CN115321551B - Intercalation method of clay material, two-dimensional material, preparation method and application thereof - Google Patents
Intercalation method of clay material, two-dimensional material, preparation method and application thereof Download PDFInfo
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- CN115321551B CN115321551B CN202210908723.6A CN202210908723A CN115321551B CN 115321551 B CN115321551 B CN 115321551B CN 202210908723 A CN202210908723 A CN 202210908723A CN 115321551 B CN115321551 B CN 115321551B
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
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- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
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- 238000011056 performance test Methods 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 8
- 229910052901 montmorillonite Inorganic materials 0.000 description 8
- 239000004570 mortar (masonry) Substances 0.000 description 8
- 238000004299 exfoliation Methods 0.000 description 7
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- 229920002521 macromolecule Polymers 0.000 description 2
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical group [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 2
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- 235000019322 gelatine Nutrition 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/44—Products obtained from layered base-exchange silicates by ion-exchange with organic compounds such as ammonium, phosphonium or sulfonium compounds or by intercalation of organic compounds, e.g. organoclay material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The invention discloses an intercalation method of a clay material, a two-dimensional material, a preparation method and application thereof. The intercalation method comprises the following steps: taking a mixture of a polymer solution and a clay material, and grinding or ball milling the mixture, wherein the polymer intercalates and exfoliates the clay material; wherein the mass fraction of the polymer in the polymer solution is 0.5-3%. The invention can realize the green, efficient and large-scale stripping preparation of the large-diameter and high-quality two-dimensional mineral material, has simple and convenient operation process, natural and pollution-free operation process and low energy consumption, and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to an intercalation method of a clay material, a two-dimensional material, a preparation method and application thereof.
Background
The clay mineral material is a current hot spot field due to the characteristics of abundant reserves, sustainable sources, nature, no pollution and the like. The precondition of large-scale application of the two-dimensional clay mineral material is that the controllable preparation of the two-dimensional clay mineral material is realized, and the preparation method of the two-dimensional material mainly comprises a chemical vapor deposition method from bottom to top and an stripping method from top to bottom. The chemical vapor deposition method can prepare a high-quality single-layer two-dimensional material, but the method is small in scale and high in cost, and is not suitable for preparing a multi-element material with complex components and structures such as clay minerals. In contrast, the exfoliation method can be used to prepare a two-dimensional material of clay minerals, however, the two-dimensional material obtained by the conventional exfoliation method of clay minerals at present has a smaller sheet diameter, takes a longer time, and sometimes uses corrosive agents.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides an intercalation method of clay materials, which can realize green, efficient and large-scale stripping preparation of large-diameter and high-quality two-dimensional mineral materials.
The invention also provides a preparation method of the two-dimensional material.
The invention also provides a two-dimensional material.
The invention also provides a composite material.
The invention also provides a preparation method of the composite material.
The invention also provides a glass coating material.
The invention also provides application of the two-dimensional material or the composite material.
In a first aspect of the present invention, there is provided a clay material intercalation method comprising the steps of: taking a mixture of a polymer solution and a clay material, and grinding or ball milling the mixture, wherein the polymer intercalates and exfoliates the clay material; wherein the mass fraction of the polymer in the polymer solution is 0.5-3%.
The intercalation method of the clay material has at least the following beneficial effects:
the invention provides a method for obtaining a two-dimensional clay mineral material by polymer intercalation adhesion and exfoliation of a clay material, which comprises the steps of grinding or ball-milling a mixture of a layered clay material and a polymer solution to enable polymers to adhere and intercalate inside the layered clay material, thereby expanding interlayer spacing of the layered clay, reducing interlayer interaction, and simultaneously promoting slip and exfoliation of a two-dimensional clay material sheet layer through shearing force applied between the layers. The mass fraction of the polymer in the polymer solution is 0.5-3%, so that the green, efficient and large-scale stripping preparation of the large-diameter and high-quality two-dimensional mineral material can be realized, the operation process is simple and convenient, the preparation time is short, the natural pollution-free performance is realized, the energy consumption is low, and the method is suitable for large-scale industrial production.
The clay material is clay mineral material.
In a second aspect of the present invention, a method for preparing a two-dimensional material is provided, the method comprising: and (3) using the intercalation method to enable the polymer to intercalate and exfoliate the clay material, so as to obtain the two-dimensional material.
The preparation method of the two-dimensional material has at least the following beneficial effects:
the two-dimensional clay mineral material is prepared by adopting polymer intercalation adhesion, the prepared two-dimensional clay mineral material has large sheet diameter and high quality, the preparation process is natural and pollution-free, the green, efficient and large-scale stripping preparation of the large-sheet-diameter and high-quality two-dimensional clay mineral material can be realized, the operation process is simple and convenient, the natural and pollution-free processes are realized, the energy consumption is low, and the preparation method is suitable for large-scale industrial production.
