TWI248376B - Preparation of hollow structure material by interfacial precipitation - Google Patents

Abstract

The present invention relates to prepare a hollow structure material by interfacial precipitation comprising: using a first solvent to dissolve a material forming a solution; applying a spray method to spray the solution into a small droplet with a shape to pass through a second solvent, then precipitation occurring on the interface of the small droplet to form a solid shell; and removing the first solvent and the second solvent to form the hollow structure material.

Description

1248376 V. INSTRUCTIONS INSTRUCTIONS (1) In the field of invention, especially in the micro-system, there is a method for manufacturing a non-card-class hollow spherical material, which is a kind of hollow-material material of the shape of a hollow material. BACKGROUND OF THE INVENTION Hollow material catalysis, adsorption and medicinal stencils used by PharmaTech, through the appropriate filtration, washing to produce some rules using emulsifier 948-951, C Ding Nature 359, with two molecules with Science 279, Used to make hollow go 'and crystal treatment, 4 can be expensive and consistent. In view of this empty material method, or the application of porous materials is very wide, it is commonly used in the touch of 'capsule' gene grab bullets, hollow tubes, etc. , Industrial use ^ 1 The general method for the manufacture of hollow-shaped materials is to pick /i: 'The organic molecular stencil and inorganic water glass into the solution hydrothermal reaction arranged into a regular crystal shape, after the 'Honggan' calcination Among them, the organic matter slowly decomposes thermally, = hollow or porous. For example, A. Imhof et al. stencils to make macroporous materials, Nature 38 9, (1 9 97 )

Kresge, et al. used liquid crystal stencil to synthesize mesoporous material (1 9 9 2 ) 7 1 0-7 1 2, and S· a. Jenekhe et al. arranged the stick-line end features into a spherical shape to make hollow spheres (1 9 9 8 ) 1 9 0 3 - 1 9 0 9. Due to molecular stencil technology or porous materials, it is often necessary to arrange at high temperature or high pressure for a long time. It must be destroyed by high temperature calcination to destroy some low temperature materials. At the same time, the current molecular template will be used in production. The price of the hollow material is relatively high, and the object of the present invention is to provide a practical and simple manufacturing property in which the first solvent has a dissolved material, and

1248376 V. DESCRIPTION OF THE INVENTION (2) The two solvents have the characteristics of a crystalline precipitation material, and a dispersion technique contacts the first solution to the second solvent to form a precipitate, forming a rigid solid interface, which can be widely used at room temperature to manufacture various kinds of materials. Micron and nano hollow materials. SUMMARY OF THE INVENTION The present invention is a micron and nano-scale hollow material manufacturing technique comprising: dissolving a material using a first solvent to form a solution; dispersing the solution into a shaped liquid using a dispersion technique; The liquid passes through a second solvent, and when the shaped liquid touches the second solvent, the material in the liquid inside the shaped liquid immediately produces a solid precipitated at the interface of the shaped liquid, and The first solvent inside the shaped liquid will gradually diffuse through the solid interface of the spherical droplets into the second solvent to form a hollow solid material; and the first field of the invention is removed. Shape hollow material technology, especially the manufacturing method of micron and nano-sized hollow spherical materials. BACKGROUND OF THE INVENTION Hollow materials or porous materials are widely used, and are commonly used in catalyst carriers, adsorbents, capsules, gene gun bullets, hollow tubes, etc., industrial and medical high-tech applications. A common method for generally manufacturing a hollow material is to use a molecular stencil method in which an organic molecular stencil and an inorganic water glass are placed in a solution and arranged into a regular crystal shape by a suitable hydrothermal reaction.

Page 7 1248376 V. Description of invention (3) From the filtration, washing to produce some rules using emulsifier 948-951, CT Nature 359, using polymer with Science 279, used to make hollow method, and crystal treatment, may price Expensive, practical. , drying, calcining, which slowly decomposes organic matter, nature: empty or porous. For example: A. Imh〇f et al. 提 制造 Manufacture of macroporous materials, Nature 38 9, (1 9 97)

