CN111499253B - Microwave controlled release-based additive microcapsule and preparation method thereof - Google Patents
Microwave controlled release-based additive microcapsule and preparation method thereof Download PDFInfo
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- CN111499253B CN111499253B CN202010294070.8A CN202010294070A CN111499253B CN 111499253 B CN111499253 B CN 111499253B CN 202010294070 A CN202010294070 A CN 202010294070A CN 111499253 B CN111499253 B CN 111499253B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
- B01J13/046—Making microcapsules or microballoons by physical processes, e.g. drying, spraying combined with gelification or coagulation
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Abstract
The invention relates to the field of additives for building materials, in particular to an additive microcapsule based on microwave controlled release and a preparation method thereof; the microcapsule consists of a capsule wall, a capsule core and an encapsulating material, wherein the capsule wall is polyvinylidene fluoride fiber; the capsule core is an additive needing to be controlled to release; the packaging material is a thermosensitive phase-change material; the PDVF material in the method has high strength and acid and alkali resistance, and is suitable for being used in building materials; most importantly, the PDVF material can realize microwave response, so that the active controlled release of the admixture in the concrete can be realized, and the problem of performance loss caused by the early release of the admixture is effectively solved.
Description
Technical Field
The invention relates to the field of additives for building materials, in particular to an additive microcapsule based on microwave controlled release and a preparation method and application thereof.
Background
In modern engineering construction, concrete is one of the most widely used building materials, and additives play an increasingly important role in concrete. The proper addition of different additives can bring different performance improvements to the concrete: the water reducing agent can adjust the working performance of the fresh concrete and is beneficial to later strength; the early strength agent can promote hydration and improve the early strength of concrete; the setting retarder or the setting accelerator can adjust the setting time of the cement; the air entraining agent or the rust inhibitor is beneficial to the durability of concrete and the like. From the beginning of concrete mixing of raw materials to the hardening maturity, different admixtures need to play a role in different time periods to achieve the optimal effect.
In current practical engineering application, additives are usually added directly in the concrete mixing process, so that some types of additives are diffused in advance and the target effect of the additives is lost. If the water reducing agent is mixed, the effect is quickly achieved, but the slump loss problem is very prominent along with the increase of time, and the distribution of commercial concrete is further influenced; if the rust inhibitor is dispersed in the concrete matrix after mixing, only the rust inhibitor which can be near the surface of the reinforcing steel bars actually influences the final rust inhibition effect.
The controlled release technique is a technique for releasing a target to the environment at a certain rate in a predetermined time in an artificially controlled manner, and is well suited to solve the problem of premature or unnecessary loss of the performance of concrete admixture.
Patent CN105174783A describes a slow-release type polycarboxylate superplasticizer, which not only possesses a certain initial water reducing effect, but also can gradually release effective water reducing components through ester group and alkali hydrolysis reaction in cement by grafting and copolymerizing different functional groups in the molecular structure of the polycarboxylate superplasticizer. Patent CN102351459B describes a slow-release water reducing agent microcapsule, which generates response stimulation behavior through the high pH environment generated by hydration of microcapsule wall shells and cement concrete, gradually releases water reducing agent molecules in the capsule, and improves the fluidity retention of the water reducing agent over time. In addition, patent CN110776270A describes a self-repairing microcapsule particle, which can be ruptured in response to micro-cracks generated in concrete, and release a capsule core repairing agent to repair the cracks.
However, the controlled release techniques of concrete admixture in the above patents are all triggered based on passive environmental response, and the release of admixture cannot be actively controlled by external signals. The introduction of an active controlled release technology is urgently needed for additives which need to play a role after the concrete mixing process, such as an early strength agent, an expanding agent, a rust inhibitor, a tackifier and the like.
Disclosure of Invention
The technical problem is as follows: in order to solve the technical problem of active release of concrete admixtures, the invention provides microcapsule particles with high strength and microwave response capability. After the microcapsule is added into concrete, the additive stored in the capsule is released in response to a microwave signal given from the outside.
The invention provides an additive microcapsule for microwave controlled release.
