CN115028171B - Basalt nano-sheet prepared by ion exchange method and preparation method - Google Patents
Basalt nano-sheet prepared by ion exchange method and preparation method Download PDFInfo
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- CN115028171B CN115028171B CN202210759607.2A CN202210759607A CN115028171B CN 115028171 B CN115028171 B CN 115028171B CN 202210759607 A CN202210759607 A CN 202210759607A CN 115028171 B CN115028171 B CN 115028171B
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 67
- 238000005342 ion exchange Methods 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 114
- 238000005530 etching Methods 0.000 claims abstract description 32
- 150000002500 ions Chemical class 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 64
- 239000000243 solution Substances 0.000 claims description 60
- 238000003756 stirring Methods 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 230000001804 emulsifying effect Effects 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 22
- 239000000725 suspension Substances 0.000 claims description 21
- 238000001291 vacuum drying Methods 0.000 claims description 21
- 238000000967 suction filtration Methods 0.000 claims description 15
- 238000004108 freeze drying Methods 0.000 claims description 11
- 238000000643 oven drying Methods 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- NEUSVAOJNUQRTM-UHFFFAOYSA-N cetylpyridinium Chemical compound CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 NEUSVAOJNUQRTM-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 3
- 150000004706 metal oxides Chemical class 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- 239000000945 filler Substances 0.000 abstract description 2
- 239000011810 insulating material Substances 0.000 abstract description 2
- 230000003075 superhydrophobic effect Effects 0.000 abstract description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 20
- 239000002086 nanomaterial Substances 0.000 description 19
- 238000007689 inspection Methods 0.000 description 18
- 230000007935 neutral effect Effects 0.000 description 18
- 238000005303 weighing Methods 0.000 description 18
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 12
- 239000011521 glass Substances 0.000 description 9
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 9
- 238000010907 mechanical stirring Methods 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- OBFSQMXGZIYMMN-UHFFFAOYSA-N 3-chloro-2-hexadecylpyridine Chemical compound CCCCCCCCCCCCCCCCC1=NC=CC=C1Cl OBFSQMXGZIYMMN-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000002064 nanoplatelet Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000000089 atomic force micrograph Methods 0.000 description 2
- 229960001927 cetylpyridinium chloride Drugs 0.000 description 2
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000599 controlled substance Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
Abstract
The invention provides a method for controlling the flow of liquid throughThe basalt nano sheet is prepared by adopting basalt flakes as raw materials, carrying out preliminary etching by acetic acid, removing partial metal oxides and impurities on the surface of the basalt nano sheet to form a rough structure on the surface of the basalt nano sheet, and further utilizing ions with smaller atomic radius to enter the inside of the basalt flakes and K in the basalt flakes + 、Na + 、Ca 2+ Ion exchange is carried out by plasma, so that more holes are formed in the basalt flakes, then the basalt flakes are subjected to hole action by mechanical force, so that the basalt flakes form a multi-layer structure, and finally the basalt flakes are formed by falling off; the basalt nanosheets prepared by the invention are used as a novel lamellar material, have large specific surface area and good acid and alkali resistance and corrosion resistance, can be used in the fields of super-hydrophobic coatings, anti-corrosion coatings, wear-resistant fillers and the like, and particularly have stable temperature resistance and excellent corona resistance, so that the basalt nanosheets have a very strong development prospect in the field of preparation of insulating materials.
Description
Technical Field
The invention belongs to the technical field of preparation of inorganic nano materials, and relates to a basalt nano sheet prepared by an ion exchange method and a preparation method thereof.
Background
Basalt is formed by condensing magma eruption, is dark gray rock with rough surface, and mainly comprises silicon oxide, iron oxide, aluminum oxide, magnesium oxide and the like. The basalt flakes are flake-like in shape, and are very similar to fish scales, and are therefore called basalt flakes. Basalt flakes can be prepared from basalt by special processes, and have a planar dimension of about 50 μm and a longitudinal dimension of 2 μm to 5 μm. At present, the basalt scales are rarely researched, and the basalt scales are researched to be used in the fields of corrosion prevention, water repellency, wear-resistant material preparation and the like, so that the effect is outstanding. Compared with other flake materials, the basalt flakes have the following advantages:
(1) The basalt flakes have smooth surfaces, can be arranged in other resin coatings or other polymers in parallel, are blocked by flakes after corrosive media enter the coatings, increase the transmission path of the media, and improve the corrosion resistance of the coatings.
