CN112093774A - Method for large-scale directional arrangement of halloysite nanotubes - Google Patents
Method for large-scale directional arrangement of halloysite nanotubes Download PDFInfo
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Abstract
The invention belongs to the field of halloysite nanotube self-assembly, and particularly relates to a method for large-scale directional arrangement of halloysite nanotubes. The method comprises the steps of selecting materials, purifying, modifying, dispersing and directionally arranging the halloysite nanotubes, wherein the directional arrangement is used for adjusting the pH value of dispersed liquid obtained after dispersion, then placing the dispersion in a container with a vertically placed substrate, and carrying out isothermal evaporation to obtain the large-scale directional halloysite nanotubes deposited on the substrate. According to the method, the halloysite nanotubes are modified by sodium hexametaphosphate, and then are subjected to isothermal evaporation to obtain the halloysite nanotubes in large-scale directional arrangement, so that the method is convenient to operate and simple in process.
Description
Technical Field
The invention belongs to the field of halloysite nanotube self-assembly, and particularly relates to a method for large-scale directional arrangement of halloysite nanotubes.
Background
As a natural tubular clay mineral, the halloysite nanotube is widely concerned due to the excellent structure and performance, and has high development and research values. The halloysite nanotube has a length and a tube diameter of nanometer level, a hollow nanotube structure with two open ends and a larger length-diameter ratio, the length of the halloysite nanotube is distributed in the range of 400-1500nm, the inner diameter and the outer diameter are respectively about 10-30nm and 50-100nm, and chemical Al is used2Si2O5(OH)4·nH2O (n ═ 0 or 2). The wall of the halloysite nanotube consists ofA plurality of layers of laminated structure units are stacked, and the laminated structure units are composed of external silicon-oxygen tetrahedrons and internal aluminum-oxygen octahedrons, the outer surfaces of HNTs mainly consist of Si-O-Si bonds, and the inner surfaces of the HNTs are mainly aluminum hydroxyl; Si/Al hydroxyl exists on the edges of HNTs or on the end faces of the HNTs, the aluminum octahedron consists of one aluminum atom and six surrounding oxygen atoms, and four of the six oxygen atoms are hydroxyl oxygen and are shared with the adjacent aluminum octahedron; the other two oxygens are linking oxygens, shared with the silicon-oxygen tetrahedra. The aluminum occupies only two thirds of the octahedral voids, and the remaining octahedral voids form six-membered ring holes; the silicon-oxygen tetrahedron is composed of a silicon atom and four surrounding oxygen atoms, wherein one oxygen atom is a connecting oxygen and is connected with the aluminum-oxygen octahedron; the other three are basal oxygens, shared with adjacent silicon-oxygen tetrahedra. Halloysite nanotubes exhibit electronegativity at pH greater than 2.4 and-50 mv at pH 6. The halloysite nanotube has different internal and external chemical compositions, so that the halloysite nanotube has the phenomena of positive internal charge and negative external charge. When the pH value of the halloysite nanotube solution is 2.5-8.5, the inner surface can be selectively modified.
Chinese patent with application number CN201410582392.7 discloses a directional arrangement method of halloysite nanotubes, a coating and application thereof, the method comprises the following steps: (1) constructing a limited evaporation space device: two substrates are oppositely arranged in a plane, and gaskets with the same height are clamped at two sides of the middle of the two substrates to form a space position with limited evaporation in the middle; (2) injecting an aqueous halloysite nanotube suspension into the confined vapor space device of step (1) in spatial position; (3) and horizontally standing the device spread with the halloysite nanotube water suspension, and obtaining a directionally arranged halloysite nanotube coating on the surface of the substrate after the suspension is gradually evaporated in a limited way. But the evaporation device needs to be independently constructed, and the arrangement of the halloysite nanotubes is not compact enough.
In 2014, Zhaoyao 23124. The above preparation method does not have the effect of orienting the halloysite in the same direction on a large scale.
