CN115536316B - Flexible membrane capable of generating driving response under stimulation of ammonia gas and carbon dioxide and preparation method thereof - Google Patents

Flexible membrane capable of generating driving response under stimulation of ammonia gas and carbon dioxide and preparation method thereof Download PDF

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CN115536316B
CN115536316B CN202211323037.9A CN202211323037A CN115536316B CN 115536316 B CN115536316 B CN 115536316B CN 202211323037 A CN202211323037 A CN 202211323037A CN 115536316 B CN115536316 B CN 115536316B
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montmorillonite
quaternary ammonium
ammonium salt
carbon dioxide
salt surfactant
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CN115536316A (en
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杨志红
孟莹
陈惠琳
孔苗苗
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China University of Geosciences
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China University of Geosciences
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/001—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing unburned clay
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61—Coating or impregnation
    • C04B41/62—Coating or impregnation with organic materials

Abstract

The invention discloses a flexible membrane capable of generating driving response under the stimulation of ammonia gas and carbon dioxide and a preparation method thereof. The flexible film comprises a montmorillonite monolayer film, one surface of which is spin-coated with a quaternary ammonium salt surfactant layer. A method for preparing flexible film generating drive response under the stimulation of ammonia and carbon dioxide includes preparing montmorillonite single layer film from nano montmorillonite dispersion liquid by casting method, spin-coating quaternary ammonium salt surfactant solution on surface of montmorillonite single layer film, and drying to obtain asymmetric double layer film, i.e. flexible film with asymmetric structure. The invention obtains the flexible driving material which can generate stimulus response to gases such as ammonia gas, carbon dioxide and the like by synthesizing and designing the double-layer structure film with the characteristics of specific material composition and asymmetric structure.