In some embodiments of the invention, the polymer comprises a naturally modified polymer.
In some embodiments of the invention, the polymer comprises at least one of a hydroxyl group or a carboxyl group.
In some embodiments of the invention, the polymer comprises at least one of sodium carboxymethyl cellulose, sodium alginate, chitin, chitosan, gelatin, or protein.
By the above embodiment, the polymer is selected from natural modified polymers rich in hydroxyl and carboxyl functional groups. The clay mineral material has wide sources in nature, is natural and nontoxic, has low cost, can be recycled, has suspended hydroxyl groups on the surface, has self-charge among layers, and can form rich interaction with macromolecules so as to promote intercalation and adhesion of the macromolecules.
In some embodiments of the invention, the polymer solution includes a polymer and a solvent. Preferably, the solvent comprises at least one of water, acetic acid, ethanol or acetone. More preferably, the water is deionized water.
In some embodiments of the invention, the mass ratio of the polymer to clay material is (0.1-50): 1.
In some embodiments of the invention, the clay material comprises at least one of a kaolin group clay, a montmorillonite group clay, an illite group clay, a chlorite group clay, or a vermiculite clay.
In some preferred embodiments of the present invention, the clay material includes at least one of kaolinite, montmorillonite, illite, chlorite, or vermiculite.
In some embodiments of the invention, the clay material has a particle size of 3-8mm.
In some embodiments of the invention, the clay material comprises particles of vermiculite from Shanghai sigma aldrich trade, particles of montmorillonite from Shanghai sigma aldrich trade, particles of vermiculite from Xinjiang company, particles of vermiculite from Hebei Jili, or particles of vermiculite from Shanghai Meilin Biochemical technology.
In some embodiments of the invention, the method of preparation comprises the steps of: and (3) taking a mixture of a polymer solution and a clay material, grinding or ball milling, and intercalating and exfoliating the clay material by the polymer to obtain a dispersion liquid I, and removing the polymer to obtain the two-dimensional material.
In some preferred embodiments of the invention, the milling time is within 12 hours.
In some more preferred embodiments of the invention, the milling time is within 8 hours.
In some preferred embodiments of the invention, the milling speed is in the range of 90-110r/min.
In some more preferred embodiments of the invention, the mixture is milled using a mortar mill for a period of less than 8 hours at a milling speed of 100r/min.
The grinding process adopts the full-automatic treatment of the mortar grinding instrument, has low power consumption, convenient operation and simple and quick process flow, and is suitable for industrial production.
In some embodiments of the present invention, the method for preparing the mixture of the polymer solution and the clay material includes the steps of: mixing the polymer solution with clay material to obtain the mixture.
The specific steps include adding prepared polymer solution with certain viscosity into a mortar, adding layered clay mineral with certain mass ratio, and stirring and mixing uniformly.
In some preferred embodiments of the present invention, the polymer removal method includes: at least one of centrifugation, washing, or suction filtration, washing, or dialysis.
In some more preferred embodiments of the present invention, the polymer removal method comprises the following operations:
sa-1, standing the dispersion liquid I, taking supernatant, centrifuging to obtain supernatant I and precipitate, and removing the supernatant I;
sa-2, mixing the obtained precipitate with a solvent, centrifuging to obtain a supernatant II and a precipitate I, and removing the supernatant II;
sa-3, repeating the step Sa-2n times, wherein n is more than or equal to 1, and n is an integer.
In some more preferred embodiments of the present invention, in steps Sa-1 to Sa-3, the rate of centrifugation is not less than 5000r/min.
In some more preferred embodiments of the present invention, in steps Sa-1 to Sa-3, the centrifugation time is not less than 30 minutes.
In some more preferred embodiments of the present invention, in steps Sa-2-Sa-3, the solvent is deionized water.
In some more preferred embodiments of the present invention, the polymer removal method comprises the following operations:
sb-1, standing the dispersion liquid I, taking supernatant fluid thereof, and carrying out suction filtration to obtain a filter cake;
sb-2, mixing the obtained filter cake with a solvent, and carrying out suction filtration to obtain a filter cake I;
sb-3, repeating the step Sb-2n times, wherein n is more than or equal to 1, and n is an integer.
In some more preferred embodiments of the present invention, the polymer removal method comprises the following operations:
sc-1, standing the dispersion liquid I, taking supernatant, placing the supernatant in a dialysis bag, placing the dialysis bag in deionized water, dialyzing for 6-10h, and taking out the dialysis bag;
sc-2, repeating dialysis for 3 times or more.
In some more preferred embodiments of the invention, the dialysis bag used for the dialysis has a molecular weight cut-off of 10-350k D.