The present invention has been made in view of this situation.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for large-scale directional arrangement of the halloysite nanotubes, which can realize large-scale directional arrangement of the halloysite nanotubes and has the advantages of simple and rapid operation and less flow.
In order to solve the technical problems, the invention adopts the technical scheme that:
a method for large-scale directional arrangement of halloysite nanotubes comprises the steps of selecting materials, purifying, modifying, dispersing and directionally arranging halloysite nanotubes, wherein the directional arrangement is used for adjusting the pH value of dispersed liquid obtained after dispersion, then placing the dispersed liquid in a container with a vertically placed substrate, and carrying out isothermal evaporation to obtain the large-scale directional halloysite nanotubes deposited on the substrate.
The modified halloysite nanotubes have improved dispersibility. The halloysite nanotubes are uniformly dispersed in a dispersion medium, the top of the curved liquid surface of the medium solution is contacted with a glass sheet in the evaporation process of the solution, and the flow of the halloysite nanotubes from bottom to top is generated due to the evaporation induction of the solution, so that the halloysite nanotubes are brought to the part, contacted with the glass sheet, of the top of the curved liquid surface, and the nanotubes are gradually deposited on the surface of the substrate. When the concentration of the halloysite nanotubes is proper, the deposition rate of the halloysite nanotubes on the substrate and the liquid level descending rate are in a balanced state, and finally the continuous large-scale oriented halloysite film is obtained. Since the halloysite nanotubes have a large aspect ratio and are unbalanced in stress, in order to minimize the energy consumed in the alignment process, the nanotubes are aligned in a direction parallel to the liquid surface to form a large-scale aligned aggregate, thereby obtaining a large-scale aligned halloysite nanotube deposited on a substrate, and the mechanism diagram is shown in fig. 1.
According to the invention, isothermal evaporation induction self-loading method is utilized, halloysite are arranged in the same direction in a large scale, and mechanical, optical and electronic properties different from microcosmic properties are generated macroscopically. Well-aligned halloysite nanotube structures may exhibit superior properties not found in disordered counterparts, making them promising for different applications.
Specifically, the method for large-scale directional arrangement of the halloysite nanotubes comprises the following steps:
(1) selecting materials for the halloysite nanotubes;
(2) purifying the selected halloysite nanotubes to obtain pure halloysite nanotubes;
(3) modifying the pure halloysite nanotube to obtain a modified halloysite nanotube;
(4) dispersing the modified halloysite nanotubes in a dispersion medium to obtain a dispersion liquid;
(5) adjusting the pH value of the dispersion, then placing the dispersion in a container with a vertically placed substrate, and carrying out isothermal evaporation to obtain the halloysite nanotubes in large-scale oriented arrangement deposited on the substrate.
In the invention, the substrate is a material with a smooth surface, which is commonly used in the field, and can be a commercially available glass slide, a quartz plate, a silicon wafer, a metal plate or a glass plate.
Preferably, the substrate is a glass sheet.
Further, the pH value is adjusted to 4-7, and the pH value is preferably 6.
The application investigates the influence of the pH value of the dispersion liquid on the directional arrangement of the halloysite nanotubes, and the test result shows that the directional arrangement of the halloysite nanotubes is the best when the pH value is 6.
Furthermore, the material is selected from the halloysite nanotubes with the length of 800-.
The present application examined the effect of different halloysite nanotube lengths on alignment. The results show that the longer length halloysite nanotubes are not well aligned. When the halloysite nanotubes with the length of 800-1000nm are selected, the directional arrangement is better.
Further, the dispersion is to disperse the modified halloysite nanotubes in a dispersion medium and perform ultrasonic treatment to obtain a dispersion liquid.
Further, the dispersion medium is a mixed solution of water and ethanol, preferably a mixed solution of water and ethanol in a volume ratio of 98: 2.
Further, the temperature of the isothermal evaporation is 78-82 ℃, and preferably 80 ℃.
