is 1:0.8-1:1.5, and stirring at 5000-10000rpm at 40-60 ℃ for 4-5h to obtain uniform and stable oil-in-water type composite emulsion, namely silane emulsion 1;
(2) preparing a nano microcapsule emulsion: (2a) weighing a proper amount of isocyanate repairing agent, solvent and emulsifier, and stirring at the normal temperature of 3000-7000rpm for 60-100min to obtain isocyanate repairing agent emulsion 2a 1; the weight ratio of the isocyanate repairing agent to the solvent to the emulsifier is 1 (15-20) to 0.08-0.15; (2b) weighing a proper amount of curing agent, solvent and emulsifier, and stirring for 80-120min at normal temperature under 5000-9000rpm to obtain curing agent emulsion 2b 1; the weight ratio of the curing agent, the solvent and the emulsifier is 1 (10-15) to 0.08-0.18; (2c) dropwise adding the curing agent emulsion 2b1 into the isocyanate repairing agent emulsion 2a1, and stirring at the normal temperature of 2000-6000rpm for 1-2h to obtain the nano-scale microcapsule emulsion 2 coated with the repairing agent; the weight ratio of the isocyanate repair agent emulsion 2a1 to the curing agent emulsion 2b1 is 1:1-1: 5;
(3) preparing oxygen plasma modified graphene emulsion: placing a proper amount of graphene powder in an oxygen plasma instrument, carrying out vacuum treatment, and introducing oxygen to connect functional groups on the surface of graphene to obtain modified graphene powder; dissolving modified graphene powder in a proper amount of solvent, and uniformly stirring at 1000-2000rpm to obtain a modified graphene emulsion 3;
(4) preparing an internal-repairing external-fixing type graphene functionalized self-repairing microcapsule with a cellular structure: (4a) weighing a proper amount of isocyanate reagent, emulsifier and solvent, and uniformly stirring at the normal temperature of 3000-6000rpm for 70-100min to obtain isocyanate emulsion 4a 2; the weight ratio of the isocyanate reagent to the solvent to the emulsifier is 1 (15-20) to 0.06-0.12; (4b) weighing a proper amount of curing agent, modified graphene emulsion 3, dispersing agent and solvent, and stirring at the normal temperature of 2000-5000rpm for 50-70min to obtain curing agent-graphene dispersion liquid 4b 2; the weight ratio of the curing agent to the graphene emulsion 3 to the solvent to the dispersant is 1 (0.4-0.8): (10-15): (0.06-0.15); (4c) adding a certain amount of silane emulsion 1, nano microcapsule emulsion 2 and an emulsifier into the curing agent-graphene dispersion liquid 4b2, and emulsifying at the normal temperature at the rotation speed of 1500-; then dropwise adding isocyanate emulsion 4a2 into the composite emulsion, and stirring for 2-3h under the temperature condition of 50-70 ℃ and the rotating speed of 1000-2500rpm to obtain the internal-modification external-fixation type graphene functional self-repairing microcapsule emulsion with the cellular structure; the weight ratio of the curing agent-graphene dispersion liquid 4b2 to the silane emulsion 1 to the nano-microcapsule emulsion 2 to the emulsifier to the isocyanate emulsion 4a2 is 1 (0.5-0.8) to (0.15-0.25): (1-3); (4d) and (4) centrifuging, washing and drying the emulsion obtained in the step (4c) to obtain the internal-modification external-fixation graphene functional self-repairing microcapsule with a cellular structure.
2. The preparation method of the internally-modified externally-fixed graphene functional self-repairing microcapsule with the cellular structure as claimed in claim 1, wherein: in the step (3), the vacuum condition of the vacuum treatment is 200mTorr-400Torr, and the treatment time is 3-5 min; introducing oxygen at a flow rate of 3-5ml/min for 3-5 min; the functional group is carbonyl, hydroxyl or carboxyl.