In some embodiments of the invention, the method of preparation comprises the steps of:
s1, mixing a high molecular solution with a clay material to obtain a mixture;
s2, grinding or ball milling the mixture, and intercalating and exfoliating the clay material by the polymer to obtain a dispersion liquid I;
s3, standing, taking supernatant, centrifuging, removing the polymer to obtain a dispersion liquid II, and obtaining the two-dimensional material.
The preparation method further comprises a step S4 of diluting the dispersion liquid II to obtain the two-dimensional material.
In a third aspect of the present invention, a two-dimensional material is provided, which is prepared by using the preparation method of the two-dimensional material.
In some embodiments of the invention, the sheet diameter of the two-dimensional material is greater than 0.1 μm.
In some embodiments of the invention, the two-dimensional material may be present in a dispersion or in solid form.
In a fourth aspect of the present invention, a method for preparing a composite material is provided, the method comprising: and (3) using the intercalation method to enable the polymer to intercalate and exfoliate the clay material, so as to obtain the composite material.
The preparation method of the composite material provided by the embodiment of the invention has at least the following beneficial effects:
the two-dimensional clay mineral material is prepared by adopting polymer intercalation adhesion, and the prepared two-dimensional clay mineral material has large sheet diameter and high quality, is natural and pollution-free in the preparation process, and can be prepared in a large scale. The invention can realize continuous and uniform preparation of the composite film of the two-dimensional clay mineral and the polymer, and the obtained composite material of the two-dimensional clay mineral/the polymer has excellent mechanical property, thermal stability, visible light transmittance, ultraviolet blocking property and circularity, can be applied to the fields of environmental protection, electronic devices, sensors or functional composite materials, is particularly suitable for multifunctional glass coatings, and has good application prospect.
The composite material comprises the two-dimensional material or the two-dimensional material prepared by the preparation method of the two-dimensional material.
In some embodiments of the invention, the method of preparation comprises the steps of: and (3) taking a mixture of a polymer solution and a clay material, grinding or ball milling, and conducting intercalation and exfoliation on the clay material by the polymer to obtain a dispersion liquid I, and conducting evaporation-induced self-assembly to obtain the composite material. The dispersion I contains the two-dimensional material.
The evaporation self-assembly time can depend on the humidity and the temperature of the experimental environment.
In some embodiments of the invention, the method of preparation comprises the steps of: and (3) taking a mixture of a polymer solution and a clay material, grinding or ball milling, and conducting intercalation and exfoliation on the clay material by the polymer to obtain a dispersion liquid I, carrying out ultrasonic treatment, stirring, removing bubbles, and conducting evaporation-induced self-assembly to obtain the composite material.
In some preferred embodiments of the invention, the ultrasound is water bath ultrasound. Preferably, the ultrasonic power is 100-400W, and the ultrasonic duration is 10-30min.
In some preferred embodiments of the invention, the stirring is at a rate of 400-800r/min for a period of 10-30min. Preferably, the stirring is performed using an overhead stirrer.
In some preferred embodiments of the invention, the removal of bubbles is performed using a vacuum oven evacuation mode.
In some preferred embodiments of the invention, dispersion I is subjected to ultrasonic and agitation treatment, the bubbles in dispersion I are removed, and then poured into a mold, placed in an indoor environment, and waited for evaporation self-assembly.
In some more preferred embodiments of the invention, the mold comprises at least one of a plastic petri dish, a polyethylene terephthalate flexible substrate, a glass slide, or a polytetrafluoroethylene substrate.
In a fifth aspect of the present invention, a composite material is provided, the composite material comprising the two-dimensional material described above or a two-dimensional material produced by the production method of the two-dimensional material described above, or the composite material being produced by the production method of the composite material described above.
In some embodiments of the invention, the composite material is a composite film.
In a sixth aspect of the invention, a glass coating material is provided, the glass coating material comprising the composite material described above. Preferably, the glass coating is a multifunctional glass coating. The obtained multifunctional glass coating can simultaneously meet aesthetic and privacy requirements, mechanical requirements, thermal stability requirements, visible light transmission requirements, ultraviolet blocking requirements and recyclable requirements, and has good application prospect.
In a seventh aspect of the invention, the use of the above-described two-dimensional material or composite in a sensor or functional composite is presented.
In some embodiments of the invention, the two-dimensional material or composite described above is used in the preparation of a glass coating.