(2) The basalt flake has good environmental adaptability, wide working temperature range, and strong weather resistance, and the service performance of the flake can not be changed even the temperature is 1000 ℃.
(3) The basalt flakes have high specific surface area, low Zeta potential and more stable dispersion effect, and can have enough space to grow transversely or longitudinally when being compounded with other materials such as polyaniline, so that the coating effect is better.
(4) The basalt flakes have rich sources and low cost, and have great contribution to low-carbon sustainable development.
In addition, the basalt flakes are nontoxic and harmless in the production process, raw materials are almost free of loss, the basalt flakes are novel environment-friendly materials, the basalt nano sheets are used as derivative products of the basalt flakes, the environment adaptability is good, the electrochemical performance is excellent, the basalt flakes are clean and low in cost, and the basalt flakes are good heart products capable of sustainable development and have wide application prospects in the fields of daily life, urban construction and even national defense and military industry. However, at present, the research on preparing basalt nano-sheets from basalt flakes by adopting an ion exchange method at home and abroad is very little.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a basalt nano sheet prepared by an ion exchange method and a preparation method, and the basalt nano sheet is prepared by successfully adopting the ion exchange method so as to fill the blank of the prior industry technology, and the invention uses basalt flakes as raw materials, performs preliminary etching through acetic acid to remove partial metal oxides and impurities on the surfaces of the basalt flakes, so that the surfaces of the basalt flakes form a coarse structure, and further uses ions with smaller atomic radius and strong hydration capability to enter the basalt flakes and K in the basalt flakes + 、Na + 、Ca 2+ Ion exchange is carried out on the plasma, and the ions with small atomic radius can be combined with water to formThe hydrated ions with larger radius are formed, so that the compact structure inside the basalt flakes is expanded, and then cavitation is carried out on the basalt flakes by mechanical force, so that the basalt flakes form a multi-layer structure, and finally the basalt nano-flakes are formed by falling off.
The invention is realized by the following technical scheme:
basalt nanosheets prepared by an ion exchange method, comprising the steps of:
step (1), adding an acetic acid solution into basalt flakes, heating, stirring, reacting, and washing to obtain primarily etched basalt flakes;
step (2), placing the primarily etched basalt flakes into a specific ionic water solution, performing ion exchange reaction at a set temperature, and after the reaction is finished, performing suction filtration and washing to obtain ion exchanged basalt flakes;
and (3) adding water into the ion-exchanged basalt flakes to prepare mixed suspension, then carrying out high-shear stirring treatment, standing, taking out the turbid liquid at the upper layer, and drying to obtain basalt nanosheets.
Preferably, the dosage ratio of basalt flake to acetic acid solution in the step (1) is 0.5g:50mL of the acetic acid solution was at a concentration of 3moL/L.
Preferably, the reaction time in the step (1) is 8-12 hours, the reaction temperature is 30-60 ℃, and the stirring speed is 1000rpm.
Preferably, the concentration of the specific ion aqueous solution in the step (2) is 0.5mol/L to 3mol/L, and the dosage ratio of the primarily etched basalt flakes to the specific ion aqueous solution is 1.0g:50 mL-200 mL.
Preferably, the specific ionic aqueous solution in the step (2) includes one of a lithium ion solution, a tetrabutylammonium ion solution and a cetylpyridinium ion solution.
Preferably, the temperature of the ion exchange reaction in the step (2) is 80-120 ℃, the stirring rate of the ion exchange reaction is 500-1500 rpm, and the time of the ion exchange reaction is 6-12 h.
Preferably, the dosage ratio of the basalt flake deeply etched in the mixed suspension in the step (3) to water is 0.75g:200 mL-300 mL.
Preferably, the time of the high-shear stirring treatment is 2-6 h, and the standing time is 36-48 h; the high-shear stirring treatment adopts a high-shear emulsifying stirrer, and the stirring speed is 3000r/min-8000r/min.
Preferably, the drying mode in the step (3) is one of vacuum drying, oven drying and freeze drying.
The basalt nano sheet prepared by the ion exchange method is prepared by the preparation method.
