An ordered assembly method and its application

Abstract

The present invention discloses a gelation-induced ordered assembly method. The method is based on the electrostatic interaction between the assembly substrate and the assembly primitives to achieve the ordered assembly of the assembly primitives. Specifically, a substrate that can release charged particles is placed in an assembly liquid to obtain an ordered assembled material; the assembly liquid includes assembly primitives, and the assembly primitives can form an electrostatic interaction with the charged particles. Furthermore, the present invention further improves the orientation degree of the assembly material based on gel-induced orientation. The present invention simply realizes the orderly assembly preparation of nanomaterials and microstructure control, and realizes the preparation of nanocomposite materials with various forms and functions using substrates of complex shapes and various materials as templates.

Description

Technical Field

[0001] The invention relates to a nano material assembly method and application. Background Art

[0002] The exceptional performance of nanomaterial assemblies has attracted numerous scientists to assemble nanomaterials to create a range of functionalized micro- and nano-integrated devices, bringing about significant changes in human life. The controlled and ordered assembly of nanomaterials is crucial for their application in various industries. Although numerous nanomaterial assembly methods have been developed over the past two decades, the challenge of assembling nanomaterials over large areas, efficiently, cost-effectively, and precisely remains a significant obstacle to their wider and deeper application. The controlled and ordered assembly of nanomaterials is a key development direction in nanoscience and technology, both currently and for decades to come.

[0003] One-dimensional nanomaterials, including various metal and semiconductor nanowires, carbon nanotubes, core-shell nanowires, and hybrid structures, have been a hot topic of research in nanoscience and nanotechnology in recent years due to their unique and exceptional properties. They possess exceptional mechanical and electrical properties along the axial direction, high tensile strength and Young's modulus, and excellent flexibility, leading to their widespread application in electronics, optoelectronics, energy storage, and biology. However, effectively assembling nanowires into macroscale materials has become a fundamental challenge for the future development of nanowire applications. Common approaches include nanowire assembly at liquid interfaces, nanowire assembly in liquids, and nanowire assembly between solid gaps.

[0004] Two-dimensional materials possess superior electronic, thermal, and mechanical properties. Assembling these materials into thin films or bulk structures is crucial for achieving advanced nanomaterial properties. Their superior electrical and mechanical properties, high surface area, and internal structures or networks make them suitable for a wide range of applications. Common two-dimensional materials include graphene nanosheets and boron nitride nanosheets. Common assembly methods include layer-by-layer self-assembly, interfacial superspreading, ice templating, and filtration.

[0005] The layer-by-layer assembly method initially used charged substrates to alternately deposit oppositely charged polyelectrolyte solutions to prepare polyelectrolyte self-assembled multilayers. Later, by introducing one-dimensional or two-dimensional materials into the solution, the layer-by-layer assembly method could precisely control the microstructure and achieve high loadings of inorganic phases with a high degree of orientation. However, the time-consuming preparation process and the difficulty of large-scale production have limited the practical application of this method to a certain extent. While the ion diffusion method has increased the assembly rate to a certain extent, it has not achieved highly oriented assembly of nanomaterials. Currently reported articles use ion diffusion to achieve disordered fixation of nanosheets and utilize the capillary force of water evaporation to achieve stacking and orientation of flexible nanosheets, but the degree of orientation is limited and orientation of rigid nanosheets cannot be achieved.

[0006] The assembly methods for both one-dimensional and two-dimensional nanomaterials are time-consuming or lack a high degree of order, and they are unable to create complex frameworks using materials of arbitrary shapes as templates. Therefore, how to quickly, easily, and controllably prepare framework materials with diverse morphologies is an important issue that needs to be addressed. Summary of the Invention

[0007] The present invention aims to address the deficiencies of the prior art and propose a method for orderly assembly of nanomaterials. The method is based on the electrostatic interaction between the assembly substrate and the assembly primitives to achieve orderly assembly of the assembly primitives.

[0008] Specifically, the following scheme is adopted: a substrate capable of releasing charged particles is placed in an assembly liquid to obtain an ordered assembled material; the assembly liquid includes assembly primitives, and the assembly primitives can form electrostatic interactions with the charged particles.

[0009] The substrate for releasing charged particles can be: a metal that releases charged particles in situ through reaction, a hydrophilic material that adsorbs charged particles (including water-absorbing materials, hydrophobic materials after hydrophilic modification, such as plastics, etc.). The charged particles can be: charged ions or charged polymers (polyelectrolytes). For example: cations (Na + , Ca 2+ 、Zn 2+ 、Ba 2+ 、Cu 2+ 、Fe 3+ 、Al 3+ 、Zr 4+ At least one of the following: (a) (b) (c) (d) (e) (e) (f) (g) (h) (h) (i) (i) (i) (i) (ii) (ii) (iii) (iv) (v ...

[0010] The assembly unit is either inherently charged or surface-charged through surface modification. The assembly unit can be at least one of a zero-dimensional material, a one-dimensional material, a two-dimensional material, or a three-dimensional material. Zero-dimensional materials include gold particles and PMMA particles; one-dimensional materials include carbon nanotubes, silver nanowires, silicon carbide nanowires, silicon nitride nanowires, cellulose nanofibers, glass fibers, carbon fibers, and polyimide fibers; two-dimensional materials include boron nitride nanosheets, aluminum oxide nanosheets, glass sheets, mica sheets, clay sheets, graphene, and molybdenum disulfide; and three-dimensional materials include bismuth oxychloride nanoflowers.