Drawings
The invention is further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is a diagram showing a two-dimensional vermiculite dispersion prepared in example 1 of the present invention under laser irradiation;
FIG. 2 is a transmission electron microscope image and a sheet diameter statistical chart of the two-dimensional vermiculite prepared in the embodiment 1 of the present invention;
FIG. 3 is a graphical representation of six two-dimensional vermiculite dispersions prepared in examples 2-7 of the present invention;
FIG. 4 is a graph showing the results of the diameter test of six kinds of two-dimensional vermiculite sheets prepared in examples 2 to 7 of the present invention;
FIG. 5 is a physical diagram of two-dimensional vermiculite dispersion prepared in examples 8-9 of the present invention;
FIG. 6 is a two-dimensional vermiculite transmission electron microscope image prepared in examples 8-9 of the present invention;
FIG. 7 is a physical diagram of a two-dimensional montmorillonite dispersion liquid prepared in example 10 of the present invention;
FIG. 8 is a graph showing the results of the sheet diameter test of the two-dimensional montmorillonite prepared in example 10 of the present invention;
FIG. 9 is a graph showing the results of the diameter test of four kinds of two-dimensional vermiculite sheets prepared in example 11 of the present invention;
FIG. 10 is a physical image and a scanning electron microscope image of the two-dimensional vermiculite/sodium carboxymethylcellulose composite film prepared in example 12 of the present invention;
FIG. 11 is a physical diagram of a color two-dimensional vermiculite/sodium carboxymethylcellulose composite film prepared in example 13 of the present invention;
FIG. 12 is a stress-strain curve of a color two-dimensional vermiculite/sodium carboxymethylcellulose composite film prepared in example 13 of the present invention;
FIG. 13 is a thermogravimetric analysis graph of the colored two-dimensional vermiculite/sodium carboxymethylcellulose composite film prepared in example 13 of the present invention;
FIG. 14 is an ultraviolet-visible spectrum of a color two-dimensional vermiculite/sodium carboxymethylcellulose composite film prepared in example 13 of the present invention;
FIG. 15 is a graph showing the results of tensile strength tests after initial, 1 cycle and 3 cycles of the colored two-dimensional vermiculite/sodium carboxymethylcellulose composite film prepared in example 13 of the present invention;
FIG. 16 is a scanning electron microscope image of the two-dimensional vermiculite prepared in comparative example 1;
FIG. 17 is a scanning electron microscope image of the two-dimensional vermiculite prepared in comparative example 2.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
In the description of the present invention, the meaning of a number is one or more, the meaning of a number is two or more, and greater than, less than, exceeding, etc. are understood to exclude the present number, and the meaning of a number is understood to include the present number. The description of the first and second is for the purpose of distinguishing between technical features only and should not be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated.
The raw materials, reagents and the like used in the following examples are those commercially available from conventional markets and the like unless otherwise specified.
Example 1
The embodiment discloses a two-dimensional material, which is a two-dimensional clay mineral material, and the preparation process comprises the following steps:
1.0g of particles of exfoliated vermiculite (Sigma Aldrich trade Co., shanghai, Z765422, particle size 2-3 mm) were taken. 1.0g of sodium carboxymethylcellulose (Sigma Aldrich trade Co., ltd., shanghai, viscosity: 5000-10000 mPa.s) was dissolved in 99.0g of deionized water to prepare a sodium carboxymethylcellulose solution having a mass fraction of 1%. And then adding the sodium carboxymethyl cellulose solution and the lamellar vermiculite particles into a mortar of a mortar grinder, and manually and uniformly stirring in advance. Starting a mortar grinder, wherein the grinding rotating speed is 100r/min, and grinding for 8 hours to obtain the two-dimensional vermiculite/sodium carboxymethyl cellulose mixed dispersion liquid.
(II) standing the obtained two-dimensional vermiculite/sodium carboxymethyl cellulose mixed dispersion liquid, taking supernatant, and removing sodium carboxymethyl cellulose in the supernatant, wherein the specific steps comprise: centrifuging the supernatant at a centrifugation rate of 11000r/min for 1h, taking a precipitate, adding water for centrifugation again, repeating centrifugation for 5 times to remove sodium carboxymethylcellulose to obtain a precipitate (two-dimensional clay mineral material), and adding water into the precipitate to obtain a two-dimensional vermiculite dispersion (wherein the concentration of the two-dimensional vermiculite is 1-2 mg/mL) to obtain the two-dimensional clay mineral material. For ease of detection and application, the concentration of the two-dimensional vermiculite dispersion may be diluted as desired.
Example 2
The present example discloses a two-dimensional material, which is a two-dimensional clay mineral material, and the preparation process is the same as that of example 1, and the difference from example 1 is only that: the layered vermiculite in the embodiment is vermiculite particles (the particle size of the particles is 3-5 mm) produced by the Xinjiang luli ore deposit.
Example 3
The present example discloses a two-dimensional material, which is a two-dimensional clay mineral material, and the preparation process is the same as that of example 1, and the difference from example 1 is only that: the layered vermiculite in the embodiment is vermiculite particles (the particle size of the particles is 5-8 mm) produced by the Xinjiang luli ore deposit.
Example 4
The present example discloses a two-dimensional material, which is a two-dimensional clay mineral material, and the preparation process is the same as that of example 1, and the difference from example 1 is only that: the layered vermiculite in the embodiment is vermiculite particles (particle size is 3-5 mm) produced by Hebei life deposit.