Preferably, the size of the basalt nanosheets prepared by the ion exchange method is 50nm-100nm.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention provides a basalt nanosheet prepared by an ion exchange method, which is prepared by taking basalt flakes as a raw material, carrying out preliminary etching by acetic acid to remove partial metal oxides and impurities on the surface of the basalt nanosheet, so that a rough structure is formed on the surface of the basalt nanosheet, and then utilizing ions with smaller atomic radius to enter the inside of the basalt flakes and K in the basalt flakes + 、Na + 、Ca 2+ The ions with small atomic radius can be combined with water to form hydrated ions with larger radius, so that the compact structure in the basalt flakes is expanded, and then the compact structure is subjected to cavitation by mechanical force, so that the basalt flakes form a multi-layer structure, finally fall off to form basalt nano-sheets, and the blank of the existing basalt nano-sheet preparation technology can be filled.
The basalt nanosheets prepared by the invention are used as a novel lamellar material, have large specific surface area and good acid and alkali resistance and corrosion resistance, can be used in the fields of super-hydrophobic coatings, anti-corrosion coatings, wear-resistant fillers and the like, and particularly have stable temperature resistance and excellent corona resistance, so that the basalt nanosheets have a very strong development prospect in the field of preparation of insulating materials.
Furthermore, the nano-sheet prepared by the invention has higher yield and better dispersion property, which indicates that the system is more stable, the storage time is long, and the transportation is convenient.
Furthermore, the basalt nanosheets are prepared by the simple and effective preparation method, experimental reaction medicines are not common controlled medicines, the reaction equipment is simple, the flow and the operation steps are simple and convenient, the reaction conditions are mild, the nanosheets yield is high, and industrialization is easy to realize.
Drawings
FIG. 1 is an AFM image of basalt flakes, primarily etched basalt flakes, basalt nanoplatelets of example 1; wherein, the figure (a) is basalt flake, the figure (b) is basalt flake which is etched preliminarily, and the figure (c) is basalt nano-sheet;
FIG. 2 is an SEM image of basalt flakes, primarily etched basalt flakes, basalt nanoplatelets of examples 2-7; wherein, fig. (a) is example 2, fig. (b) is example 3, fig. (c) is example 4, fig. (d) is example 5, fig. (e) is example 6, and fig. (f) is example 7;
FIG. 3 is a TEM image of basalt nanoplatelets of example 8; wherein, the drawing (a) is basalt nano-sheet with 500 times magnification, and the drawing (b) is basalt nano-sheet with 1000 times magnification.
Detailed Description
The invention will now be described in further detail with reference to specific examples, which are intended to illustrate, but not to limit, the invention.
Embodiments of the invention are described in further detail below:
(1) Preliminary etching of basalt flakes: weighing basalt flakes of a certain mass, placing into a three-necked flask, and preparing a certain amount of acetic acid solution (CH 3 COOH), and the dosage ratio of basalt flake to acetic acid solution is 0.5g:50mL, the concentration of acetic acid solution is 3moL/L, and the preliminary etching reaction is carried out by mechanical stirring for 6 to 12 hours under the water bath condition of 25 to 60 ℃. And after the reaction is finished, carrying out suction filtration and washing to be neutral (pH test paper inspection), and obtaining the primarily etched basalt flakes through the modes of vacuum drying, oven drying and freeze drying.
(2) Ion exchange reaction of basalt flakes: weighing a certain mass of primarily etched basalt scales, placing the primarily etched basalt scales into a three-necked flask, and adding prepared lithium chloride, tetrabutylammonium chloride and cetylpyridinium chloride solution with the concentration of 0.5-3 mol/L into the three-necked flask, wherein the dosage ratio of the primarily etched basalt scales to the lithium chloride, the tetrabutylammonium chloride and the cetylpyridinium chloride solution is 1.0g:50 mL-200 mL. The reaction temperature is 80-120 ℃, the stirring speed is 500-1500 rpm, and the reaction time is 6-12 h. And after the reaction is finished, carrying out suction filtration and washing to be neutral (pH test paper inspection), and obtaining the ion-exchanged basalt flakes through the modes of vacuum drying, oven drying and freeze drying.
(3) Preparation of basalt nanosheets: putting a certain mass of ion-exchanged basalt flakes into a plastic beaker, and adding a certain volume of water into the plastic beaker, wherein the mass ratio of the ion-exchanged basalt flakes to the water is 0.75g:200 mL-300 mL. Transferring the beaker with the sample into a cell grinder, placing the bottom of an amplitude transformer of the cell grinder at 2/3 of the sample in the beaker, opening the cell grinder, adjusting the power to 600-1000W to start the reaction, taking out the sample after the reaction is completed, and placing the sample into a glass bottle for later use. And after standing for 24 hours, taking out the turbid liquid at the upper layer, and obtaining the basalt nanosheets by means of vacuum drying, oven drying and freeze drying.