The present inventors have surprisingly found that when water and a small amount of ethanol are used as the dispersion medium, the temperature required for the good alignment of the halloysite nanotubes is reduced, which allows the contact of the halloysite nanotubes with the substrate to be increased during the alignment process, and promotes the dense alignment of the halloysite nanotubes.
Further, the purification comprises the steps of dispersing the halloysite nanotubes in deionized water, stirring, standing, taking supernatant, and obtaining pure halloysite nanotubes through ultrasound, centrifugation and drying.
Further, the ultrasonic frequency is 25KHz-35KHz, and the ultrasonic time is 20-50min, preferably 30 min.
Further, the modification is that the purified halloysite nanotube and sodium hexametaphosphate are added into deionized water, stirred at room temperature, kept stand, collected supernatant, centrifuged, washed and dried to obtain the modified halloysite nanotube.
The invention uses sodium hexametaphosphate modification to prepare the sodium Hexametaphosphate (HPO)4]2-Ions are adsorbed on the surface of the end part of the halloysite nanotube AlOH, the time required in the modification process is short, and the modification effect is good; the purification process is simple, and the high-purity halloysite nanotubes can be obtained only by separating supernatant; hydrochloric acid and the like are not needed, so that the integrity of the halloysite nanotube is ensured, and the halloysite nanotube is not corroded by acid.
Further, the mass ratio of the purified halloysite nanotube to sodium hexametaphosphate is 1:0.5-5, preferably 1: 1;
further, stirring for 20-28h at room temperature, preferably 24 h;
further, the mixture is stirred at room temperature and then is allowed to stand for 1 to 5 hours, preferably 3 hours.
After the technical scheme is adopted, compared with the prior art, the invention has the following beneficial effects.
1. The purification process is simple, and the halloysite nanotube with high purity can be obtained only by separating supernatant liquor;
2. according to the invention, sodium hexametaphosphate is adopted to modify the halloysite nanotubes, so that the dispersibility of the halloysite nanotubes is improved, the arrangement effect of the halloysite nanotubes is enhanced, and the large-scale oriented halloysite nanotubes are obtained;
3. according to the invention, water and a small amount of ethanol are used as a dispersion medium, so that the required temperature for good arrangement of the halloysite nanotubes is reduced, the contact between the halloysite nanotubes and a substrate can be increased in the arrangement process of the halloysite nanotubes, the halloysite nanotubes are enabled to be compactly arranged, and the thickness of the halloysite nanotubes has uniformity;
4. the invention improves the arrangement effect of the halloysite nanotubes by adjusting the pH value of the dispersion liquid, so that the halloysite nanotubes are arranged on the substrate more orderly and more compactly, and when the pH value is 6, the directional arrangement of the halloysite nanotubes is best.
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention, are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention without limiting the invention to the right. It is obvious that the drawings in the following description are only some embodiments, and that for a person skilled in the art, other drawings can be derived from them without inventive effort. In the drawings:
FIG. 1 is a schematic diagram of the mechanism of formation of the large scale oriented halloysite nanotubes of the invention;
FIG. 2-a is an SEM image of large scale aligned halloysite nanotubes of the invention;
FIG. 2-b is another SEM image of large scale aligned halloysite nanotubes of the invention;
FIG. 2-c is another SEM image of large scale aligned halloysite nanotubes of the invention;
FIG. 2-d is another SEM image of large scale aligned halloysite nanotubes of the invention;
FIG. 3 is an AFM image of large scale aligned halloysite nanotubes of the invention;
FIG. 4-a is an SEM image of large scale aligned halloysite nanotubes prepared at pH 4 of the dispersion;
FIG. 4-b is an SEM image of large scale aligned halloysite nanotubes prepared at pH 5 of the dispersion;
FIG. 4-c is an SEM image of large scale aligned halloysite nanotubes prepared at pH 6 of the dispersion;
FIG. 4-d is an SEM image of large scale aligned halloysite nanotubes prepared at pH 7 of the dispersion;
FIG. 5 is an SEM image of halloysite nanotubes prepared under different conditions;
FIG. 6 is a polarized optical image of halloysite nanotubes prepared under different conditions.