[0011] In certain embodiments of the present invention, the method further comprises injecting a functional material into the assembled material to obtain a functional composite material. The functional material includes, but is not limited to, prepolymer resin and polymer monomer to achieve functionalization of the material.

[0012] Furthermore, the present invention also relates to gel-induced assembly, which further improves the assembly effect and efficiency. The gel component mixed with the assembly unit, that is, the assembly liquid also includes a gel component, which can form a gel under the induction of the charged particles. This allows the diffusion of the charged particles to synchronize with the formation of the gel. The gel interface contains a large number of charged particles, making the interface electrically charged, and the interface continuously attracts nanoparticles of opposite charge to migrate to the interface. When the assembly unit contacts the gel interface, as the charged particles further diffuse, the assembly unit is fixed at the interface, while the charged particles continue to diffuse forward in a direction perpendicular to the substrate, which continues to assemble and fix the subsequent particles in an orderly manner.

[0013] Especially when the assembly units are anisotropic one- or two-dimensional materials, they maximize their contact area when parallel to the gel surface, achieving their most stable state, with the one- or two-dimensional materials oriented parallel to the gel interface. Therefore, gel-induced assistance can significantly aid the oriented assembly of one- or two-dimensional material systems.

[0014] When using gels for induced, aligned, and ordered assembly of one- and two-dimensional materials, the concentration of assembly units should be between 0 and 20 vol%. If the concentration is too high, the steric hindrance between the nanowires and nanosheets will be significant, hindering their orientation and reducing the degree of orientation. Those skilled in the art can conveniently and quickly measure the weight of assembly units based on the volumetric content requirement and the formula weight = density * volume. In the embodiments of the present invention, all measurements are by weight.

[0015] In the present invention, the content of the gel component is subject to the following prerequisites: ① The concentration cannot be too low, otherwise, gel formation cannot occur under the induction of the charged particles; as long as the concentration can form a gel, it can provide a force for the assembly of nanomaterials. ② The concentration cannot be too high, otherwise the viscosity of the assembly solution will be too high, resulting in orientation resistance; generally, the viscosity of the assembly solution should be below 500 mPa·s. It is common knowledge in the art to formulate the required concentrations of the various assembly solution components based on these two prerequisites.

[0016] In the present invention, the gel component is a polymerizable monomer and the charged particles are anions of an initiator; or the gel component is a polyelectrolyte and the charged particles are ions or polyelectrolytes with opposite electrical properties to the gel component. Specifically, one of the following combinations can be used:

[0017] 1) The gel component is selected from at least one of negatively charged polyelectrolytes (carboxyl, thiol, imidazole), such as carboxyl polyelectrolytes (sodium alginate, pectin, cellulose, carboxyl polyurethane, carboxylated chitosan, sodium polygalacturonate, etc.), and the charged particles are selected from cationic (Na + , Ca 2+ 、Zn 2+ 、Ba 2+ 、Cu 2+ 、Fe 3+ 、Al 3+ 、Zr 4+ At least one of the following;

[0018] 2) The gel component is at least one selected from positively charged polyelectrolytes (amino groups, etc.), such as amino polyelectrolytes (chitosan, branched polyethyleneimine, cationic polyacrylamide, etc.), and the charged particles are at least one selected from multivalent anions (citrate, tripolyphosphate);

[0019] 3) The gel component is selected from at least one of negatively charged polyelectrolytes (carboxyl, thiol, imidazole, etc.), and the charged particles are selected from at least one of positively charged polyelectrolytes (amino, etc.);

[0020] 4) The gel component is selected from at least one of negatively charged polyelectrolytes (carboxyl, thiol, imidazole), and the charged particles are selected from at least one of positively charged polyelectrolytes (amino, etc.);

[0021] 5) The gel component is selected from at least one of positively charged polyelectrolytes (amino groups, etc.), and the charged particles are selected from at least one of negatively charged polyelectrolytes (carboxyl groups, thiol groups, imidazole groups, phosphate groups, etc.);

[0022] 6) The gel component is selected from at least one monomer (acrylamide, acrylic acid, etc.), the charged particles are selected from at least one negatively charged initiator (persulfate, etc.), and the assembly unit is positively charged;

[0023] 7) The gel component is selected from at least one monomer (acrylamide, acrylic acid, etc.), the charged particles are selected from at least one positive initiator (Lewis acid, etc.), and the assembly unit is negatively charged.