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. 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 present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
Example 1
Basalt nanosheets prepared by an ion exchange method, comprising the steps of:
(1) Preliminary etching of basalt flakes: weighing basalt flakes of a certain mass, placing into a three-necked flask, adding acetic acid solution (CH 3 COOH), and the dosage ratio of basalt flake to acetic acid solution is 0.5g:50mL of acetic acid solution with the concentration of 3moL/L is mechanically stirred for 12h under the water bath condition of 30 ℃ to carry out preliminary etching reaction. And after the reaction is finished, carrying out suction filtration and washing to be neutral (pH test paper inspection), and obtaining the primarily etched basalt flakes through a vacuum drying mode.
(2) Ion exchange reaction of basalt flakes: weighing a certain mass of primarily etched basalt scales, placing the primarily etched basalt scales into a three-necked flask, and adding prepared lithium chloride solution with the concentration of 0.5mol/L into the three-necked flask, wherein the dosage ratio of the primarily etched basalt scales to the lithium chloride solution is 1.0g:50mL. The reaction temperature was 80℃and the stirring rate was 500rpm, and the reaction time was 6 hours. And after the reaction is finished, filtering and washing to be neutral (pH test paper inspection), and obtaining the ion-exchanged basalt flakes through a vacuum drying mode.
(3) Preparation of basalt nanosheets: putting a certain mass of ion-exchanged basalt flakes into a plastic beaker, adding a certain volume of water into the basalt flakes to prepare a mixed suspension, wherein the mass ratio of the ion-exchanged basalt flakes to the water is 0.75g:200mL. Transferring the beaker with the sample into a high-speed emulsifying stirrer, putting the rotary head of the high-speed emulsifying stirrer into the beaker with the sample, starting the high-speed emulsifying stirrer, controlling the stirring speed to be 3000r/min, continuously stirring for 6 hours, taking out the sample, and placing the sample into a glass bottle for later use. And after standing for 36h, taking out the turbid liquid at the upper layer, and obtaining the basalt nanosheets by a vacuum drying mode.
As shown in fig. 1, fig. 1 (a) is a basalt flake, fig. b is a primarily etched basalt flake, and fig. c is an atomic force microscope image of a basalt nanosheet; analysis of basalt scales in the embodiment by an atomic force microscope shows that the roughness of the basalt scales is lower (1.668 nm), which indicates that the surface of the basalt scales is smoother; the roughness of basalt flakes treated by acetic acid is increased to 20.87nm, which indicates that the surface of basalt flakes is corroded to a certain extent by acetic acid, so that the surface of basalt flakes is roughened. And from fig. 1 (c), it can be found that basalt nano-sheets are formed after being subjected to high shear stirring treatment.
Example 2
Basalt nanosheets prepared by an ion exchange method, comprising the steps of:
(1) Preliminary etching of basalt flakes: weighing basalt flakes of a certain mass, placing into a three-necked flask, adding acetic acid solution (CH 3 COOH), and the dosage ratio of basalt flake to acetic acid solution is 0.4g:30mL, acetic acid solution concentration of 3moL/L, and under 40 ℃ water bath condition mechanical stirring 8h to carry out preliminary etching reaction. And after the reaction is finished, carrying out suction filtration and washing to be neutral (pH test paper inspection), and obtaining the primarily etched basalt flakes through the modes of vacuum drying, oven drying and freeze drying.
(2) Ion exchange reaction of basalt flakes: weighing a certain mass of primarily etched basalt scales, placing the primarily etched basalt scales into a three-necked flask, and adding a prepared tetrabutylammonium chloride solution with the concentration of 0.5mol/L into the three-necked flask, wherein the dosage ratio of the primarily etched basalt scales to the tetrabutylammonium chloride solution is 1.0g:50mL. The reaction temperature was 80℃and the stirring rate was 1000rpm, and the reaction time was 8 hours. And after the reaction is finished, carrying out suction filtration and washing to be neutral (pH test paper inspection), and obtaining the ion-exchanged basalt flakes through the modes of vacuum drying, oven drying and freeze drying.