Description

Flexible membrane capable of generating driving response under stimulation of ammonia gas and carbon dioxide and preparation method thereof
Technical Field
The invention relates to the technical field of response materials, in particular to a flexible film capable of generating driving response under the stimulation of ammonia and carbon dioxide and a preparation method thereof.
Background
The flexible intelligent material can generate specific deformation response under external stimulation of light, heat, solvent gas, electricity or magnetic fields and the like, thereby showing great application prospect in the fields of sensors, soft robots, artificial muscles and the like. Wherein, the gas in the environment is one of the most common stimulation sources, and the gas and the flexible material generate substance exchange to further induce the asymmetric swelling or deswelling of the flexible material, thereby generating the memory type deformation function. Among the gases that can drive flexible materials, the stimulation studies of water vapor are most common, followed by gases of volatile solvents, such as ethanol, isopropanol, carbon tetrachloride, tetrahydrofuran, acetone, and the like.
In the gas driving research of flexible materials, a lot of blanks exist, such as the current stimulus is limited to humidity and organic solvents, and the research workers have not been involved in the stimulus response driving of some common non-solvent gases, such as ammonia and carbon dioxide.
Disclosure of Invention
The invention aims to provide a flexible film capable of generating drive response under the stimulation of ammonia gas and carbon dioxide and a preparation method thereof, aiming at the defects of the prior art, and the flexible film can generate the stimulation response to sources of ammonia gas, carbon dioxide and the like.
The invention relates to a flexible film generating driving response under the stimulation of ammonia gas and carbon dioxide, which comprises a montmorillonite single-layer film, wherein a quaternary ammonium salt surfactant layer is spin-coated on one surface of the montmorillonite single-layer film.
A method for preparing a flexible film generating drive response under the stimulation of ammonia and carbon dioxide comprises the steps of preparing a montmorillonite single-layer film from a nano montmorillonite dispersion liquid by a casting method, then spin-coating a quaternary ammonium salt surfactant solution on the surface of the montmorillonite single-layer film, and drying to obtain an asymmetric double-layer film, namely the flexible film generating drive response under the stimulation of ammonia and carbon dioxide.
Further, the preparation method of the nano montmorillonite dispersion liquid comprises the following steps: dispersing montmorillonite in water according to the mass content of 5wt%, magnetically stirring at room temperature for one week, centrifuging at 4000r/min for 8min to remove the lower layer of montmorillonite, collecting the nanometer montmorillonite dispersion liquid with the upper layer completely stripped, and diluting to make the concentration of the nanometer montmorillonite dispersion liquid be 2-4wt%.
Further, the preparation method of the quaternary ammonium salt surfactant solution comprises the following steps: weighing a certain mass of quaternary ammonium salt surfactant in a beaker, then adding a certain amount of ethanol, stirring for 30min until the quaternary ammonium salt surfactant is completely dissolved to obtain 8.0-9.5wt% of quaternary ammonium salt surfactant solution.
Furthermore, 0.1-0.3wt% of methylene blue or rhodamine B is added into the obtained quaternary ammonium salt surfactant solution to adjust the color of the solution.
Further, the quaternary ammonium salt surfactant comprises cetyl trimethyl ammonium bromide or \ and octadecyl trimethyl ammonium chloride.
Further, the procedure for preparing a montmorillonite monolayer film by casting method is as follows: adding a certain amount of the nano-montmorillonite dispersion liquid into a culture dish, and then drying to obtain the montmorillonite single-layer film covering the bottom of the culture dish.
Further, the process of spin coating the quaternary ammonium surfactant solution is as follows: and step-by-step spin-coating a certain amount of the quaternary ammonium salt surfactant solution on a montmorillonite membrane, wherein the spin-coating amount is not more than 2mL each time, drying at 40-50 ℃ after spin-coating, then performing next spin-coating of the quaternary ammonium salt surfactant solution until all the quaternary ammonium salt surfactant solution is completely spin-coated, drying at a certain temperature until the membrane is about to fall off, and then peeling the membrane from a culture dish to obtain the asymmetric double-layer membrane with one side of the montmorillonite and the other side of the quaternary ammonium salt surfactant, namely the flexible membrane which generates drive response under the stimulation of ammonia gas and carbon dioxide.
In order to break through the deformation response of the flexible intelligent material in the field of non-solvent gases (such as ammonia gas, carbon dioxide and the like) and further expand the application range of the flexible intelligent material in the fields of sensors, flexible robots and the like, the invention obtains the flexible driving material which generates stimulus response to the gases such as ammonia gas, carbon dioxide and the like by synthesizing and designing the double-layer structure film with specific material composition and asymmetric structure characteristics.
The flexible membrane which can generate drive response under the stimulation of ammonia and carbon dioxide is an asymmetric double-layer membrane, one side of the flexible membrane adopts a montmorillonite clay material with rich sources and a layered structure, and the other side of the flexible membrane adopts a quaternary ammonium surfactant (such as hexadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride and the like) material. Wherein the montmorillonite on one side is 2: the type 1 clay has strong hydration ability and good water molecule adsorption, and has montmorillonite (aluminosilicate sheet) with negative charge and cation NH 4 + Has good adsorbability, and can be used as an active layer reacting to ammonia stimulation. The quaternary ammonium salt surfactant on the other side is prepared by reacting amine with CO due to functional groups 2 Has good interaction force between them and is used for CO 2 Has good adsorptivity, selectivity and safety, and can be used for treating CO 2 Stimulating the responsive active layer. The film can generate bending deformation in different directions and different degrees under different gas environments.
The asymmetric double-layer film has the advantages of simple preparation method, low raw material cost, large response discrimination on different gas medium stimuli and the like.
In order to enhance the identification degree of two sides of the flexible membrane and simultaneously not reduce the stimulation responsiveness of the flexible membrane to carbon dioxide, a small amount of dye containing functional group amine, such as methylene blue or rhodamine B, is added into the quaternary ammonium salt surfactant solution, so that the quaternary ammonium salt surfactant side of the membrane is blue or red, and forms color difference with milky white or grey white of a montmorillonite layer on the other side, and simultaneously the side of organic amine facing CO is not reduced 2 The stimulus responsive activity of (2).
Drawings
FIG. 1 shows NH of an asymmetric bilayer film prepared in example 1 3 A medium response speed map;