The second purpose of the invention is to provide a preparation method of the additive microcapsule for microwave controlled release.
The third purpose of the invention is to provide the application of the preparation method of the microwave controlled-release additive microcapsule.
The technical scheme is as follows: in order to achieve the purpose, the invention adopts the following technical means:
the invention discloses a microwave controlled-release additive microcapsule, which consists of a capsule wall, a capsule core and an encapsulating material, wherein the capsule wall is made of polyvinylidene fluoride (PVDF) fiber material; the capsule core is an additive needing to be controlled to release; and the outer side of the capsule wall is provided with a packaging material, and the packaging material is made of a thermosensitive phase-change material.
Furthermore, the capsule wall is a hollow membrane filament composed of polyvinylidene fluoride fibers, the diameter of a hollow tube of the capsule wall is 1-2.2mm, the length of the hollow tube is 1-2cm, and the wall thickness of the hollow tube is 50-200 mu m.
Furthermore, micropores are arranged on the capsule wall, and the pore diameter of each micropore is 0.01-0.2 μm.
Further, the additive is any one of a water reducing agent, a rust inhibitor, a tackifier, an expanding agent and an epoxy repairing agent.
Further, the thermosensitive phase-change material is any one of paraffin, stearic acid, hydrogel and polymer gel.
Secondly, the invention discloses a preparation method of the microwave controlled release additive microcapsule, which comprises the following steps:
(1) putting the PVDF hollow fiber tube into the additive solution, then putting the PVDF hollow fiber tube into a vacuum drying dish, pumping negative pressure to fully fill the additive in the tube, and taking the PVDF hollow fiber tube out of the additive solution after filling to obtain a target capsule wall and a capsule core;
(2) and (3) immersing the PVDF hollow fiber tube filled with the additive into the heated and melted packaging material, taking out and cooling the PVDF hollow fiber tube to cool and solidify the packaging material so as to block the internal additive, and repeating the steps for a plurality of times to thoroughly block the capsule to obtain the PVDF hollow fiber capsule.
Further, in the step (1), under the vacuum negative pressure condition, the reaction pressure is 0-20Kpa, and the reaction time is 12-24 hours.
Further, the temperature after the temperature reduction in the step (2) is 17-23 ℃.
Finally, the invention discloses the application of the microwave controlled-release additive microcapsule and the product prepared by the preparation method thereof in the field of buildings; such as for actively controlled release of the admixture, etc.
Has the advantages that: compared with the prior art, the invention has the following beneficial effects:
(1) the PVDF material used as the material of the capsule wall in the method disclosed by the invention is a resistance type wave-absorbing material, and can effectively absorb the energy of microwaves and convert the energy into heat energy, thereby realizing microwave response. The temperature of the wall material will cause the encapsulating material to melt, thereby releasing the admixture from the core. After the microcapsule taking PVDF as the capsule wall material is added into concrete, even after the slurry is hardened, the release of the admixture can be actively controlled outside. The method effectively solves the problems of the adverse effect caused by the early loss or the early release of the admixture and the like, and has wide application prospect.
(2) The PVDF material in the method disclosed by the invention has high strength and acid and alkali resistance, and is suitable for being used in building materials; the production is convenient, and the hollow fiber pipe wall composed of PVDF can effectively realize the encapsulation of macromolecular admixture by designing the pipe wall aperture size; the capsule has simple structure and design and large additive storage capacity.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a schematic structural diagram of an additive microcapsule for microwave controlled release in the invention;
FIG. 2 is a diagram showing the phase change conditions of paraffin wax added with PVDF fiber material, paraffin wax added with ferroferric oxide powder and paraffin wax added with ferroferric oxide powder in microwave;
FIG. 3 is a graph showing the results of the release of the microcapsules of the external agent in example 1 by the action of microwaves;
in the figure: 1. capsule wall, 2, capsule core, 3, packaging material.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As mentioned in the background and foregoing, the current art of concrete admixtures lacks active controlled release technology. In order to solve the above problems, the present invention provides an additive microcapsule for microwave controlled release, and the technical scheme is further described as follows:
the invention discloses a microwave controlled-release additive microcapsule, which consists of a capsule wall 1, a capsule core 2 and an encapsulating material 3.