(3) Preparation of basalt nanosheets: placing a certain mass of deeply etched basalt scales into a plastic beaker, adding a certain volume of water into the plastic beaker to prepare a mixed suspension, wherein the mass ratio of the deeply etched basalt scales to the water is 0.75g:200mL. Transferring the beaker with the mixed suspension into a high-speed emulsifying stirrer, putting the rotary head of the high-speed emulsifying stirrer into the beaker with the mixed suspension, starting the high-speed emulsifying stirrer, controlling the stirring speed to be 8000r/min, continuously stirring for 2 hours, taking out the sample, and placing the sample into a glass bottle for later use. And after standing for 40 hours, taking out the turbid liquid at the upper layer, and obtaining the basalt nanosheets by a vacuum drying mode. As can be seen from fig. 2a, the detection result of the nano material prepared by the implementation by using the field emission scanning electron microscope shows that the nano material after the preliminary etching, the ion exchange treatment and the high-shear stirring treatment is of a lamellar structure, and the thickness of the nano material is about 100nm.
Example 3
Basalt nanosheets prepared by an ion exchange method, comprising the steps of:
(1) Preliminary etching of basalt flakes: weighing basalt flakes of a certain mass, placing into a three-necked flask, adding acetic acid solution (CH 3 COOH), and the dosage ratio of basalt flake to acetic acid solution is 0.4g:30mL, acetic acid solution concentration of 3moL/L, and under the water bath condition of 60 ℃ and mechanical stirring for 10h, carrying out preliminary etching reaction. And after the reaction is finished, carrying out suction filtration and washing to be neutral (pH test paper inspection), and obtaining the primarily etched basalt flakes in an oven drying mode.
(2) Ion exchange reaction of basalt flakes: weighing a certain mass of primarily etched basalt scales, placing the primarily etched basalt scales into a three-necked flask, and adding prepared lithium chloride solution with the concentration of 1.0mol/L into the three-necked flask, wherein the dosage ratio of the primarily etched basalt scales to the lithium chloride solution is 1.0g:150mL. The reaction temperature was 100deg.C, the stirring rate was 1500rpm, and the reaction time was 8 hours. And after the reaction is finished, carrying out suction filtration and washing to be neutral (pH test paper inspection), and obtaining the ion-exchanged basalt flakes through an oven drying mode.
(3) Preparation of basalt nanosheets: putting a certain mass of ion-exchanged basalt flakes into a plastic beaker, adding a certain volume of water into the basalt flakes to prepare a mixed suspension, wherein the mass ratio of the ion-exchanged basalt flakes to the water is 0.75g:250mL. Transferring the beaker with the mixed suspension into a high-speed emulsifying stirrer, putting the rotary head of the high-speed emulsifying stirrer into the beaker with the mixed suspension, starting the high-speed emulsifying stirrer, controlling the stirring speed to be 5000r/min, continuously stirring for 4 hours, taking out the sample, and placing the sample into a glass bottle for later use. And standing for 48 hours, taking out the turbid liquid at the upper layer, and obtaining the basalt nanosheets by a vacuum drying mode.
The nanomaterial obtained by this implementation is detected by using a field emission scanning electron microscope, as shown in fig. 2b, and the detection result shows that the nanomaterial after the treatment of preliminary etching, deep etching and high shear stirring is of a lamellar structure, and the thickness of the nanomaterial is about 80 nm.
Example 4
Basalt nanosheets prepared by an ion exchange method, comprising the steps of:
(1) Preliminary etching of basalt flakes: weighing basalt flakes of a certain mass, placing into a three-necked flask, adding acetic acid solution (CH 3 COOH), and the dosage ratio of basalt flake to acetic acid solution is 0.4g:30mL, acetic acid solution concentration of 3moL/L, and mechanical stirring at 50deg.C water bath for 9h for preliminary etching reaction. And after the reaction is finished, carrying out suction filtration and washing to be neutral (pH test paper inspection), and obtaining the primarily etched basalt flakes in a freeze drying mode.
(2) Ion exchange reaction of basalt flakes: weighing a certain mass of primarily etched basalt scales, placing the primarily etched basalt scales into a three-necked flask, and adding a prepared tetrabutylammonium chloride solution with the concentration of 1.0mol/L into the three-necked flask, wherein the dosage ratio of the primarily etched basalt scales to the tetrabutylammonium chloride solution is 1.0g:150mL. The reaction temperature was 100deg.C, the stirring rate was 1500rpm, and the reaction time was 8 hours. And after the reaction is finished, filtering and washing to be neutral (pH test paper inspection), and obtaining the ion-exchanged basalt flakes through a vacuum drying mode.