[0024] When the assembly solution contains a gel component, it is necessary to consider the formation of the gel and the assembly speed of the nanowires / nanosheets; since the formation speed of the gel is directly related to the release speed of the substrate charged particles, it has been shown through experiments that when the formation speed of the gel is below 0.2 mm / min, the effective orientation induction of the gel for the assembly unit can be guaranteed. For example, for divalent calcium ions, in the case of adsorption, the concentration of the charged particles adsorbed by the substrate is set to below 5 mol / L, which can ensure that the speed of gel formation is below 0.2 mm / min; and for trivalent iron ions, in the case of adsorption, the concentration of the charged particles adsorbed by the substrate is set to below 1 mol / L to ensure that the speed of gel formation is below 0.2 mm / min. Those skilled in the art can regulate the concentration of the adsorbed charged particles by detecting the formation speed of the gel, or regulate the electrochemical reaction speed (such as the current size, for the metal that releases the charged particles in situ in the reaction), so as to achieve the best promoting effect of the gel.

[0025] When the assembly fluid contains a gel component, it can directly act as a modifying group on the assembly unit, modifying the unit's surface. For example, sodium alginate, as a gel component, can physically adsorb onto alumina nanosheets, imparting a negative charge to the nanosheets, allowing them to form an electrostatic interaction with the positively charged assembly substrate. Similarly, chitosan, as a gel component, can physically adsorb onto alumina nanosheets, imparting a positive charge to the nanosheets, allowing them to form an electrostatic interaction with the negatively charged assembly substrate.

[0026] In certain embodiments of the present invention, the method further comprises removing the gel component to obtain a skeleton material composed of assembly units. The method of removing the gel component comprises: physical high-temperature burning, chemical dissociation.

[0027] In certain embodiments of the present invention, the method further includes injecting functional materials into the above-mentioned assembly material or the assembly material after further removing the gel, wherein the functional materials include but are not limited to: prepolymer resin and polymer monomer to achieve functionalization of the material.

[0028] Based on the assembly method of the present invention or the gel-induced assembly method, a thermally conductive film can be obtained, comprising thermally conductive elements oriented along a plane. The thermally conductive elements include but are not limited to boron nitride nanosheets, graphene nanosheets, and aluminum oxide nanosheets.

[0029] Based on the assembly method of the present invention or the gel-induced assembly method, a thermal interface material can be obtained, comprising vertically oriented thermally conductive elements; the substrate surface has vertically oriented pillars, and the thermally conductive elements are assembled on the pillars. The thermally conductive elements include, but are not limited to, boron nitride nanosheets, graphene nanosheets, and aluminum oxide nanosheets.

[0030] When the gel-induced assembly scheme is adopted, the above-mentioned thermal conductive elements are assembled in a gel system, and the gel system can be polyurethane gel or sodium alginate gel.

[0031] Based on the assembly method of the present invention or through the gel-induced assembly method, a lightweight, high-strength composite material can be obtained, including a lightweight framework composed of planar-oriented rigid elements. The rigid elements are at least one of silicon carbide nanosheets, aluminum oxide nanosheets, glass fibers, and carbon fibers.

[0032] Based on the assembly method of the present invention or the gel-induced assembly method, a light-weight high-strength resin can be obtained. This light-weight high-strength resin is obtained by resin filling, polymerization, and curing on the basis of the aforementioned light-weight frame.

[0033] In certain embodiments of the present invention, a lightweight, high-strength transparent glass can be obtained by using transparent rigid elements (e.g., glass nanosheets) filled with a specific resin and then polymerized and cured. The refractive index of this specific resin matches the refractive index of the rigid elements.

[0034] In certain embodiments of the present invention, the gel-induced assembly is performed using the following steps:

[0035] 1) Disperse the assembly unit and gel components in a suitable solvent and stir to disperse them evenly. The concentrations of the two can be adjusted adaptively according to the application of the assembly. The higher the concentration of the assembly unit, the higher the assembly density.

[0036] 2) taking a substrate material and adsorbing a charged particle solution on the substrate material;

[0037] 3) immersing the above-mentioned base material in the nanomaterial dispersion for a certain period of time;

[0038] 4) Proposing a substrate material with a nanomaterial gel adhered thereto;

[0039] 5) If necessary, the gel can be dried or freeze-dried to remove the base material to obtain a nanomaterial skeleton or composite material;

[0040] 6) As needed, the nanomaterial skeleton can be selectively post-treated, including heat treatment to remove organic matter, physical or chemical modification of the skeleton, pre-polymerization of resin or high molecular monomer filling, etc.

[0041] Furthermore, the residence time in step 3) is 1 second to 30 minutes.

[0042] Furthermore, the base material used in step 3) includes wood, plastic, rubber, ceramic, metal, etc. Non-hydrophilic materials can be made hydrophilic by pre-treatment, including plasma treatment, commercial hydrophilic spray, polydopamine modification, etc.

[0043] Furthermore, the material shape of the base material used in step 2) includes one-dimensional, two-dimensional, three-dimensional, two-dimensional mesh, three-dimensional mesh, etc.

[0044] Furthermore, the prepolymer resin used in step 6) includes one of epoxy resin, polyester resin, vinyl ester, bismaleimide, thermosetting polyimide, cyanate ester, etc., or the polymer monomer includes one of acrylic acid, epoxy, styrene, alcohol, anhydride, etc.

[0045] Compared with the prior art, the present invention has the following beneficial effects:

[0046] 1) A wide range of applicable elementary nanomaterials, including most one-dimensional and two-dimensional materials;

[0047] 2) The rapid gelation process is used to achieve the orderly assembly of nanomaterials. The time for constructing the oriented skeleton is short, the operation is simple, and water is used as the solvent, which is green and environmentally friendly.