Example 5
The present example discloses a two-dimensional material, which is a two-dimensional clay mineral material, and the preparation process is the same as that of example 1, and the difference from example 1 is only that: the layered vermiculite in the embodiment is vermiculite particles (the particle size of the particles is 5-8 mm) produced by Hebei life deposit.
Example 6
The present example discloses a two-dimensional material, which is a two-dimensional clay mineral material, and the preparation process is the same as that of example 1, and the difference from example 1 is only that: the layered vermiculite in this example was purchased from Shanghai sigma aldrich trade company as vermiculite particles (Z765422, particle size 2-3 mm).
Example 7
The present example discloses a two-dimensional material, which is a two-dimensional clay mineral material, and the preparation process is the same as that of example 1, and the difference from example 1 is only that: the layered vermiculite in this example was purchased from vermiculite particles (V885843) from shanghai macelin biochemical technology limited.
Example 8
The present example discloses a two-dimensional material, which is a two-dimensional clay mineral material, and the preparation process is the same as that of example 1, and the difference from example 1 is only that: in this example, sodium alginate solution was used instead of the sodium carboxymethyl cellulose solution in example 1. Wherein the sodium alginate is purchased from Shanghai sigma Aldrich trade company, the viscosity is more than or equal to 2000cP,2% (25 ℃) (lite) and is derived from brown algae.
The preparation of the sodium alginate solution comprises the following operations: 1.0g of sodium alginate powder is taken and dissolved in 99.0g of deionized water, and is stirred into uniform sodium alginate solution with the mass fraction of 1% by an overhead stirrer.
Example 9
The present example discloses a two-dimensional material, which is a two-dimensional clay mineral material, and the preparation process is the same as that of example 1, and the difference from example 1 is only that: in this example, a chitosan solution was used instead of the sodium carboxymethyl cellulose solution of example 1. Wherein the chitosan is purchased from Shanghai sigma Aldrich trade company, the deacetylation degree is more than or equal to 95%, the viscosity is 100-200 mPa.s, and the chitosan is derived from chitin.
Wherein the preparation of the chitosan solution comprises the following operations: 1.0g of chitosan powder was dissolved in a mixed solvent of 99.0g of deionized water and 1.0g of glacial acetic acid (AR, 99.5%, mw=60.05), and then heated for 12 hours at 60 ℃ under stirring (300 rpm) to obtain a uniformly mixed chitosan solution.
Example 10
The present example discloses a two-dimensional material, which is a two-dimensional clay mineral material, and the preparation process is the same as that of example 1, and the difference from example 1 is only that: in this example, montmorillonite K10 (281522, powder) was used instead of the exfoliated vermiculite particles of example 1.
Example 11
The present example provides four two-dimensional materials, which are two-dimensional clay mineral materials, specifically two-dimensional vermiculite dispersion, and the preparation process is the same as that of example 1, and the difference from example 1 is that the grinding time periods in step S1 are respectively 4h,12h,24h and 48h.
Example 12
The embodiment discloses a composite material, in particular a two-dimensional vermiculite/sodium carboxymethyl cellulose composite film, and the preparation process comprises the following steps:
1.0g of sodium carboxymethyl cellulose is weighed and dissolved in 99.0g of deionized water, and uniformly stirred to obtain sodium carboxymethyl cellulose solution.
(II) adding 1.0g of vermiculite particles (Z765422, particle size is 2-3 mm) and the sodium carboxymethyl cellulose solution prepared in the step (I) into a mortar of a mortar grinder, and starting the grinder after manual pre-stirring uniformly, and grinding for 8 hours to obtain the two-dimensional vermiculite/sodium carboxymethyl cellulose composite dispersion liquid.
(III) the two-dimensional vermiculite/sodium carboxymethyl cellulose composite dispersion liquid is subjected to ultrasonic treatment for 20min at 100W for 10min at 600rpm, air bubbles are removed by a vacuum drying oven, the two-dimensional vermiculite/sodium carboxymethyl cellulose composite dispersion liquid is poured into a plastic culture dish (6 cm multiplied by 6 cm), and the two-dimensional vermiculite/sodium carboxymethyl cellulose composite film is obtained after being placed at room temperature for 5 days.
The embodiment also provides a multifunctional glass coating material, which comprises the composite material prepared in the embodiment.
Example 13
The embodiment discloses a composite material, in particular a two-dimensional vermiculite/sodium carboxymethyl cellulose composite film, the preparation process is the same as that of the embodiment 12, and the difference from the embodiment 12 is that:
in step (III): and (3) uniformly mixing the supernatant obtained after standing the obtained two-dimensional vermiculite/sodium carboxymethyl cellulose composite dispersion liquid for 4 hours with 1-2 drops of edible pigments (compound coloring agent, the production place is Guangzhou city of Guangdong province) with different colors.