(3) Preparation of basalt nanosheets: placing a certain mass of deeply etched basalt scales into a plastic beaker, adding a certain volume of water into the plastic beaker to prepare a mixed suspension, wherein the mass ratio of the deeply etched basalt scales to the water is 0.75g:250mL. Transferring the beaker with the mixed suspension into a high-speed emulsifying stirrer, putting the rotary head of the high-speed emulsifying stirrer into the beaker with the mixed suspension, starting the high-speed emulsifying stirrer, controlling the stirring speed to 6500r/min, continuously stirring for 3 hours, taking out the sample, and placing the sample into a glass bottle for later use. And standing for 48 hours, taking out the turbid liquid at the upper layer, and obtaining the basalt nanosheets by a vacuum drying mode.
The nanomaterial obtained by this implementation is detected by using a field emission scanning electron microscope, as shown in fig. 2c, and the detection result shows that the nanomaterial after the treatment of preliminary etching, deep etching and high shear stirring is of a lamellar structure, and the thickness of the nanomaterial is about 60 nm.
Example 5
Basalt nanosheets prepared by an ion exchange method, comprising the steps of:
(1) Preliminary etching of basalt flakes: weighing basalt flakes of a certain mass, placing into a three-necked flask, adding acetic acid solution (CH 3 COOH), and the dosage ratio of basalt flake to acetic acid solution is 0.4g:30mL, acetic acid solution concentration of 3moL/L, and under the water bath condition of 45 ℃ and mechanical stirring for 12h, carrying out preliminary etching reaction. And after the reaction is finished, carrying out suction filtration and washing to be neutral (pH test paper inspection), and obtaining the primarily etched basalt flakes in a freeze drying mode.
(2) Ion exchange reaction of basalt flakes: weighing a certain mass of primarily etched basalt scales, placing the primarily etched basalt scales into a three-necked flask, and adding prepared lithium chloride solution with the concentration of 2.0mol/L into the three-necked flask, wherein the dosage ratio of the primarily etched basalt scales to the lithium chloride solution is 1.0g:150mL. The reaction temperature was 110℃and the stirring rate was 1500rpm, and the reaction time was 8 hours. And after the reaction is finished, filtering and washing to be neutral (pH test paper inspection), and obtaining the ion-exchanged basalt flakes through a freeze drying mode.
(3) Preparation of basalt nanosheets: placing a certain mass of ion-exchanged basalt flakes into a plastic beaker, adding a certain volume of water into the basalt flakes to prepare a mixed suspension, wherein the mass ratio of the ion-exchanged basalt flakes to the water is 0.75g:200mL. Transferring the beaker with the mixed suspension into a high-speed emulsifying stirrer, putting the rotary head of the high-speed emulsifying stirrer into the beaker with the mixed suspension, starting the high-speed emulsifying stirrer, controlling the stirring speed to 6500r/min, continuously stirring for 3 hours, taking out the sample, and placing the sample into a glass bottle for later use. And standing for 48 hours, taking out the turbid liquid at the upper layer, and obtaining the basalt nanosheets by a vacuum drying mode. The nanomaterial obtained by this implementation is detected by using a field emission scanning electron microscope, as shown in fig. 2d, and the detection result shows that the nanomaterial after the treatment of preliminary etching, deep etching and high shear stirring is of a lamellar structure, and the thickness of the nanomaterial is about 50 nm.
Example 6
Basalt nanosheets prepared by an ion exchange method, comprising the steps of:
(1) Preliminary etching of basalt flakes: weighing basalt flakes of a certain mass, placing into a three-necked flask, adding acetic acid solution (CH 3 COOH), and the dosage ratio of basalt flake to acetic acid solution is 0.4g:30mL, acetic acid solution concentration of 3moL/L, and under the water bath condition of 60 ℃ and mechanical stirring for 12h to carry out preliminary etching reaction. And after the reaction is finished, carrying out suction filtration and washing to be neutral (pH test paper inspection), and obtaining the primarily etched basalt flakes through a vacuum drying mode.
(2) Ion exchange reaction of basalt flakes: weighing a certain mass of primarily etched basalt scales, placing the primarily etched basalt scales into a three-necked flask, and adding prepared cetyl pyridine chloride solution with the concentration of 2.0mol/L into the three-necked flask, wherein the dosage ratio of the primarily etched basalt scales to the cetyl pyridine chloride solution is 1.0g:200mL. The reaction temperature was 110℃and the stirring rate was 1500rpm, and the reaction time was 8 hours. And after the reaction is finished, filtering and washing to be neutral (pH test paper inspection), and obtaining the ion-exchanged basalt flakes through a vacuum drying mode.