[0048] 3) Doping with functional polymers or ions can further broaden the application range of materials;

[0049] 4) By adjusting the concentration of charged particles and nanosheets, the thickness of oriented nanomaterials can be easily controlled, and the controllable preparation of material thickness from nanometer to millimeter level can be achieved.

[0050] 5) Oriented nanomaterials with various shapes and functions can be prepared by using any shape and material as a template and three-dimensional structural design. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 Figure a is a schematic diagram of the gel-induced assembly method for the orientation fixation of nanomaterials. In the figure, the large dots are negatively charged assembly units, the small dots are calcium ions, the dotted line represents the gel interface, and the left side of the dotted line represents the gel formation under the induction of calcium ions. Figure 1 Figure b is a schematic diagram of the mechanism of anisotropic particle orientation by gel-induced assembly method, in which the long rectangular boxes are negatively charged one-dimensional or two-dimensional assembly units.

[0052] Figure 2 a in the figure is a scanning electron microscope image of the assembly effect of nanosheets by the ion diffusion method without gel induction in Example 1. Figure 2b in Figure 2 High magnification of a in .

[0053] Figure 3 a in the figure is a scanning electron microscope image of a planar sample prepared by the gel-induced assembly method in Example 2. Figure 3 b in Figure 3 High magnification of a in .

[0054] Figure 4 This is the relationship between the nanosheet assembly time and the dry sample thickness in Example 2.

[0055] Figure 5 This is a scanning electron microscope image of the effect of magnesium ion adsorption on the assembly of nanosheets in comparative example 1.

[0056] Figure 6 This is a scanning electron microscope image of a flat sample prepared as a substrate after plastic hydrophilic treatment.

[0057] Figure 7 This is a scanning electron microscope image of nanosheets assembled using carboxymethyl cellulose as a gel component.

[0058] Figure 8 To utilize Zr 4+ This is a scanning electron microscope image of charged ion-induced assembly of nanosheets.

[0059] Figure 9 a in the figure is a scanning electron microscope image of positively charged nanosheets assembled using citrate as negative ion induction. Figure 9 b in Figure 9 High magnification of a in .

[0060] Figure 10 This is a scanning electron microscope image of gel-induced assembly of glass fibers. Figure 10 a in the figure is a schematic diagram of the gel induction process. Figure 10 b in the figure is the cross-sectional view in the x direction. Figure 10 c is a high-magnification view of the cross-section in the y direction;

[0061] Figure 11 This is a scanning electron microscope image of the effect of ion diffusion method without gel induction on the assembly of glass fibers. Figure 11 a in the figure is a schematic diagram of the ion induction process. Figure 11 b in the figure is the cross-sectional view in the x direction. Figure 11 c is a high-magnification view of the cross-section in the y direction;

[0062] Figure 12 This is a scanning electron microscope image of gel-induced co-assembly of glass fibers and alumina nanosheets. Figure 12 a in the figure is a schematic diagram of the gel induction process. Figure 12b in the figure is the cross-sectional view in the x direction. Figure 12 c is a high-magnification view of the cross-section in the y direction;

[0063] Figure 13 This is a scanning electron microscope image of gel-induced co-assembly of spherical particles and alumina nanosheets. Figure 13 a in the equation is the alumina ball / sheet skeleton, Figure 13 b is a high-magnification image of the alumina ball / sheet skeleton;

[0064] Figure 14 This is a scanning electron microscope image of a micro-curved surface structure prepared using copper wire as a substrate.

[0065] Figure 15 To expand the assembly method: Scanning electron microscope images of nanosheet assembly achieved by spraying the suspension, where Figure 15 The a in the code is the spray bottle spray mode. Figure 15 b in which is the obtained alumina skeleton;

[0066] Figure 16 To expand the assembly method: Scanning electron microscope images of complex three-dimensional structures achieved through array design. Figure 16 a in the equation is a copper wire array. Figure 16 b in the figure is a copper wire array that absorbs the alumina dispersion. Figure 16 In figure c, the alumina skeleton is removed from the copper wire array.

[0067] Figure 17 This is the SEM image of the alumina skeleton obtained in Example 18. DETAILED DESCRIPTION

[0068] The present invention provides a method for orderly assembly of nanomaterials. The method realizes orderly assembly of assembly elements based on the electrostatic interaction between an assembly substrate and assembly elements.

[0069] Furthermore, the present invention also relates to gel-induced assembly to further improve the assembly effect and efficiency.

[0070] Assembly fluid: gel component, water, assembly unit;

[0071] Assembly driving fluid: charged particle solution (needs to be attached to a hydrophilic substrate);

[0072] Prerequisites: 1. The charged particles and gel components can form a gel (physical or chemical cross-linking, electrostatic effect, etc.); 2. The charged particles and the assembly units have opposite charges and attract each other through electrostatic effect.