The embodiment provides a multifunctional glass coating material, which comprises the composite material prepared in the embodiment.
Example 14
The present embodiment discloses a two-dimensional material, which is a two-dimensional clay mineral material, and differs from embodiment 1 only in the removal step of sodium carboxymethyl cellulose in step (ii), and specifically in this embodiment:
in the step (II), standing the obtained two-dimensional vermiculite/sodium carboxymethyl cellulose mixed dispersion liquid, taking supernatant, and removing sodium carboxymethyl cellulose in the supernatant, wherein the specific steps comprise: and (3) carrying out suction filtration on the supernatant, taking a filter cake, adding water for secondary suction filtration, and repeating the suction filtration for 5 times to remove sodium carboxymethyl cellulose, thereby obtaining a precipitate (two-dimensional clay mineral material).
Example 15
The present embodiment discloses a two-dimensional material, which is a two-dimensional clay mineral material, and differs from embodiment 1 only in the removal step of sodium carboxymethyl cellulose in step (ii), and specifically in this embodiment:
in the step (II), standing the obtained two-dimensional vermiculite/sodium carboxymethyl cellulose mixed dispersion liquid, taking supernatant, and removing sodium carboxymethyl cellulose in the supernatant, wherein the specific steps comprise: and (3) placing the supernatant into a dialysis bag, placing the dialysis bag into deionized water, dialyzing for 6-10h, taking out the dialysis bag (the molecular weight cut-off of the dialysis bag is 10-350 and k D), and repeating dialysis for 5 times to obtain the two-dimensional clay mineral material.
The experimental results of examples 14-15 are comparable to example 1.
Comparative example 1
This comparative example provides a two-dimensional vermiculite, prepared in the same way as example 1, which differs from example 1 only in that the mass fraction of sodium carboxymethyl cellulose solution used in step S1 is 0.1%.
Comparative example 2
This comparative example provides a two-dimensional vermiculite, prepared in the same way as example 1, which differs from example 1 only in that the mass fraction of sodium carboxymethyl cellulose solution used in step S1 is 5%.
Test examples
The present test example performed performance tests on the dispersions, two-dimensional materials, or composite films obtained in the examples and comparative examples, and specifically included:
(1) Performance test of the two-dimensional material prepared in example 1:
taking the two-dimensional vermiculite dispersion liquid prepared in the step (II) in the example 1, centrifuging at a rotating speed of 3000rpm for 15min, taking supernatant, and irradiating with laser, wherein the clear two-dimensional vermiculite dispersion liquid shows obvious tyndall phenomenon under the irradiation of the laser, so that the example 1 successfully exfoliates lamellar vermiculite into two-dimensional vermiculite.
Taking the two-dimensional vermiculite dispersion liquid prepared in the step (II) in the embodiment 1, centrifuging at a rotating speed of 3000rpm for 15min, taking supernatant, and preparing a transmission electron microscope sample, wherein a transmission electron microscope image and a sheet diameter distribution statistical result are shown in fig. 2, wherein fig. 2 (a) is a low-power transmission electron microscope image of a two-dimensional vermiculite nano sheet, fig. 2 (b) is a high-power transmission electron microscope image of the two-dimensional vermiculite nano sheet, and fig. 2 (c) is a two-dimensional vermiculite sheet diameter statistical chart, and it can be seen that the two-dimensional vermiculite prepared in the embodiment 1 has a larger sheet diameter size and a thinner thickness, and the average sheet diameter is 1.83 mu m.
(2) Performance test of two-dimensional materials prepared in examples 2-7:
taking the two-dimensional vermiculite dispersion liquid prepared in the step (II) in the examples 2-7 respectively, centrifuging at 3000rpm for 15min, taking supernatant, and obtaining a physical diagram shown in figure 3, wherein the six prepared two-dimensional vermiculite dispersion liquid is transparent and stable except for slight differences in the color of the final solution caused by different element compositions due to different production places, which indicates that the six layered vermiculite particles can be effectively peeled through polymer intercalation grinding. The dynamic light scattering results of the various two-dimensional vermiculite supernatants obtained in examples 2-7 are shown in fig. 4, and the results show that the average sheet diameter sizes of the two-dimensional vermiculite obtained by polymer intercalation adhesion are respectively as follows: 959.5nm,1052.6nm,1010nm,1002nm,1830nm,961nm, and the difference in the sheet diameter is mainly caused by different surface charges brought by different production places, different numbers of dangling bonds and the like.
(3) Performance test of two-dimensional materials prepared in examples 8-9:
and (3) respectively taking the two-dimensional vermiculite dispersion liquid prepared in the step (II) in the examples 8-9, diluting to the concentration of the two-dimensional vermiculite at 1mg/mL, and obtaining a physical diagram shown in figure 5, wherein the two-dimensional vermiculite dispersion liquid obtained by intercalation, adhesion and stripping of sodium alginate and chitosan solution is uniform and stable, so that the sodium alginate and chitosan can assist in stripping lamellar vermiculite minerals.