It should be noted that the drawings and the description are not intended to limit the scope of the inventive concept in any way, but to illustrate it by a person skilled in the art with reference to specific embodiments.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and the following embodiments are used for illustrating the present invention and are not intended to limit the scope of the present invention.
Example 1
(1) Selecting halloysite nanotubes with the length of 800-1000nm, the inner diameter of the tube of 20-30nm and the outer diameter of the tube of 50-70nm as raw materials;
(2) dispersing 10g of halloysite nanotubes in 1000mL of deionized water, stirring for 1h, standing for 10min, taking supernatant, and performing ultrasonic treatment, centrifugation and drying to obtain pure halloysite nanotubes, wherein the ultrasonic treatment is performed for 30min, and the ultrasonic frequency is 25 KHz;
(3) respectively adding 2g of dried halloysite nanotube and 2g of sodium hexametaphosphate into 200ml of deionized water, stirring at room temperature for 24h, standing for 3h to precipitate aggregate and impurities, collecting supernatant, centrifuging, washing for 3-4 times, and drying to obtain modified halloysite nanotube;
(4) dispersing 300mg of modified halloysite nanotubes in 30mL of solution (water: 98% and ethanol: 2%), and performing ultrasonic treatment for 30min at the ultrasonic frequency of 25KHz to obtain a dispersion liquid;
(5) adjusting the pH value of the dispersion liquid to 6, placing 30mL of sample into a beaker with a vertically placed glass sheet, and drying at 80 ℃ to obtain the halloysite nanotubes deposited on the glass sheet and having large-scale orientation;
SEM images of the large-scale aligned halloysite nanotubes of this example are shown in FIGS. 2-a through 2-d, and it can be seen that the halloysite nanotubes exhibit a good orientation, are aligned substantially in the same direction, and are densely aligned. AFM images of the large-scale aligned halloysite nanotubes of this example are shown in FIGS. 3-a to 3-c, and it can be seen that the halloysite nanotubes are large-scale aligned, the mean square roughness (Rq) is 40.6nm (FIGS. 3-a, b), and the thickness of the halloysite nanotubes is uniform (FIG. 3-c).
Example 2
(1) Selecting halloysite nanotubes with the length of 800-1000nm, the inner diameter of the tube of 20-30nm and the outer diameter of the tube of 50-70nm as raw materials;
(2) dispersing 10g of halloysite nanotubes in 1000mL of deionized water, stirring for 1h, standing for 10min, taking supernatant, and performing ultrasonic treatment, centrifugation and drying to obtain pure halloysite nanotubes, wherein the ultrasonic treatment is performed for 20min, and the ultrasonic frequency is 35 KHz;
(3) respectively adding 2g of dried halloysite nanotube and 1g of sodium hexametaphosphate into 200ml of deionized water, stirring at room temperature for 20h, standing for 1h to precipitate aggregate and impurities, collecting supernatant, centrifuging, washing for 3-4 times, and drying to obtain modified halloysite nanotube;
(4) dispersing 300mg of modified halloysite nanotubes in 30mL of solution (water: 98% and ethanol: 2%), and performing ultrasonic treatment for 20min at the ultrasonic frequency of 35KHz to obtain a dispersion liquid;
(5) adjusting the pH value of the dispersion to 4, placing 30mL of sample into a beaker with a vertically placed glass sheet, and drying at 78 ℃ to obtain the halloysite nanotubes deposited on the glass sheet and having large-scale orientation;
SEM images and AFM images of the large scale aligned halloysite nanotubes of this example are similar to example 1.