[0073] like Figure 1The "a" in the figure represents the gelation process, which describes the orientation process: When a substrate with charged particles attached contacts a suspension of assembly units, the charged particles rapidly form a gel with the gel components. Simultaneously, as the charged particles continue to diffuse into the suspension, the gel continues to grow. The large number of charged particles at the gel interface makes the interface electrically charged, continuously attracting assembly units of opposite charge to migrate toward it. When the assembly units contact the gel interface, further diffusion of the charged particles immobilizes them at the interface, while the charged particles continue to diffuse forward perpendicular to the substrate, further assembling and immobilizing the particles behind them.

[0074] For one-dimensional and two-dimensional materials with anisotropy, such as Figure 1 b in the figure has the largest contact area when it is parallel to the gel surface and reaches the most stable state. The one-dimensional and two-dimensional materials are oriented parallel to the gel interface and are fixed by the gel.

[0075] The present invention is described in detail below through examples. These examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Those skilled in the art may make some non-essential changes and adjustments based on the contents of the present invention, which all fall within the scope of protection of the present invention.

[0076] Since the concentration of the assembly units, the viscosity of the assembly liquid, and the concentration of charged particles in the solution adsorbed on the substrate can all be adjusted according to needs through simple experiments, in the following embodiments, unless otherwise specified, the concentration of the assembly units is calculated to be 0-20 vol%, the viscosity of the assembly liquid is tested to be below 500 mPa·s, the concentration of charged particles adsorbed on the substrate is above 0.1 mol / L, and the gel speed is ensured to be below 0.2 mm / min.

[0077] Example 1

[0078] 1) 50 parts by weight of alumina flakes, 100 parts by weight of water, and 2 parts by weight of Darvan liquid (a nanosheet modifier that imparts a negative charge to the alumina and allows for uniform dispersion in water; it does not cross-link with calcium ions and does not form a gel) were added to a container and stirred to obtain an alumina dispersion; the concentration of the alumina flakes was approximately 12 vol%.

[0079] 2) Take filter paper and adsorb enough 5 mol / L calcium chloride solution on the filter paper;

[0080] 3) Immerse the filter paper in the alumina dispersion for 10 minutes;

[0081] 4) Remove the filter paper with aluminum oxide attached;

[0082] 5) Dry the gel and remove the filter paper to obtain an alumina skeleton.

[0083] The product of this embodiment is Figure 2 .

[0084] Example 2:

[0085] The steps of a gel-induced assembly two-dimensional nano-skeleton material and a preparation method thereof are as follows:

[0086] 1) Add 50 parts by weight of alumina flakes, 100 parts by weight of water, and 2 parts by weight of sodium alginate to a container and stir them evenly to obtain an alumina dispersion (viscosity below 500 mPa·s); the concentration of the alumina flakes is approximately 12 vol%.

[0087] 2) Take filter paper and adsorb enough 5 mol / L calcium chloride solution on the filter paper;

[0088] 3) Immerse the filter paper in the alumina dispersion for 10 minutes;

[0089] 4) removing the filter paper adhered with the alumina gel;

[0090] 5) Dry the gel and remove the filter paper to obtain an alumina skeleton, such as Figure 3 The dry skeleton thickness and assembly time are shown in Figure 4 As shown in the figure, it can be seen that in the same time, the skeleton thickness of the gel-induced assembly method is 3 times that of the non-gel-induced assembly method.

[0091] Comparative Example 1: The difference from Example 2 is that a sufficient concentration of 5 mol / L magnesium chloride solution is adsorbed on the filter paper. Since magnesium ions do not have a cross-linking effect with sodium alginate (gel component), no gelation effect occurs and the nanosheets can only be attracted to migrate. In contrast, calcium ions have a cross-linking effect with sodium alginate (gel component), which can produce a gelation effect and attract the migration of nanosheets. Figure 5 The electrostatic attraction of magnesium ions has a limited effect on the orientation of nanosheets. As the ions diffuse further, the stacking of nanosheets becomes disordered. In contrast, the gelation effect produced by calcium ions can achieve long-range orientation of nanosheets.

[0092] Example 3:

[0093] 1) 4 parts by weight of spherical alumina particles, 100 parts by weight of water, and 2 parts by weight of sodium alginate were added to a container and stirred to obtain an alumina dispersion; the concentration of the alumina flakes was about 1 vol%.

[0094] 2) Take filter paper and adsorb enough 5 mol / L calcium chloride solution on the filter paper;

[0095] 3) Immerse the filter paper in the alumina dispersion for 10 minutes;

[0096] 4) removing the filter paper adhered with the alumina gel;

[0097] 5) removing the filter paper and freeze-drying the gel to obtain an ordered assembled alumina particle skeleton.

[0098] Example 4:

[0099] 1) Add 50 parts by weight of aluminum oxide flakes, 100 parts by weight of water, and 2 parts by weight of sodium alginate into a container and stir them evenly to obtain an aluminum oxide dispersion; the concentration of the aluminum oxide flakes is about 12 vol%.

[0100] 2) A polyethylene terephthalate plastic plate (PET, 10*10*1 mm) was plasma treated to make the surface hydrophilic.

[0101] 3) Add enough 5 mol / L calcium chloride solution onto the plastic plate;

[0102] 3) Immerse the plastic plate in the alumina dispersion for 10 minutes;

[0103] 4) Providing a plastic plate adhered with aluminum oxide gel;

[0104] 5) Dry the gel and remove the plastic plate to obtain an alumina skeleton, such as Figure 6 As shown, an oriented alumina skeleton was successfully grown on the plastic surface.