3. The preparation method of the internally-modified externally-fixed graphene functional self-repairing microcapsule with a cellular structure as claimed in claim 1 or 2, wherein: in the step (4c), when the isocyanate emulsion 4a2 is added dropwise into the mixed solution, an appropriate amount of acid is added dropwise at the same time, so that the pH value of the system is 4-6.
4. The preparation method of the internally-modified externally-fixed graphene functional self-repairing microcapsule with the cellular structure as claimed in claim 3, wherein: the silane is one or more of vinyl triethoxysilane, vinyl trimethoxysilane, isobutyl triethoxysilane, trimethylsiloxy silane and octyl triethoxysilane;
the emulsifier is one or more of Op-10, polyvinyl alcohol, span 80, Arabic gum, sodium dodecyl benzene sulfonate and octadecyl alcohol polyoxyethylene ether;
the dispersant is one or more of polyethylene glycol, potassium citrate, sodium silicate and sodium linoleate;
the isocyanate repairing agent is one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate and 2, 2, 5-trimethylhexane diisocyanate;
the solvent is one or more of ethyl acetate, ethylene glycol dimethyl ether, cyclohexane, cyclopentane, cyclohexanol, toluene, xylene and chlorobenzene;
the curing agent is a hydroxyl compound or an amino compound; the hydroxyl compound is one or more of 1, 4-butanediol, n-butanol, pentanediol, 1, 6-hexanediol, cyclohexanedimethanol, pentaerythritol, polyoxypropylene polyol and polytetrahydrofuran polyol; the amino compound is diethyl toluene diamine, dimethyl sulfur toluene diamine, N ' -dialkyl methyl diphenylamine, cyclohexane diamine, chlorinated MDH, ethylene diamine, 1, 3-diaminopropane, 1, 4-diaminobutane, diethylene amine, pentaethylene hexamine, hexaethylene diamine, tetraethylene pentamine, polyether amine D400, polyether amine D230, ethylene diamine or 3,3' -4,4' -diamino-diphenylmethane MOCA.
5. The internally-modified externally-fixed graphene functionalized self-repairing microcapsule with the cellular structure prepared by the method of any one of claims 1-4, wherein the self-repairing microcapsule comprises a capsule wall and a capsule wall-coated curing agent, and is characterized in that: graphene is dispersed in the capsule wall; a series of nano-scale microcapsules are dispersed in the curing agent, so that a cellular structure is formed; the nano-scale microcapsule is coated with a repairing agent.
6. The internally-modified externally-fixed graphene functional self-repairing microcapsule with a cellular structure according to claim 5, wherein: the capsule wall of the self-repairing microcapsule is a silane modified capsule wall obtained by reacting a curing agent coated by the self-repairing microcapsule and dispersed with graphene with isocyanate emulsion and silane emulsion outside the self-repairing microcapsule; the curing agent is hydroxyl compound emulsion or amino compound emulsion, and the repairing agent is isocyanate emulsion.
7. The internally-modified externally-fixed graphene functional self-repairing microcapsule with a cellular structure according to claim 6, wherein: the capsule wall of the nano-scale microcapsule is obtained by reacting a repairing agent coated by the nano-scale microcapsule with a curing agent outside the nano-scale microcapsule, and the graphene is plasma modified graphene.
8. The self-repairing system adopting the internally-repaired externally-fixed graphene functionalized self-repairing microcapsule with the cell structure as claimed in any one of claims 5 to 7, is characterized in that: the mass fraction of the internal-repair external-fixation graphene functional self-repair microcapsule with the cellular structure in a self-repair system is 5% -18%; the self-repairing system is self-repairing concrete or a self-repairing coating.
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| CN111233366B (en) * | 2020-01-13 | 2022-07-29 | 沈阳大学 | Preparation of corrosion-resistant self-repairing reinforced concrete member with built-in microcapsules |
| CN111334176A (en) * | 2020-03-09 | 2020-06-26 | 沪宝新材料科技（上海）股份有限公司 | Solvent-free double-component finish paint for plastic track |
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