Fig. 6 is a transmission electron microscope image of a two-dimensional vermiculite nano sheet obtained by intercalation adhesion and stripping of sodium alginate and chitosan, and it can be seen from the figure that the two-dimensional vermiculite nano sheet obtained by auxiliary stripping of sodium alginate and chitosan has the sheet diameter sizes of about 0.5-1 μm and about 1-2 μm respectively.
(4) Performance test of the two-dimensional material prepared in example 10:
taking the two-dimensional montmorillonite dispersion liquid prepared in the step (II) in the example 10, centrifuging at 3000rpm for 15min, and taking supernatant, wherein the obtained physical diagram is shown in figure 7, and the two-dimensional montmorillonite dispersion liquid is in a stable and uniform state, which shows that the invention can realize effective stripping of other clay mineral materials.
The result of measuring the plate size distribution of the two-dimensional montmorillonite dispersion liquid prepared in example 10 by using a dynamic light scattering instrument is shown in FIG. 8, and it can be seen from FIG. 8 that the average plate size of the two-dimensional montmorillonite obtained in example 10 is 836.8nm.
(5) Performance test of the two-dimensional material prepared in example 11:
four two-dimensional vermiculite dispersion solutions prepared in example 11 are respectively taken, the two-dimensional vermiculite dispersion solutions are centrifuged at 3000rpm for 15min, and then supernatant is taken, dynamic light scattering is shown in fig. 9, and the results show that the average sheet diameter sizes of the two-dimensional vermiculite dispersion solutions obtained by adopting different grinding time periods are respectively as follows: 1322nm,1589nm,480.9nm and 347.6nm, it is shown that a proper grinding time can obtain two-dimensional vermiculite with larger sheet diameter, and a longer grinding time can lead to a reduction of the sheet diameter.
(6) Performance test of the composite film prepared in example 12:
fig. 10 is a physical diagram and a scanning electron microscope diagram of a two-dimensional vermiculite/sodium carboxymethyl cellulose composite film prepared in example 12 of the present invention, and it can be seen that the two-dimensional vermiculite/sodium carboxymethyl cellulose composite film prepared in the present invention has a uniform and continuous surface morphology.
(7) Performance test of the composite film prepared in example 13:
fig. 11 is a physical diagram of a color two-dimensional vermiculite/sodium carboxymethyl cellulose composite film prepared in example 13 of the present invention, and it can be seen that the color two-dimensional vermiculite/sodium carboxymethyl cellulose composite film prepared in the present invention has uniform coloring, and good processibility and machinability.
Fig. 12 is a stress-strain curve of the two-dimensional vermiculite/sodium carboxymethylcellulose composite film prepared in example 13 of the present invention, and as can be seen from fig. 12, the tensile strength is 75.51MPa, the young modulus is 7.66GPa, and good mechanical strength is exhibited.
FIG. 13 is a thermogravimetric analysis curve of the two-dimensional vermiculite/sodium carboxymethylcellulose composite film prepared in example 13 of the present invention, which shows good thermal stability up to 300℃as seen in FIG. 13, with the weight remaining almost unchanged in air below 300 ℃.
Fig. 14 shows the uv-vis spectrum of the two-dimensional vermiculite/sodium carboxymethylcellulose composite film prepared in example 13 of the present invention, and as can be seen from fig. 14, the transmittance of the two-dimensional vermiculite/sodium carboxymethylcellulose composite film in the visible light range is more than 60%, the transmittance in the uv light range is less than 20%, and the two-dimensional vermiculite/sodium carboxymethylcellulose composite film exhibits good visible light transmittance and uv blocking.
FIG. 15 shows the initial and 3 cycle tensile strengths of a two-dimensional vermiculite/sodium carboxymethylcellulose composite film prepared in example 13 according to the present invention, which is specifically prepared by:
the two-dimensional vermiculite/sodium carboxymethyl cellulose composite film prepared in the embodiment 13 of the invention is shredded into small pieces, a proper amount of deionized water is added, then ultrasonic treatment is carried out to form a uniformly mixed two-dimensional vermiculite/sodium carboxymethyl cellulose composite dispersion liquid, and then the assembly step (namely evaporation induction self-assembly) of the invention is repeated to obtain the two-dimensional vermiculite/sodium carboxymethyl cellulose composite film which circulates for 1 time.
As can be seen from fig. 15, after three cycles, the tensile strength of the two-dimensional vermiculite/sodium carboxymethyl cellulose composite film is still kept to be 93.8% of the tensile strength of the initial composite film, and the two-dimensional vermiculite/sodium carboxymethyl cellulose composite film prepared by the method provided by the invention has the circulability.