[0105] Example 5:

[0106] 1) adding 50 parts by weight of aluminum oxide flakes, 100 parts by weight of water, and 2 parts by weight of sodium carboxymethyl cellulose into a container, and stirring them uniformly to obtain an aluminum oxide dispersion;

[0107] 2) Take filter paper and adsorb enough 5 mol / L calcium chloride solution on the filter paper;

[0108] 3) Immerse the filter paper in the alumina dispersion for 10 minutes;

[0109] 4) removing the filter paper adhered with the alumina gel;

[0110] 5) Dry the gel and remove the filter paper to obtain an alumina skeleton, such as Figure 7 As shown in the figure, it can be seen that carboxylated polyelectrolytes can be used for gelation-induced oriented nanosheets, further demonstrating the universality of the gelation-induced orientation method.

[0111] Example 6:

[0112] 1) Add 50 parts by weight of aluminum oxide flakes, 100 parts by weight of water, and 2 parts by weight of sodium alginate into a container, and stir them evenly to obtain an aluminum oxide dispersion;

[0113] 2) Take filter paper and adsorb enough basic zirconium chloride (Zr) with a concentration of 5 mol / L on the filter paper. 4+ ) solution;

[0114] 3) Immerse the filter paper in the alumina dispersion for 10 minutes;

[0115] 4) removing the filter paper adhered with the alumina gel;

[0116] 5) Dry the gel and remove the filter paper to obtain an alumina skeleton, such as Figure 8 As shown in the figure, it can be seen that the gelation-induced orientation method can also be achieved by using different types of ions, further proving the universality of the gelation-induced orientation method.

[0117] Example 7:

[0118] 1) adding 15 parts by weight of aluminum oxide sheets, 100 parts by weight of water, and 2 parts by weight of chitosan into a container, and stirring them uniformly to obtain a glass fiber dispersion;

[0119] 2) Take filter paper and adsorb enough 5 mol / L sodium citrate solution on the filter paper;

[0120] 3) Immerse the filter paper in the alumina dispersion for 10 minutes;

[0121] 4) removing the filter paper adhered with the alumina gel;

[0122] 5) Dry the gel and remove the filter paper to obtain an alumina skeleton, such as Figure 9 As shown in the figure, it can be seen that the gelation-induced orientation method is applicable to positively charged nanosheets (chitosan adsorbed on the nanosheets, making them positively charged). At the same time, the gelation-induced orientation is achieved by using anions (citrate), further proving the universality of the gelation-induced orientation method.

[0123] Example 8:

[0124] 1) adding 1 part by weight of glass fiber, 100 parts by weight of water, and 2 parts by weight of sodium alginate into a container, and stirring them uniformly to obtain a glass fiber dispersion;

[0125] 2) Take filter paper and adsorb enough 5 mol / L calcium chloride solution on the filter paper;

[0126] 3) Immerse the filter paper in the alumina dispersion for 10 minutes;

[0127] 4) removing the filter paper adhered with the alumina gel;

[0128] 5) Dry the gel and remove the filter paper to obtain a glass fiber skeleton. Figure 10 shown.

[0129] Comparative Example: Different from Example 6, Darwin's solution was used instead of sodium alginate, i.e., no gelation was performed. Figure 11 .

[0130] contrast Figure 10 and Figure 11 , the gelation-induced orientation method also has a certain orientation effect on one-dimensional materials.

[0131] Example 9:

[0132] 1) adding 15 parts by weight of glass fiber, 15 parts by weight of alumina flakes, 100 parts by weight of water, and 2 parts by weight of sodium alginate into a container, and stirring them uniformly to obtain a glass fiber dispersion;

[0133] 2) Take filter paper and adsorb enough 3 mol / L barium chloride solution on the filter paper;

[0134] 3) Immerse the filter paper in the glass fiber / alumina dispersion for 10 minutes;

[0135] 4) Producing filter paper with glass fiber / alumina gel attached;

[0136] 5) Dry the gel and remove the filter paper to obtain a glass fiber / alumina skeleton, such as Figure 12 As shown in the figure, a glass fiber skeleton with uniform alternating orientation of sheets and fibers was successfully prepared. From the figure, it can be seen that the gelation orientation induction method can be used to prepare composite structure skeletons, broadening the application of materials.

[0137] Example 10:

[0138] 1) adding 15 parts by weight of alumina particles, 15 parts by weight of alumina flakes, 100 parts by weight of water, and 2 parts by weight of sodium alginate into a container, and stirring them uniformly to obtain a glass fiber dispersion;

[0139] 2) Take filter paper and adsorb enough zinc chloride solution with a concentration of 3 mol / L on the filter paper;

[0140] 3) Immerse the filter paper in the alumina ball / plate dispersion for 10 minutes;

[0141] 4) Remove the filter paper with the alumina ball / sheet gel attached;

[0142] 5) Dry the gel and remove the filter paper to obtain the alumina sphere / sheet skeleton. Figure 13As shown in the figure, an oriented alumina sheet skeleton with attached alumina spheres was successfully prepared. From the figure, it can be seen that the gelation orientation induction method can be used to prepare composite structure skeletons, broadening the application of materials.