(3) Preparation of basalt nanosheets: putting a certain mass of ion-exchanged basalt flakes into a plastic beaker, and adding a certain volume of water into the plastic beaker, wherein the mass ratio of the ion-exchanged basalt flakes to the water is 0.75g:200mL. Transferring the beaker with the mixed suspension into a high-speed emulsifying stirrer, putting the rotary head of the high-speed emulsifying stirrer into the beaker with the mixed suspension, starting the high-speed emulsifying stirrer, controlling the stirring speed to 6500r/min, continuously stirring for 3 hours, taking out the sample, and placing the sample into a glass bottle for later use. And standing for 48 hours, taking out the turbid liquid at the upper layer, and obtaining the basalt nanosheets by a vacuum drying mode.
As can be seen from fig. 2e, the detection result shows that the nano material obtained by the implementation is in a lamellar structure, and the nano material is about 50nm thick and uniform in size after the preliminary etching, the ion exchange treatment and the high-shear stirring treatment. The nano material prepared by the implementation is detected by using a transmission electron fiber microscope, and the nano material is found to be in a transparent state under the transmission electron microscope, which shows that the thickness is lower.
Example 7
Basalt nanosheets prepared by an ion exchange method, comprising the steps of:
(1) Preliminary etching of basalt flakes: weighing basalt flakes of a certain mass, placing into a three-necked flask, adding acetic acid solution (CH 3 COOH), and the dosage ratio of basalt flake to acetic acid solution is 0.4g:30mL, acetic acid solution concentration of 3moL/L, and under the water bath condition of 60 ℃ and mechanical stirring for 12h to carry out preliminary etching reaction. And after the reaction is finished, carrying out suction filtration and washing to be neutral (pH test paper inspection), and obtaining the primarily etched basalt flakes in an oven drying mode.
(2) Ion exchange reaction of basalt flakes: weighing a certain mass of primarily etched basalt scales, placing the primarily etched basalt scales into a three-necked flask, and adding prepared cetyl pyridine chloride solution with the concentration of 3.0mol/L into the three-necked flask, wherein the dosage ratio of the primarily etched basalt scales to the cetyl pyridine chloride solution is 1.0g:200mL. The reaction temperature was 110℃and the stirring rate was 1500rpm, the reaction time was 12h. And after the reaction is finished, filtering and washing to be neutral (pH test paper inspection), and obtaining the ion-exchanged basalt flakes through a vacuum drying mode.
(3) Preparation of basalt nanosheets: putting a certain mass of ion-exchanged basalt flakes into a plastic beaker, adding a certain volume of water into the basalt flakes, wherein the mass ratio of the deeply etched basalt flakes to the water is 0.75g:200mL. Transferring the beaker with the sample into a cell grinder, placing the bottom of an amplitude transformer of the cell grinder at 2/3 of the sample in the beaker, opening the cell grinder, adjusting the power to 1000W to start the reaction, taking out the sample after the reaction is completed for use in a glass bottle. And after the solution is placed for 24 hours, taking out the turbid liquid at the upper layer, and obtaining the basalt nanosheets by freeze drying.
As can be seen from fig. 2f, the detection result shows that the nano material obtained by the implementation is in a lamellar structure and has a thickness of about 50nm after the preliminary etching, the ion exchange treatment and the high-shear stirring treatment.
Example 8
Basalt nanosheets prepared by an ion exchange method, comprising the steps of:
(1) Preliminary etching of basalt flakes: weighing basalt flakes of a certain mass, placing into a three-necked flask, adding acetic acid solution (CH 3 COOH), and the dosage ratio of basalt flake to acetic acid solution is 0.4g:30mL, acetic acid solution concentration of 3moL/L, and under the water bath condition of 60 ℃ and mechanical stirring for 12h to carry out preliminary etching reaction. And after the reaction is finished, carrying out suction filtration and washing to be neutral (pH test paper inspection), and obtaining the primarily etched basalt flakes through a vacuum drying mode.
(2) Ion exchange reaction of basalt flakes: weighing a certain mass of primarily etched basalt scales, placing the primarily etched basalt scales into a three-necked flask, and adding prepared lithium chloride solution with the concentration of 3.0mol/L into the three-necked flask, wherein the dosage ratio of the primarily etched basalt scales to the lithium chloride solution is 1.0g:200mL. The reaction temperature was 120℃and the stirring rate was 1500rpm, and the reaction time was 12 hours. And after the reaction is finished, carrying out suction filtration and washing to be neutral (pH test paper inspection), and obtaining the ion-exchanged basalt flakes through an oven drying mode.