Kresge, et al. used a liquid crystal template to synthesize mesoporous materials (1992) 710-712, and s, A·Jenekhe et al. arranged the stick-line end features into a spherical shape to make a hollow sphere U 9 9 8 ) 1 9 0 3 - 1 9 0 9 . Due to molecular stencil technology or porous materials, it is often necessary to arrange at high temperature or high pressure for a long time. It is necessary to decompose and decompose some low-temperature materials during high-temperature calcination. At the same time, molecular templates are in practical mass production. The price of the hollow material is made high, and the object of the present invention is to provide a practical and simple method for manufacturing a hollow material, which utilizes the first solvent to have the property of dissolving the material, and the second solvent has the property of producing a precipitated material, and A dispersing technique contacts the first > trough liquid to the second solvent to form a precipitate that forms a rigid solid interface. This technique can be widely applied at room temperature to produce hollow materials of various micrometers or even nanometers. SUMMARY OF THE INVENTION The present invention is a micron and nanoscale/shape hollow material manufacturing technique comprising: dissolving a material using a first solvent to form a solution; dispersing the solution into a shaped liquid using a dispersion technique; The liquid passes through a second solvent, and when the shaped liquid touches the second solution 1248376 5. The invention (4) agent, the material in the liquid inside the shaped liquid immediately precipitates solids in the liquid The interface of the shaped liquid, and the first solvent inside the shaped liquid will gradually diffuse through the solid interface of the spherical droplets into the σ 苐 ' 谷 谷 , , , , , , , , , , The first solvent and the second solvent form the shaped hollow material. The first solvent includes at least: water, an acid, an alcohol, a sterol, an ethanol, an ethylene glycol, a glycerin, an amine or the like. The above material is soluble in the first solvent and comprises: a colloid and a metal salt. Such colloids include: organic colloids such as proteins, polymers, etc., inorganic colloids such as aluminum chlorodydrate (ACH), sulfuric acid, aluminum hydroxide, water glass, and the like. The metal salt includes at least: Z r C 12 〇. 8 H2 0,

SnCl4·5H20, A1C13. 6H20, etc. Dispersion techniques according to the above concept include: spray method, ultrasonic steam, and electric vaporization. The spherical droplets described above range in size from micron to nanometer (5 〇 um um - 50 Onm). The second solvent includes at least water, alcohol, acetone, organic amines such as 'triethylamine, tributylamine, and the like. The first solvent and the second solvent are mutually soluble and partially miscible. The method of removing the first solvent and the second solvent according to the above concept includes a method of "filtering", vacuum drying, natural evaporation, drying, calcination, and the like. The case can be explained by the following diagrams, and a deeper understanding is obtained: Figure 1 · S E Μ 呈现 呈现 呈现 呈现 呈现 传统 传统 传统 传统 传统 传统 传统 传统 形状 形状 形状 形状 形状 形状 形状 形状 形状 形状 形状 形状 形状 形状 形状 形状 形状 形状 形状 形状 形状 形状 形状 形状 形状 形状 形状 形状 形状 形状 形状 形状

1248376 罾 η

Figure 2: The technology of this case is very strong (5) · One of the techniques used to prepare the hollow material by the spray method, Figure 2 · SEM image shows the technology of the production of ACH large particles (a) - group = 2 wide,士* open, hole 'shape regular image - blank shape (b) shape shows the monthly opening / c spherical shape (d) rough spherical surface; Figure 4: SEM image (a) % one +, A Smcate has a concave water glass solution S〇dlUm., ^ ya , the spherical particles of the spoon (b), after adding glycerin, the sprayed water glass only obtains spherical particles and does not have a concave hole. Figure 5 (a) shows the AM sinking small about 1 · 8um, dried and presented as 颏_山★ f.I ώ/ιΛ See the hollow concave shape. Figure 4 (b) Al2Q3 oxidized Mingqiu ball with a temperature of 80 °C and a small silver ball has a hole; body six, · flat figure is not taken out and dried, and the calcined body presents a hollow sphere structure of about 5_2〇 Um, Fig. 5 (8) magnified observation of the droplets:: ΐ ί ί 生 中空 中空 中空 中空 中空 中空 中空 中空 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当) Private / cereal agent into a hollow bad machine: (:), '容本有案; ιΛ_ι empty sphere generation diagram when the spray mist kinetic energy is small, U) The first solvent of cold material is so small ( b) When entering the second solvent, the product is discharged into a spherical shape in the process, and the ball is discharged into the sphere. The raw material: = circle, (4) the internal liquid 遂 遂 u u α 夕 洛 形成 形成 形成 形成埭