[0143] Example 11:

[0144] 1) Add 50 parts by weight of aluminum oxide flakes, 100 parts by weight of water, and 2 parts by weight of sodium alginate into a container, and stir them evenly to obtain an aluminum oxide dispersion;

[0145] 2) Plasma treatment of copper wire (100 μm diameter) to make the surface hydrophilic;

[0146] 3) Add enough 5 mol / L calcium chloride solution onto the copper wire;

[0147] 3) Immerse the copper wire in the alumina dispersion for 5 minutes;

[0148] 4) Proposing a copper wire adhered with alumina gel;

[0149] 5) Dry the gel and remove the copper wire to obtain a micro-curved alumina skeleton, such as Figure 14 As shown in the figure, a micro-curved alumina skeleton oriented along the surface of the copper wire was successfully prepared. The figure shows that the gelation orientation induction method can be used to produce skeletons of different shapes, including micron-scale oriented structures, which can broaden the application of the material.

[0150] Example 12:

[0151] 1) Add 50 parts by weight of aluminum oxide flakes, 100 parts by weight of water, and 2 parts by weight of sodium alginate into a container, and stir them evenly to obtain an aluminum oxide dispersion;

[0152] 2) Plasma treatment of the curved acrylic plastic sphere to make the surface hydrophilic;

[0153] 3) Add enough 5 mol / L calcium chloride solution onto the plastic ball;

[0154] 3) Immerse the plastic balls in the alumina dispersion for 10 minutes;

[0155] 4) Producing plastic balls adhered with alumina gel;

[0156] 5) The gel was dried and the plastic spheres removed, resulting in a curved alumina skeleton. This successfully produced a curved alumina skeleton oriented along the spherical surface. This demonstrates that the gelation-induced orientation method can be used to create skeletons of various shapes, including large-scale (millimeters or larger) oriented structures, broadening the material's applications.

[0157] Example 13:

[0158] 1) Add 50 parts by weight of aluminum oxide flakes, 100 parts by weight of water, and 2 parts by weight of sodium alginate into a container, and stir them evenly to obtain an aluminum oxide dispersion;

[0159] 2) Take filter paper and adsorb enough 5 mol / L calcium chloride solution on the filter paper;

[0160] 3) Disperse the aluminum oxide in a spray bottle and spray it onto the filter paper 10 times, with an interval of 10 seconds between each spray.

[0161] 4) Dry the gel and remove the filter paper to obtain an alumina skeleton, such as Figure 15 As shown in the figure, an oriented alumina skeleton was successfully prepared. As can be seen from the figure, the gelation orientation induction method can be implemented in many ways, including a simple spraying method, which broadens the application of the method.

[0162] Example 14:

[0163] 1) Add 50 parts by weight of aluminum oxide flakes, 100 parts by weight of water, and 2 parts by weight of sodium alginate into a container, and stir them evenly to obtain an aluminum oxide dispersion;

[0164] 2) Plasma treatment of the copper wire to make the surface hydrophilic;

[0165] 3) Add 5 mol / L calcium chloride solution onto the copper wire;

[0166] 4) Design two porous plates with the same array and insert the copper wire into the mold;

[0167] 5) Immerse the mold in the alumina dispersion for 10 minutes;

[0168] 6) Producing a mold with aluminum oxide gel adhered thereto;

[0169] 7) Drying the gel and removing the copper wires to obtain an alumina skeleton with an array pore structure, with the nanosheets oriented along the pores, such as Figure 16 As shown in the figure, it can be seen that the gelation orientation induction method can achieve complex three-dimensional structures, broadening the application of the method.

[0170] Example 15:

[0171] 1) Add 100 parts by weight of water to a container, add a certain amount of glass sheets so that the volume content of the glass sheets is about 20 vol%, and slowly add carboxyl chitosan while monitoring the viscosity in real time. When the viscosity of the assembly solution is about 500 mPa·s, stop adding carboxyl chitosan to complete the preparation of the assembly solution.

[0172] 2) Take filter paper and adsorb 1 mol / L ferric chloride solution on the filter paper. At this time, the gelation speed is about 0.2 mm / min;

[0173] 3) Immerse the filter paper in the alumina dispersion for 10 minutes;

[0174] 4) Remove the filter paper with aluminum oxide attached;

[0175] 5) Dry the gel and remove the filter paper to obtain an oriented glass sheet skeleton.

[0176] Example 16:

[0177] 1) 100 parts by weight of water was added to a container, and a certain amount of clay flakes and carboxyl polyurethane was added so that the volume content of the clay flakes was about 10 vol% and the viscosity of the assembly solution was about 500 mPa·s.

[0178] 2) Take filter paper and adsorb enough 0.1 mol / L calcium chloride solution on the filter paper;

[0179] 3) Immerse the filter paper in the alumina dispersion for 10 minutes;

[0180] 4) Remove the filter paper with aluminum oxide attached;

[0181] 5) Drying the gel and removing the filter paper to obtain a polyurethane elastomer with an oriented clay sheet skeleton.