In some exemplary embodiments, the admixture microcapsule is in the form of an elongated tube.
In some typical embodiments, the microcapsule wall 1 material is made of polyvinylidene fluoride (PVDF) hollow tubular fiber, the diameter of the hollow tube is 1-2.2mm, the length is 1-2cm, the wall thickness is 50-200 μm, and the pore diameter of the micropores on the wall is 0.01-0.2 μm.
In some typical embodiments, the core 2 is composed of an admixture; the encapsulating material 3 is made of a heat-sensitive phase change material.
In some exemplary embodiments, the additive is any one of a water reducing agent, a rust inhibitor, a tackifier, an expanding agent and an epoxy repairing agent.
In some typical embodiments, the encapsulating material 3 is any one of paraffin, stearic acid, hydrogel and polymer gel, and the melting point of the encapsulating material 3 is 50-55 ℃.
The PVDF material of the microcapsule wall 1 is a resistance type wave-absorbing material, and is characterized in that the larger the conductivity is, the larger the macroscopic current (current caused by an electric field and eddy current caused by magnetic field change) caused by carriers is, the more beneficial the electromagnetic energy is to be converted into heat energy. After the microcapsules are mixed into the concrete, the PVDF material is heated by external microwave, when the temperature is increased to exceed the melting point of the packaging material 3, the packaging material 3 is melted, the additive in the capsules is released, and the additive enters the concrete through diffusion to take effect.
The invention is further described with reference to the following figures and detailed description.
As shown in fig. 2, the microwave response of different materials was tested: firstly, adding the paraffin of the PVDF fiber material, secondly, adding the pure paraffin, and thirdly, adding the ferroferric oxide powder into the paraffin. All three materials contained about 15g of paraffin wax and were tested in a microwave reactor at room temperature of 20 ℃ to observe phase transitions. The method can find that after the composite material is placed under the microwave power of 400W for one minute, the paraffin added with the PVDF fiber material is obviously melted, but the paraffin added with pure paraffin and the paraffin added with ferroferric oxide powder are not obviously melted; after the mixture is placed under the microwave power of 400W for two minutes, the paraffin added with the PVDF fiber material is completely melted, the paraffin added with the ferroferric oxide powder is partially melted, and the phenomenon of pure paraffin is not obvious. As the proportion of paraffin in the actual microcapsule is smaller, the experiment proves that the PVDF fiber material can convert the energy of electromagnetic waves into heat energy, so that the encapsulating material 3 is melted, the internal additive is released, and the feasibility of the microwave controlled release microcapsule is proved.
Example 1
The preparation of the microwave controlled-release additive microcapsule and the test of the microwave controlled-release additive thereof comprise the following steps:
1. preparing a microwave controlled-release microcapsule:
commercial grade PVDF fiber tube is cut to 2cm long, the diameter of the selected fiber tube is 2mm, the wall thickness is about 200 μm, and the pore diameter of the wall micropore is 0.2 μm. And completely soaking the cut PVDF fiber tube into a polycarboxylic acid water reducing agent aqueous solution (a small amount of methyl orange indicator is added) with the solid content of 10%, and then placing the PVDF fiber tube into a vacuum drying dish to be vacuumized until the pressure is less than 20Kpa and keeping the pressure for 24 hours, so that the water reducing agent is fully filled in the PVDF fiber tube. And taking out the fiber tube filled with the liquid water reducing agent from the solution, quickly immersing the fiber tube into molten paraffin, and taking out the fiber tube to enable the paraffin to be quickly solidified and seal and wrap the whole fiber tube at room temperature (20 ℃), wherein the melting point of the paraffin is 50-55 ℃. And (3) repeating the steps of immersing the fiber tube in the molten paraffin and taking out the fiber tube for a plurality of times, so that the fiber tube is completely encapsulated, and the target microcapsule is obtained.