Page 10 J248376, V. Description of invention (6) Body. Description: Precipitation method organic solvent to induce the agglomeration of the temple can also be used to produce the temple. It is often the uniform mixing of the shoal. The chlorohydrat makes the two liquids touch the mixed flow field. The case will use two and two solvents, evaporation, etc. The material solvent and the control material droplets or pipelines pass through the sphere or the f-viscosity 'surface sheets can dissolve each other to form a hollow. As a result, the following results have been shown that the solid agent that is transmitted through is rapidly moving as shown in Figure 1 e (ACH) surface, and the solvent is used to produce the ultrasonic agent dispersion/length to make the shape of the precipitating line and so on. The precipitated acid-base is usually formed by adding the indicated material to form a shape, and the precipitate is oscillated into a small solution. In order to make the solid body crystallization, the neutralization of the original material is traditionally nucleated, and the shape is often precipitated and evaporated. The liquid droplets of the ball can still be small and the inside of the droplet The material, especially the use is a well-known technique 'usually, the shape, the solution of the solution is prepared to be irregular, and the long crystal 'sink can't control the solvent can be reused by the partial evaporation method or the pipeline-like surface. The dissolution of the dissolved portion of the heart control material is also considered to be due to the fact that during the precipitation process, the aluminum which is stirred by the agitation is due to the rapid mixing of the temple, due to the regularity of the liquid. The material is dispersed, the injection, and the selection force are so that the dissolving agent and the sediment in the boundary material are gradually dispersed in a more dissolving surface than in the form of a dissolution, for example, a spray molding method, and the concentration is not diffused. Good example

Page 11 I248376 1 V. Description of the invention (7) One of the examples, Aluminum chlorohydrate (ACH) is a commonly used flocculant, which can be used in wastewater treatment as a settling agent, the sedimentation effect is better than alum, or Ge makeup σ The anti-sweat agent of the mouth can be used to absorb sweat. In this study, an aqueous solution of ACH was prepared by electrolysis, using 3x5 cm2 aluminum sheet as anode, 2x2 cm2 titanium sheet as = pole, 〇·6N hydrochloric acid 500 mL as electrolyte, and 7 amps. After 8 hours of electrolysis, holding 2 degrees Celsius at 35 degrees Celsius, an ACH aqueous solution is produced, and then filtered through a 〇·45um filter paper. 2' The structure of the device used in the present invention is shown in Fig. 2, and the obtained filtrate is taken out.

Second, a solution 1, and then using a sprayer 3 connected to a cylinder 4 to disperse the solution into tiny droplets, which are deposited into the acetone liquid 2 and immediately precipitated.

The sediments are dried or dried, and the resulting shape is shown in Fig. 3. The SEM image shows that the ACH large particles are made from 5-10Oum. Figure 3(a) - The hollow material has an opening and the shape is like a blank. Shape, Figure 3 (b) The shape is elliptical, Figure 3 (c) hollow spherical fish | face view, Figure 3 (d) rough spherical surface. Second embodiment

^Sodium silicate solution (Aldrich Chemical C〇I^Pany) is a mixture of 50 mL of water glass solution and 100 mL of water in a general water glass solution, and the spherical particles with concave holes as shown in Fig. 4(a) can be obtained in the same way as: ^力口入1 ◦ m L glycerin and water glass solution 50 m L plus water 1 0 0 m L mixed sentence 'will increase the viscosity of the solution, so that the sprayed particles will not produce a concave hole as shown in Figure 4 (b) Show only spherical particles.

Page 12 1248376, V, invention description (8) Example 3 using A1C13· 6H20 Showa reagent grade 10g dissolved in 100mL aqueous solution, the aqueous solution was sprayed in organic amine tri butyl ai me, the pressure of the sprayer The increase makes the dispersed particles thinner to the nano-sized droplets, and accelerates the impact on the tributylamine liquid surface. Figure 5 (a) shows the SEM image, and the size of a § micron particle of the shoal is dried to give a hollow concave shape. . Figure 5 (b) The alumina balloon after calcination for 4 hours at 80 °C has a hole. In the fourth embodiment, ZrCl2 〇.8H2 〇Showa special-grade reagent i〇g was dissolved in water, and dispersed in a beaker containing 00 mL of organic amine tributylamine in a beaker, and a misty precipitate was formed in the beaker. The precipitate is taken out and dried, and calcined at 800 degrees Celsius. From Fig. 6 (a), the spheroids are dry, the spheres are formed by calcination, and the average spherical diameter is large =,: The dispersion technique can be used to determine the size of the droplets. Straight: large and small particles can reach um5um, P1 gentleman mountain ~ cited technology to take small control. ° τ working spherical shell thickness can be derived from the material concentration of the technology of this case can also be free of 丨 &; 」 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体 流体Speed, and fog ^ He shot the shape of the particles of the big drop. In theory, ::::: sticky, 'to determine the possible surface of the particles after the production of liquid surface has a mouth-like ’ ‘the particles have a relatively large kinetic energy in the impact of the quilt, and its fluid shear force, will produce