FIG. 2 shows the asymmetric bilayer membrane prepared in example 1 in CO 2 A medium response speed map;
FIG. 3 shows NH of the asymmetric bilayer film prepared in example 2 3 A medium response speed map;
FIG. 4 shows the asymmetric bilayer membrane prepared in example 2 in CO 2 Medium response speed map.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
The ammonia stimulus response experiment and the carbon dioxide stimulus response experiment methods adopted in the embodiment are as follows:
the ammonia gas stimulus response experimental method comprises the following steps: the prepared asymmetric double-layer film is cut into a strip shape of 20mm multiplied by 4 mm. Preparing a transparent plastic bottle, pasting one end of the strip-shaped tinfoil paper on the bottle cap, and then pasting the strip-shaped film on the other end of the tinfoil paper. And (3) putting ammonia water into the bottle, wherein the volume of the ammonia water accounts for one third of the volume of the bottle, then covering the bottle cap to enable the strip-shaped film to be suspended above the liquid level of the ammonia water, and observing the bending change of the strip-shaped film under the stimulation of the ammonia gas.
The carbon dioxide stimulus response experimental method is that the prepared asymmetric double-layer film is cut into a strip shape of 20mm multiplied by 4 mm. Preparing a three-mouth flask, adhering one end of a strip-shaped tinfoil paper to a rubber plug, and then adhering the strip-shaped film to the other end of the tinfoil paper. And (3) slowly introducing carbon dioxide into one side of the flask for about 10 minutes, placing a rubber plug on the middle bottle mouth, and observing the bending change of the strip-shaped film under the stimulation of the carbon dioxide.
Example 1
Preparing a nano montmorillonite dispersion liquid: dispersing montmorillonite in water according to the mass content of 5wt%, magnetically stirring at room temperature for one week, centrifuging at 4000r/min for 8min to remove the lower layer montmorillonite, and collecting the upper layer montmorillonite suspension to obtain uniformly dispersed 2wt% nanometer montmorillonite dispersion.
12.5g of the above dispersion liquid of nano-montmorillonite was added to a culture dish having a diameter of 8.6cm, and then dried at 40 ℃ for 6 hours to obtain a montmorillonite single-layer film covering the bottom of the culture dish. 1.9g of cetyltrimethylammonium bromide solid was weighed into a beaker, followed by addition of ethanol to 20.0g, followed by 0.1wt% methylene blue, which completely dissolved to give a 9.5wt% solution of cetyltrimethylammonium bromide. And (2) carrying out fractional spin coating on the surface of the montmorillonite film in the culture dish by 2.63g of 9.5wt% hexadecyl trimethyl ammonium bromide solution, wherein the volume of the one-time spin coating is not more than 2mL, the one-time spin coating is followed by drying at 40 ℃ for 2mins, the next-time spin coating is followed by spin coating, after the spin coating is finished, the next-time hexadecyl trimethyl ammonium bromide solution is completely dried at 60 ℃, and then the double-layer film is separated from the culture dish.
As shown in figure 1, the prepared asymmetric double-layer film is bent towards the hexadecyl trimethyl ammonium bromide side in the air, the bending angle is 22 degrees, and then the asymmetric double-layer film is placed into NH by adopting an ammonia stimulation response experimental method 3 In the above example, it was found that the bending was continued to the hexadecyltrimethylammonium bromide side, and after 3 seconds, the maximum bending angle was reached, and the bending angle was 62 °. According to experimental tests, the prepared asymmetric double-layer film is in NH 3 The medium response speed is high, and the bending is obvious.
As shown in FIG. 2, the asymmetric double-layer film was bent toward the hexadecyl trimethyl ammonium bromide side in the air at a bending angle of-18 deg., and then stimulated with carbon dioxideIn response to the experimental procedure, it was put into CO 2 In the case of bending to the montmorillonite side, the maximum bending angle was reached after 28 seconds, and the bending angle was 54 °. According to experimental tests, the prepared asymmetric double-layer film is applied to CO 2 In addition, the bending angle is large, and the experimental phenomenon is obvious.
Example 2
Preparing a nano montmorillonite dispersion liquid: dispersing montmorillonite in water according to the mass content of 5wt%, magnetically stirring at room temperature for one week, centrifuging at 4000r/min for 8min to remove the lower layer montmorillonite, and collecting the upper layer montmorillonite suspension to obtain uniformly dispersed 4wt% nanometer montmorillonite dispersion liquid.
6.25g of the above dispersion liquid of nano-montmorillonite was added to a culture dish having a diameter of 8.6cm, and then dried at 40 ℃ for 2 hours to obtain a montmorillonite single-layer film covering the bottom of the culture dish. 1.6g of octadecyl trimethyl ammonium chloride solid is weighed into a beaker, then ethanol is added to 20.0g, then 0.3wt% of methylene blue is added, and 8.0wt% of octadecyl trimethyl ammonium chloride solution is obtained after complete dissolution. And 3.13g of octadecyl trimethyl ammonium chloride solution with the concentration of 8.0wt% is subjected to fractional spin coating on the surface of the montmorillonite membrane in a culture dish, wherein the volume of the montmorillonite membrane is not more than 2mL in one spin coating, the octadecyl trimethyl ammonium chloride solution is dried at 40 ℃ for 2mins after each spin coating, the octadecyl trimethyl ammonium chloride solution is subjected to spin coating again, the complete drying is carried out at 60 ℃ after the spin coating, and then the double-layer membrane is separated from the culture dish.
As shown in FIG. 3, the prepared asymmetric double-layer film is bent towards the octadecyl trimethyl ammonium chloride side in the air, the bending angle is 5 degrees, and then the asymmetric double-layer film is placed into NH by adopting an ammonia stimulus response experimental method 3 And the bending is continued to the side of octadecyl trimethyl ammonium chloride, and after 12 seconds, the maximum bending angle is reached, and the bending angle is 62 degrees. According to experimental tests, the prepared asymmetric double-layer film is in NH 3 The medium response speed is fast, and the bending degree is obvious.
As shown in FIG. 4, the prepared asymmetric double-layer film is bent at an angle of 0 ℃ in air, and then put into CO by adopting a carbon dioxide stimulus response experimental method 2 In (1), its direction was foundThe montmorillonite was bent laterally to a maximum bend angle after 48s, which was 90 °. According to experimental tests, the prepared asymmetric double-layer film is in CO 2 The medium curve is significant.
The above is not mentioned, is suitable for the prior art.
While certain specific embodiments of the present invention have been described in detail by way of illustration, it will be understood by those skilled in the art that the foregoing is illustrative only and is not limiting of the scope of the invention, as various modifications or additions may be made to the specific embodiments described and substituted in a similar manner by those skilled in the art without departing from the scope of the invention as defined in the appending claims. It should be understood by those skilled in the art that any modifications, equivalents, improvements and the like made to the above embodiments in accordance with the technical spirit of the present invention shall be included in the scope of the present invention.