(8) Performance test of two-dimensional materials prepared in comparative examples 1-2:
taking the two-dimensional vermiculite dispersion liquid prepared in the comparative example 1, centrifuging at a rotating speed of 3000rpm for 15min, taking supernatant, and preparing a scanning electron microscope sample, wherein a scanning electron microscope image is shown in fig. 16, and as can be seen from fig. 16, the two-dimensional vermiculite dispersion liquid prepared by assistance of a polymer solution with low mass fraction (the mass fraction of the polymer is lower than 0.5%) has larger thickness and obvious agglomeration, which indicates that a polymer with certain mass fraction is a key for realizing polymer intercalation adhesion and stripping.
Taking the two-dimensional vermiculite dispersion liquid prepared in the comparative example 2, centrifuging at a rotating speed of 3000rpm for 15min, taking supernatant, and preparing a scanning electron microscope sample, wherein a scanning electron microscope image is shown in figure 17, and it can be seen from figure 17 that the high-quality polymer solution (the high-quality polymer fraction is higher than 3%) is assisted to prepare the two-dimensional vermiculite with larger thickness, obvious agglomeration and complete stripping, so that the high-quality polymer solution cannot be effectively intercalated into vermiculite layers, and the important effect of the intercalation effect of the high polymer in stripping is also demonstrated.
In summary, the invention provides a method for preparing a two-dimensional clay mineral material by polymer intercalation adhesion and application of the two-dimensional clay mineral/polymer obtained by the one-step method in a multifunctional glass coating. Specifically, the invention adopts polymer solution with certain viscosity and lamellar clay mineral as raw materials to prepare grinding precursor liquid, and adopts a one-pot method to prepare the grinding precursor liquid, thus the operation is simple. The invention enlarges the interlayer spacing of clay materials (such as lamellar vermiculite) by utilizing the intercalation and adhesion functions of the polymer, reduces interlayer interaction, and promotes the sliding and the exfoliation of clay material lamellar layers by applying shearing force between the layers. The method can realize green, efficient and large-scale stripping of the large-diameter and high-quality two-dimensional mineral material. The prepared two-dimensional mineral material has the advantages of large sheet diameter of 1 mu m, high sheet diameter, natural pollution-free preparation process and realization of large-scale preparation, namely the large-scale, green, efficient and controllable preparation of the high-quality and large-sheet-diameter two-dimensional clay mineral, and has important significance for realizing high-valued application and further promoting the sustainable development of society. Meanwhile, the invention can also realize continuous and uniform preparation of the two-dimensional clay mineral/polymer composite film, and the prepared two-dimensional clay mineral/polymer composite material has excellent mechanical, thermal stability, optical, circulation and other performances and can be widely applied to functional composite materials.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of one of ordinary skill in the art without departing from the spirit of the present invention. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (4)
1. The preparation method of the two-dimensional clay material-polymer composite film for the glass coating is characterized by comprising the following steps of: taking a mixture of a polymer solution and a layered clay material, and carrying out grinding or ball milling, wherein the polymer intercalation adheres and strips the layered clay material to obtain a dispersion liquid I containing a polymer and a two-dimensional clay material; the polymer solution comprises a polymer and a solvent, wherein the solvent comprises at least one of water, acetic acid, ethanol or acetone;
carrying out ultrasonic treatment on the dispersion liquid I, stirring, removing bubbles, pouring into a mould, placing in a room temperature chamber in a wet manner, and waiting for solvent evaporation to obtain the composite film;
wherein the mass fraction of the polymer in the polymer solution is 0.5-3%; the polymer comprises at least one of sodium carboxymethyl cellulose, sodium alginate or chitosan;
the layered clay material is at least one of montmorillonite clay or vermiculite clay; the particle size of the layered clay material is 3-8mm;
the process of the polymer intercalation adhesion and peeling of the layered clay material is as follows: the mixture of the lamellar clay material and the polymer solution is ground or ball-milled, so that the polymer is adhered and intercalated in the lamellar clay material to obtain a dispersion liquid I; wherein the grinding time is within 12 hours; the grinding rotating speed is 90-110r/min;
the sheet diameter of the two-dimensional clay material is 0.1-2 mu m;
the film has a uniform and continuous surface topography.
2. The method for preparing a two-dimensional clay material-polymer composite film for glass coating according to claim 1, wherein the ultrasonic power is 100-400W and the ultrasonic duration is 10-30min.
3. The method for preparing a two-dimensional clay material-polymer composite film for glass coating according to claim 1, wherein the stirring speed is 400-800r/min, and the stirring time is 10-30min.
4. The method for preparing a two-dimensional clay material-polymer composite film for glass coating according to claim 1, wherein the bubble removal is performed in a vacuum oven evacuation mode.
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