[0182] Example 17:

[0183] 1) adding 50 parts by weight of alumina flakes, 100 parts by weight of water, 1 part by weight of sodium alginate, 1-30 parts by weight of sodium acrylate (AAcNa, gel comonomer 1), 1-30 parts by weight of acrylamide (AAm, gel comonomer 2), 0.1-1 parts by weight of N,N-methylenebisacrylamide (BIS, gel crosslinker), and 0.1-0.3 parts by weight of N,N,N',N'-tetramethyldiethylamine (TEMED, gel accelerator) into a container;

[0184] 2) stirring the mixture to obtain an alumina dispersion, and heating the mixture in a water bath at 60°C;

[0185] 3) Take filter paper and adsorb sufficient 2.5% potassium persulfate (gel initiator) solution on the filter paper;

[0186] 4) Immerse the filter paper in the alumina dispersion for 10 minutes;

[0187] 5) removing the filter paper adhered with the alumina gel;

[0188] 6) removing the filter paper, placing the gel in a 0.1 mol / L iron ion solution for 24 hours, rinsing with a large amount of water, and soaking for 24 hours to obtain a high-energy-dissipation porous elastic hydrogel.

[0189] Example 18:

[0190] 1) adding 50 parts by weight of aluminum oxide flakes, 100 parts by weight of water, and 2 parts by weight of sodium carboxymethyl cellulose into a container, and stirring them uniformly to obtain an aluminum oxide dispersion;

[0191] 2) Take two copper sheets (20mm*100mm*2mm) as electrodes, connect the positive and negative terminals of a DC power supply, and immerse the other ends in the dispersion to a depth of 50mm, with a distance of 1cm between the electrodes.

[0192] 3) After immersing the copper sheet, apply power for 5 minutes;

[0193] 4) removing the filter paper adhered with the alumina gel;

[0194] 5) Dry the gel and remove the filter paper to obtain an alumina skeleton, such as Figure 17 As shown in the figure, it can be seen that the in-situ copper ion release caused by electrical current can also achieve effective gelation-induced oriented nanosheets, further demonstrating the universality of the gelation-induced orientation method.

Claims

1. An ordered assembly method, characterized in that: The following steps are involved: Placing a substrate capable of releasing charged particles in an assembly liquid to obtain an ordered assembled material; the assembly liquid comprises assembly primitives, and the assembly primitives can form an electrostatic interaction with the charged particles; The assembly solution also includes a gel component, which can form a gel under the induction of the charged particles.

2. The method according to claim 1, characterized in that The substrate adsorbs a solution containing charged particles, and the concentration of the charged particles is above 0.1 mol / L.

3. The method according to claim 1, characterized in that The assembly unit itself is charged, or the surface is charged through surface modification.

4. The method according to claim 1, wherein The charged particles are charged ions or charged polymers.

5. The method according to claim 1, wherein The assembly unit is at least one of a zero-dimensional material, a one-dimensional material, a two-dimensional material, and a three-dimensional material.

6. The method according to claim 5, characterized in that The zero-dimensional materials include: gold particles, polymethyl methacrylate particles; the one-dimensional materials include: carbon nanotubes, silver nanowires, silicon carbide nanowires, silicon nitride nanowires, cellulose nanofibers, glass fibers, carbon fibers, polyimide fibers; the two-dimensional materials include: boron nitride nanosheets, aluminum oxide nanosheets, glass sheets, mica sheets, clay sheets, graphene, molybdenum disulfide; the three-dimensional materials include: bismuth oxychloride nanoflowers.

7. The method according to claim 1, characterized in that The assembly unit is a one-dimensional material or a two-dimensional material, and the concentration of the assembly unit is below 20 vol%.

8. The method according to claim 1, characterized in that The substrate adsorbs the solution containing charged particles so that the gel formation speed is below 0.2 mm / min.

9. The method according to claim 1, characterized in that The gel component is a polymerizable monomer, and the charged particles are anions of an initiator or cations of an initiator; or the gel component is a polyelectrolyte, and the charged particles are ions or polyelectrolytes with opposite electrical properties to those of the gel component.

10. The method according to claim 9, characterized in that The polyelectrolyte is a negatively charged polyelectrolyte or a positively charged polyelectrolyte, and the charged particles are cations, including: Na + , Ca 2+ 、Zn 2+ 、Ba 2+ 、Cu 2+ 、Fe 3+ 、Al 3+ 、Zr 4+ , or anions, including: citrate, tripolyphosphate; the polymerizable monomers are acrylamide, acrylic acid, dimethyldiallylammonium chloride; the anion of the initiator is persulfate; the cation of the initiator is Lewis root.

11. The method according to claim 1, wherein The surface modification of the assembly unit is achieved by using the gel component.

12. The method according to claim 1, characterized in that The method also includes removing the gel component to obtain a skeleton material composed of assembly units.

13. The method according to claim 12, characterized in that Methods for removing gel components include: physical high-temperature burning and chemical dissociation.

14. The method according to any one of claims 1 to 13, characterized in that The method also includes injecting functional materials into the assembled materials to obtain functional composite materials.

15. The method according to claim 14, characterized in that The functional materials include: prepolymer resin and high molecular monomer.

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