Example 3
(1) Selecting halloysite nanotubes with the length of 800-1000nm, the inner diameter of the tube of 20-30nm and the outer diameter of the tube of 50-70nm as raw materials;
(2) dispersing 10g of halloysite nanotubes in 1000mL of deionized water, stirring for 1h, standing for 10min, taking supernatant, and performing ultrasonic treatment, centrifugation and drying to obtain pure halloysite nanotubes, wherein the ultrasonic treatment is performed for 40min, and the ultrasonic frequency is 30 KHz;
(3) respectively taking 2g of dried halloysite nanotube and 5g of sodium hexametaphosphate, adding into 200ml of deionized water, stirring at room temperature for 26h, standing for 4h to precipitate aggregate and impurities, collecting supernatant, centrifuging, washing for 3-4 times, and drying to obtain modified halloysite nanotube;
(4) dispersing 300mg of modified halloysite nanotubes in 30mL of solution (water: 98% and ethanol: 2%), and performing ultrasonic treatment for 40min at the ultrasonic frequency of 30KHz to obtain a dispersion liquid;
(5) adjusting the pH value of the dispersion to 5, placing 30mL of sample in a beaker with a vertically placed glass sheet, and drying at 82 ℃ to obtain the halloysite nanotubes deposited on the glass sheet and having large-scale orientation;
SEM images and AFM images of the large scale aligned halloysite nanotubes of this example are similar to example 1.
Example 4
(1) Selecting halloysite nanotubes with the length of 800-1000nm, the inner diameter of the tube of 20-30nm and the outer diameter of the tube of 50-70nm as raw materials;
(2) dispersing 10g of halloysite nanotubes in 1000mL of deionized water, stirring for 1h, standing for 10min, taking supernatant, and performing ultrasonic treatment, centrifugation and drying to obtain pure halloysite nanotubes, wherein the ultrasonic treatment is performed for 50min, and the ultrasonic frequency is 28 KHz;
(3) respectively adding 2g of dried halloysite nanotube and 10g of sodium hexametaphosphate into 200ml of deionized water, stirring at room temperature for 28h, standing for 5h to precipitate aggregate and impurities, collecting supernatant, centrifuging, washing for 3-4 times, and drying to obtain modified halloysite nanotube;
(4) dispersing 300mg of modified halloysite nanotubes in 30mL of solution (water: 98% and ethanol: 2%), and performing ultrasonic treatment for 50min at the ultrasonic frequency of 28KHz to obtain a dispersion liquid;
(5) the pH of the dispersion was adjusted to 7, and 30mL of the sample was placed in a beaker with a vertically placed glass slide and dried at 80 ℃ to yield halloysite nanotubes deposited on the glass slide with large scale orientation.
SEM images and AFM images of the large scale aligned halloysite nanotubes of this example are similar to example 1.
Test example 1
This test example investigated the effect of the pH of the dispersion on the preparation of large-scale oriented halloysite nanotubes.
The test procedure was the same as in example 1, except that the pH of the dispersion in step (5) was changed to examine the effect of the pH of the dispersion on the preparation of large-scale oriented halloysite nanotubes.
The results are shown in fig. 4, where pH 4 is shown in fig. 4-a, pH 5 is shown in fig. 4-b, pH 6 is shown in fig. 4-c, and pH 7 is shown in fig. 4-d. As can be seen from the figure, the best aligned large scale aligned halloysite nanotubes were obtained when pH was 6. Therefore, the present invention preferably has a pH of 6.
Test example 2
This test example examined the effect of different dispersion media on the arrangement of halloysite nanotubes.
The test procedure was the same as in example 1, except that the dispersion medium of step (4) was changed to examine the effect of different dispersion media on the arrangement of halloysite nanotubes.
The results are shown in Table 1.
TABLE 1 temperatures required for good alignment of halloysite nanotubes
| Dispersion medium | Temperature required for good alignment of halloysite nanotubes |
| 30mL of solution (water: ethanol 98: 2) | 80℃ |
| 30mL of an aqueous solution | 90℃ |
As can be seen from the results in table 1, the use of water and a small amount of ethanol as the dispersion medium reduces the temperature required for good alignment of the halloysite nanotubes, which increases the contact of the halloysite nanotubes with the substrate during alignment, and promotes dense alignment of the halloysite nanotubes.