Claims (7)

1. A flexible membrane that produces a driving response under ammonia and carbon dioxide stimulation, comprising: the montmorillonite single-layer film comprises a montmorillonite single-layer film, wherein a quaternary ammonium salt surfactant layer is coated on one surface of the montmorillonite single-layer film in a spinning mode.
2. A method of producing a flexible membrane that produces a driving response in response to ammonia and carbon dioxide stimuli according to claim 1, wherein: firstly, preparing a montmorillonite single-layer film from a nano montmorillonite dispersion liquid by a casting method, then spin-coating a quaternary ammonium salt surfactant solution on the surface of the montmorillonite single-layer film, and drying to obtain an asymmetric double-layer film, namely a flexible film generating driving response under the stimulation of ammonia gas and carbon dioxide; the montmorillonite monolayer film was prepared by the casting method as follows: adding a certain amount of the nano-montmorillonite dispersion liquid into a culture dish, and then drying to obtain the montmorillonite single-layer film covering the bottom of the culture dish.
3. A method of producing a flexible membrane that produces a driving response in response to ammonia and carbon dioxide stimuli according to claim 2, wherein: the preparation method of the nano montmorillonite dispersion liquid comprises the following steps: dispersing montmorillonite in water according to a certain mass content, magnetically stirring at room temperature for a period of time, centrifuging at a certain rotating speed for a period of time to remove the montmorillonite at the lower layer, collecting the nano montmorillonite dispersion liquid with the upper layer completely stripped, and diluting to make the concentration of the nano montmorillonite dispersion liquid be 2-4wt%.
4. A method of producing a flexible membrane that produces a driving response in response to ammonia and carbon dioxide stimuli according to claim 2, wherein: the preparation method of the quaternary ammonium salt surfactant solution comprises the following steps: weighing a certain mass of quaternary ammonium salt surfactant into a beaker, then adding a certain amount of ethanol, and stirring until the quaternary ammonium salt surfactant is completely dissolved to obtain a quaternary ammonium salt surfactant solution with the weight percent of 8.0-9.5.
5. A method of producing a flexible membrane that produces a driving response in response to ammonia and carbon dioxide stimuli according to claim 4, wherein: adding 0.1-0.3wt% of methylene blue or rhodamine B into the obtained quaternary ammonium salt surfactant solution to adjust the color of the solution.
6. A method of producing a flexible membrane that produces a driving response in response to ammonia and carbon dioxide stimuli according to claim 2, wherein: the quaternary ammonium salt surfactant comprises cetyl trimethyl ammonium bromide or \ and octadecyl trimethyl ammonium chloride.
7. A method of producing a flexible membrane that produces a driving response in response to ammonia and carbon dioxide stimuli according to claim 2, wherein: the process of spin coating quaternary ammonium salt surfactant solution is as follows: and step-by-step spin-coating a certain amount of the quaternary ammonium salt surfactant solution on a montmorillonite membrane, wherein the amount of spin-coating is not more than 2mL each time, drying at 40-50 ℃ after spin-coating, then performing next spin-coating of the quaternary ammonium salt surfactant solution until all the quaternary ammonium salt surfactant solution is completely spin-coated, drying at a certain temperature until the membrane is about to fall off, and peeling the membrane from a culture dish to obtain the asymmetric double-layer membrane with one side of montmorillonite and the other side of quaternary ammonium salt surfactant, namely the flexible membrane with the asymmetric structure.
CN202211323037.9A 2022-10-27 2022-10-27 Flexible membrane capable of generating driving response under stimulation of ammonia gas and carbon dioxide and preparation method thereof Active CN115536316B (en)

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