2. Microwave controlled release test of microcapsules:
and (3) placing the microcapsules prepared in the last step into 30ml of deionized water, and standing for 3 hours until no internal water reducing agent leaks. And then putting the microcapsule and water into a microwave reactor together, reacting for 1 minute at the microwave power of 300W, and finding that the paraffin of the encapsulating materials 3 at the two ends of the microcapsule is melted, and the water reducing agent doped with the methyl orange indicator in the microcapsule is obviously diffused into the solution, as shown in figure 3.
Example 2
Commercial grade PVDF fiber tube is cut to 1cm long, the diameter of the selected fiber tube is 1mm, the wall thickness is about 50 μm, and the pore diameter of the wall micropore is 0.01 μm. And completely soaking the cut PVDF fiber tube into an imidazole rust inhibitor aqueous solution, then placing the PVDF fiber tube into a vacuum drying dish, and pumping negative pressure to be less than 20Kpa for 24 hours, so that the PVDF fiber tube is fully filled with the rust inhibitor. And taking out the fiber tube filled with the liquid rust inhibitor from the solution, quickly immersing the fiber tube into molten paraffin, and taking out the fiber tube to enable the paraffin to be quickly solidified and wrap the whole fiber tube at room temperature (20 ℃), wherein the melting point of the paraffin is 50-55 ℃. And (3) the step of immersing the fiber tube in the molten paraffin and then taking out the fiber tube is repeated for a plurality of times, so that the fiber tube is completely encapsulated, and the target microwave controlled-release microcapsule is obtained.
Example 3
Commercial grade PVDF fiber tube is cut to 1cm long, the diameter of the selected fiber tube is 1.5mm, the wall thickness is about 100 μm, and the pore diameter of the wall micropore is 0.01 μm. And completely soaking the cut PVDF fiber tube into a tackifier (polyethylene glycol aqueous solution, molecular weight of 400 and mass fraction of 10%), placing the PVDF fiber tube into a vacuum drying dish, and vacuumizing to less than 20Kpa for 24 hours to fully fill the tackifier in the PVDF fiber tube. And taking out the fiber tube filled with the liquid rust inhibitor from the solution, quickly immersing the fiber tube into the gel formed by the liquid stearic acid and the peanut oil, and then taking out the fiber tube, so that the gel is quickly solidified at room temperature (20 ℃) to seal and wrap the whole fiber tube, wherein the gel phase transition point is about 50-55 ℃. And completely encapsulating the fiber tube by using the gel to obtain the target microwave controlled-release microcapsule.
100mm concrete test piece (water cement ratio 0.53; raw material dosage per cubic meter cement 375kg, water 200kg, medium sand 750kg, 5-20mm continuous gradation stone 1125 kg) is formed, and tackifier microcapsule with 2% cement mass is mixed in the forming process. And controlling the release of the tackifier in the concrete through a microwave signal 28 days after the formation.
Example 4
The industrial PVDF fiber tube is cut to 2cm long, the diameter of the selected fiber tube is 2mm, the wall thickness is about 200 μm, and the pore diameter of the micropores on the wall is 0.2 μm. And filling an epoxy repairing agent into the cut PVDF fiber tube, placing the PVDF fiber tube in a vacuum drying dish, and pumping negative pressure to less than 20Kpa for 24 hours to ensure that the PVDF fiber tube is fully filled with the epoxy repairing agent. And taking out the fiber tube filled with the epoxy repairing agent from the solution, quickly immersing the fiber tube into melted paraffin, and taking out the fiber tube to enable the paraffin to be quickly solidified and seal and wrap the whole fiber tube at room temperature (20 ℃), wherein the melting point of the paraffin is 50-55 ℃. And (3) the step of immersing the fiber tube into the molten paraffin and then taking out the fiber tube is repeated for a plurality of times, so that the fiber tube is completely encapsulated, and the target microwave controlled-release microcapsule can be obtained and can be used for repairing the micro-cracks in the concrete.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A microwave controlled release additive microcapsule is characterized in that: the capsule wall is made of polyvinylidene fluoride materials, and the capsule core is made of additives; the outer side of the capsule wall is provided with a packaging material, and the packaging material is made of a thermosensitive phase-change material;
the capsule wall is a hollow membrane filament composed of polyvinylidene fluoride fibers;
the capsule wall is provided with micropores, and the pore diameter of the micropores is 0.01-0.2 μm.