Test example 3
This experiment examined the effect of different halloysite nanotube lengths on alignment.
The test procedure was the same as in example 1, except that the length of the halloysite nanotubes in step 1 was varied to examine the effect of different lengths of halloysite nanotubes on alignment. Wherein the halloysite nanotubes of figure 5 are 1100-1300nm in length. As can be seen from the figure, the arrangement of the halloysite nanotubes with longer length is not good.
Test example 4
The optical properties of the halloysite nanotubes prepared under different conditions were examined in this test example.
And drying the halloysite nanotube dispersion liquid on a glass sheet, wherein the glass sheet, air and the halloysite nanotube dispersion liquid form a three-phase contact line. The three-phase contact line moves along with the movement of the liquid level of the halloysite nanotube dispersion liquid, and the nanotubes deposit to form compact stripes along with the movement of the contact line. To study the striped pattern formed by the halloysite nanotube dispersion, the patterned surface of the halloysite nanotubes was observed with a polarizing microscope. Fig. 6 a is a polarized optical image aligned under other conditions, and it can be seen that the halloysite nanotubes are not changed in brightness under different rotation angles, which proves that the halloysite nanotubes are not aligned. The b-diagram in fig. 6 is an optical microscope image of different concentrations forming stripes. It can be seen from the b diagram in fig. 6 that dense stripes are formed by the halloysite nanotubes, when the stripes are vertical (assuming that the rotation angle is 0 °), a dark field appears, when the stripes are rotated 45 ° counterclockwise, a bright field appears, and the brightness reaches the maximum value, and when the stripes are rotated 45 °, the dark field appears again, and then, the alternation of brightness and darkness appears every 45 °. This indicates that the dried halloysite nanotube stripes have liquid crystal-like optical properties.
The above description is only for the preferred embodiment of the present invention, and not intended to limit the present invention in any way, and although the present invention has been disclosed by the preferred embodiment, it is not intended to limit the present invention, and those skilled in the art can make various changes and modifications to the equivalent embodiment without departing from the scope of the present invention.
Claims (10)
1. A method for large-scale directional alignment of halloysite nanotubes, comprising: the method comprises the steps of selecting materials, purifying, modifying, dispersing and directionally arranging the halloysite nanotubes, wherein the directional arrangement is used for adjusting the pH value of dispersed liquid obtained after dispersion, then placing the dispersion in a container with a vertically placed substrate, and carrying out isothermal evaporation to obtain the halloysite nanotubes which are deposited on the substrate and are directionally arranged in a large scale.
2. The method of mass-aligned halloysite nanotubes of claim 1, wherein: the pH value is adjusted to 4-7, and the pH value is preferably 6.
3. The method for large scale aligned halloysite nanotubes of claim 1 or 2, wherein: the material is selected from the halloysite nanotubes with the length of 800-.
4. The method for large-scale aligned halloysite nanotubes according to any one of claims 1-3, wherein the dispersing is carried out by dispersing the modified halloysite nanotubes in a dispersion medium and subjecting the dispersion to ultrasound.
5. The method for large-scale aligned halloysite nanotubes according to claim 4, wherein the dispersion medium is a mixed solution of water and ethanol, preferably a mixed solution of water and ethanol in a volume ratio of 98: 2.
6. The method of mass-aligned halloysite nanotubes of claim 5, wherein: the temperature of the isothermal evaporation is 78-82 ℃, and preferably 80 ℃.
7. The method of mass-qualitative alignment of halloysite nanotubes according to any one of claims 1-6, wherein the purification is by dispersing halloysite nanotubes in deionized water, stirring, standing, taking supernatant, sonicating, centrifuging, and drying to obtain pure halloysite nanotubes.
8. The method for large-scale aligned halloysite nanotubes according to claim 4 or 7, wherein the ultrasound frequency is 25KHz to 35KHz and the ultrasound time is 20 to 50min, preferably 30 min.