(3) Preparation of basalt nanosheets: placing a certain mass of deeply etched basalt scales into a plastic beaker, and adding a certain volume of water into the plastic beaker, wherein the mass ratio of the deeply etched basalt scales to the water is 0.75g:300mL. Transferring the beaker with the mixed suspension into a high-speed emulsifying stirrer, putting the rotary head of the high-speed emulsifying stirrer into the beaker with the mixed suspension, starting the high-speed emulsifying stirrer, controlling the stirring speed to 6500r/min, continuously stirring for 3 hours, taking out the sample, and placing the sample into a glass bottle for later use. And standing for 48 hours, taking out the turbid liquid at the upper layer, and obtaining the basalt nanosheets by a vacuum drying mode.
As can be seen from fig. 3 (a) and fig. 3 (b), the detection result shows that the nano material obtained by the implementation is in a lamellar structure after the preliminary etching, the ion exchange treatment and the high-shear stirring treatment. The basalt nano-sheet is prepared from basalt flakes through physical or chemical treatment, has a low Zeta potential, is stable in dispersion effect and high in specific surface area, and can be applied to the field of various composite materials.
Claims (7)
1. A method for preparing basalt nano-sheets by an ion exchange method, which is characterized by comprising the following steps:
step (1), adding an acetic acid solution into basalt flakes, heating, stirring, reacting, and washing to obtain primarily etched basalt flakes;
step (2), placing the primarily etched basalt flakes into a specific ionic water solution, performing ion exchange reaction at a set temperature, and after the reaction is finished, performing suction filtration and washing to obtain ion exchanged basalt flakes;
adding water into the ion-exchanged basalt flakes to prepare mixed suspension, then carrying out high-shear stirring treatment, standing, taking out an upper turbid liquid, and drying to obtain basalt nanosheets;
the dosage ratio of basalt flake to acetic acid solution in the step (1) is 0.5g:50mL, wherein the concentration of the acetic acid solution is 3moL/L;
the concentration of the specific ion aqueous solution in the step (2) is 0.5 mol/L-3 mol/L, and the dosage ratio of the basalt flake subjected to preliminary etching to the specific ion aqueous solution is 1.0g: 50-200 mL;
the specific ionic aqueous solution in the step (2) comprises one of a lithium ion solution, a tetrabutylammonium ion solution and a cetylpyridinium ion solution.
2. The method of preparing basalt nanosheets according to claim 1, wherein the reaction time in the step (1) is 8 to 12 hours, the reaction temperature is 30 to 60 ℃, and the stirring rate is 1000rpm.
3. The method of preparing basalt nano-sheet according to claim 1, wherein the temperature of the ion exchange reaction in the step (2) is 80-120 ℃, the stirring rate of the ion exchange reaction is 500-1500 rpm, and the time of the ion exchange reaction is 6-12 hours.
4. The method of preparing basalt nano-sheet according to claim 1, wherein the ratio of the amount of basalt flakes deeply etched in the mixed suspension in the step (3) to water is 0.75g:200 mL-300 mL.
5. The method of producing basalt nanosheets according to claim 1, wherein the time of the high shear stirring treatment in the step (3) is 2h to 6h, and the standing time is 36h to 48h; the high-shear stirring treatment adopts a high-shear emulsifying stirrer, and the stirring speed is 3000r/min-8000r/min.
6. The basalt nanosheets according to claim 1, wherein the drying means in the step (3) is one of vacuum drying, oven drying and freeze drying.
7. Basalt nanosheets prepared by an ion exchange process, characterized in that the size of basalt nanosheets prepared by the ion exchange process is 50nm to 100nm, based on the preparation process of any one of claims 1 to 6.
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| CN110449037A (en) * | 2019-07-08 | 2019-11-15 | 西安建筑科技大学 | A kind of two-dimensional layer vermiculite film, preparation and application |
| CN113830777A (en) * | 2021-10-27 | 2021-12-24 | 深圳先进技术研究院 | Vermiculite nanosheet and preparation method thereof |
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| CN110449037A (en) * | 2019-07-08 | 2019-11-15 | 西安建筑科技大学 | A kind of two-dimensional layer vermiculite film, preparation and application |
| CN113830777A (en) * | 2021-10-27 | 2021-12-24 | 深圳先进技术研究院 | Vermiculite nanosheet and preparation method thereof |
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