2. The microwave controlled-release additive microcapsule according to claim 1, wherein: the diameter of the hollow tube of the capsule wall is 1-2.2mm, the length is 1-2cm, and the wall thickness is 50-200 μm.
3. The microwave controlled-release additive microcapsule according to claim 1, wherein: the additive is any one of a water reducing agent, a rust inhibitor, a tackifier, an expanding agent and an epoxy repairing agent.
4. The microwave controlled-release additive microcapsule according to claim 1, wherein: the thermosensitive phase-change material is any one of paraffin, stearic acid, hydrogel and polymer gel.
5. A method for preparing the microwave controlled-release additive microcapsule according to any one of claims 1 to 4, characterized in that: the steps are as follows:
(1) soaking a polyvinylidene fluoride fiber pipe in an additive solution, filling the additive into the pipe under the vacuum negative pressure condition, and taking the polyvinylidene fluoride fiber pipe out of the additive solution after filling;
(2) and (3) immersing the filled polyvinylidene fluoride fiber tube into an encapsulating material, taking out and cooling, and repeating the steps for a plurality of times to obtain the microwave controlled-release additive microcapsule.
6. The method of claim 5, wherein: in the step (1), under the condition of vacuum and negative pressure, the reaction pressure is 0-20Kpa, and the filling time is 12-24 hours.
7. The method of claim 5, wherein: the temperature after the temperature reduction in the step (2) is 17-23 ℃.
8. The application of the microwave controlled-release additive microcapsule obtained by the preparation method according to claim 5 in the field of buildings.
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| CN112322253B (en) * | 2020-11-11 | 2022-09-16 | 南京清尚新材料科技有限公司 | Pressure-sensitive adhesive with low surface viscosity, preparation method of pressure-sensitive adhesive and functional adhesive tape |
| CN112645633A (en) * | 2020-12-26 | 2021-04-13 | 西盟司（上海）建筑工程材料有限公司 | Antifreezing concrete water reducing agent and preparation method thereof |
| CN115259731A (en) * | 2022-08-17 | 2022-11-01 | 博特新材料泰州有限公司 | Slow-release long-acting air entraining material and preparation method and application thereof |
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| JPS60161742A (en) * | 1984-01-30 | 1985-08-23 | Kobe Steel Ltd | Preparation of minute hollow sphere |
| CN101684403B (en) * | 2008-09-25 | 2013-03-20 | 中国科学院化学研究所 | Phase change material microcapsules encapsulated by natural microtubules and preparation method thereof |
| CN102127395B (en) * | 2010-12-10 | 2012-12-19 | 东南大学 | Paraffin wax phase change energy storage material and preparation method thereof |
| CN102702838B (en) * | 2012-06-28 | 2013-11-20 | 中国船舶重工集团公司第七二五研究所 | Micro-crack self-repairing microcapsule and preparation method thereof |
| WO2014053352A1 (en) * | 2012-10-03 | 2014-04-10 | Danmarks Tekniske Universitet | Ingestible capsule for remote controlled release of a substance |
| WO2017112724A1 (en) * | 2015-12-21 | 2017-06-29 | The Regents Of The University Of California | Tunable hollow poly (vinylidene difluoride) microspheres |
| CN110894623A (en) * | 2018-09-12 | 2020-03-20 | 天津工业大学 | Preparation method of hollow fiber coated with oily repairing agent |
| CN110128708A (en) * | 2019-05-29 | 2019-08-16 | 南昌大学 | A kind of suction wave-self-repairing microcapsule and preparation method thereof |
| CN110407509A (en) * | 2019-07-02 | 2019-11-05 | 东南大学 | It is a kind of can microwave heating regeneration repair bituminous concrete microcapsules and preparation method |
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