9. The method of claim 7 or 8, wherein the modification comprises adding pure halloysite nanotubes and sodium hexametaphosphate into deionized water, stirring at room temperature, standing, collecting the supernatant, centrifuging, washing, and drying to obtain modified halloysite nanotubes.
10. The method for large scale qualitative alignment of halloysite nanotubes according to claim 9, wherein the mass ratio of purified halloysite nanotubes to sodium hexametaphosphate is 1:0.5 to 5, preferably 1: 1;
the stirring is carried out for 20-28h, preferably 24 h;
the standing is 1-5h, preferably 3 h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116410627A (en) * | 2023-04-04 | 2023-07-11 | 北京航空航天大学 | Preparation method of transparent conductive coating based on evaporation self-driving and transparent conductive coating |
| CN116478566A (en) * | 2023-04-26 | 2023-07-25 | 集美大学 | Anti-corrosion self-repairing nano filler and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090092836A1 (en) * | 2007-10-04 | 2009-04-09 | Gwamgju Institute Of Science And Technology | Gold nanoparticle-halloysite nanotube and method of forming the same |
| US20120107214A1 (en) * | 2010-10-28 | 2012-05-03 | Korea Institute Of Geoscience And Mineral Resources | Method for preparing microtubular halloysite nanopowders |
| CN103601203A (en) * | 2013-10-25 | 2014-02-26 | 浙江理工大学 | Halloysite nanotube purification method |
| CN104119704A (en) * | 2013-04-27 | 2014-10-29 | 中国科学院化学研究所 | Surface modification treatment method of halloysite nanotube |
| CN104386647A (en) * | 2014-10-27 | 2015-03-04 | 暨南大学 | Directional arrangement method of halloysite nanotubes and coating and application of halloysite nanotubes |
| CN104876179A (en) * | 2015-04-16 | 2015-09-02 | 华中科技大学 | Large-area assembling method for non-contact type one-dimensional nano material |
-
2019
- 2019-06-17 CN CN201910521991.0A patent/CN112093774A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090092836A1 (en) * | 2007-10-04 | 2009-04-09 | Gwamgju Institute Of Science And Technology | Gold nanoparticle-halloysite nanotube and method of forming the same |
| US20120107214A1 (en) * | 2010-10-28 | 2012-05-03 | Korea Institute Of Geoscience And Mineral Resources | Method for preparing microtubular halloysite nanopowders |
| CN104119704A (en) * | 2013-04-27 | 2014-10-29 | 中国科学院化学研究所 | Surface modification treatment method of halloysite nanotube |
| CN103601203A (en) * | 2013-10-25 | 2014-02-26 | 浙江理工大学 | Halloysite nanotube purification method |
| CN104386647A (en) * | 2014-10-27 | 2015-03-04 | 暨南大学 | Directional arrangement method of halloysite nanotubes and coating and application of halloysite nanotubes |
| CN104876179A (en) * | 2015-04-16 | 2015-09-02 | 华中科技大学 | Large-area assembling method for non-contact type one-dimensional nano material |
Non-Patent Citations (3)
| Title |
|---|
| MINGXIAN LIU等: "Strip-like clay nanotubes patterns in glass capillary tubes for capture of tumor cells", 《ACS APPL. MATER. INTERFACES》 * |
| NADIA HOUTA等: "Dispersion of phyllosilicates in aqueous suspensions: Role of the nature and amount of surfactant", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| TEJAS A. SHASTRY等: "Large-area, electronically monodisperse, aligned single-walled carbon nanotube thin films fabricated by evaporation-driven self-assembly", 《SMALL》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116410627A (en) * | 2023-04-04 | 2023-07-11 | 北京航空航天大学 | Preparation method of transparent conductive coating based on evaporation self-driving and transparent conductive coating |
| CN116478566A (en) * | 2023-04-26 | 2023-07-25 | 集美大学 | Anti-corrosion self-repairing nano filler and preparation method thereof |
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