Page 13 I248376 --—— --〆~—— (a) The hollow expansion sphere of the hole &amplogram is generated when the kinetic energy is large, as shown in Figure 7(b) ^The first solvent dispersion of the material In the air, the droplets are spherical, and the figure 7 and the f are engraved into the second solvent to produce a streamlined extrusion into an elliptical shape. In Figure 7 (C), the limb is squeezed to discharge the sphere, Figure 7 (^) The solvent is removed to form a hollow defect. Another technical essence of the present invention is that the production of the empty particle 'hollow sphere is shown, and the first solvent of the material is dispersed in the first solvent to generate a streamlined shape to expand into the sphere boundary to enter the second solvent circle. Sphere. In the use of low kinetic energy droplets, to obtain the intention of when the kinetic energy is very small, Figure 8 (a) the droplets in the dissolved gas are spherical" Figure 8 (b) into the circle, Figure 8 (c) the internal liquid gradually 'Figure eight (d) remove the solvent to form a medium

This is a solvent that is as wide as a sphere, or the size of the pellet. This method can be used to measure the thickness of the wall. Concentration of solvent, ZrCl of salt in an example with obvious solution: It can be expressed as 'one like a colloid or can be blended. 'The air volatility obtained by dispersion can be used to reduce the south and low temperature, and the temperature is low. The situation is small: 〇, in the air ball, salt and other things to control the sphere technology can also be material and spray material dissolved material and so on. It can also obtain a π-steroid flocculant ach. It can be obtained at a proportional concentration. The technology can be applied to a single mass, and can produce a hollow sphere size and an empty sphere shell thickness: for controlling the dispersed droplet dispersion technique. The dispersion of the droplets r concentration of the grain precipitation material 2 is related, but in any case: the analogy uses the same hollow line of injection molding.

1248376, V. Description of the Invention (ίο) The present invention uses a first solvent to dissolve a material, uses a dispersion technique to disperse the solution into a spherical or tubular shape, and then uses a second solvent to immediately produce a solid precipitated solid in the droplet. The interface, which leads to the principle of sedimentation, can utilize dehydration precipitation, acid-base neutralization, etc., and the surface tension can be maintained in a certain spherical or pipeline shape under the control of appropriate material dissolution concentration, wherein the first solvent and the second solvent can be Mutually soluble and partially miscible, so the crystallized sphere will produce an empty spherical or hollow tubular shape. This method can easily make hollow or porous materials of micron or nanometer size. This is the focus of the present invention. In order to protect the creation of the invention in this case, it is necessary to modify it by those who are familiar with the profession. However, it is not necessary to protect the invention as claimed.

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Claims (1)

1248376 _6. Patent Application No. 1 · A technique for preparing a hollow aluminum crucible material by using interface precipitation includes: dissolving a material using a first solvent to form a solution; dispersing the solution into a shape using a dispersion technique a liquid that passes through the second solvent, and when the interface of the shaped liquid touches the second solvent, the material inside the shaped liquid immediately precipitates a precipitated solid in the shape The interface of the liquid forms a solid interface of the shape, and the first solvent inside the shaped liquid will gradually diffuse through the shaped solid interface into the second solvent to form a hollow material of a shape And removing the first solvent and the second solvent to form the shaped hollow material. 2. A technique for preparing a hollow aluminum cerium-zirconium material having a shape as described in claim 1, wherein the shaped liquid comprises a spherical droplet and a columnar columnar liquid. 3. The method of preparing a hollow aluminum bismuth material by using interface precipitation as described in claim 1 of the patent application, wherein the shaped hollow aluminum bismuth zirconium material comprises at least: a spherical hollow material, a ball having a hole a hollow material, with a tubular hollow material. 4 · Preparation of a shape of hollow aluminum cerium zirconium material using interface precipitation as described in claim 1 of the patent application, wherein the size of the spherical hollow material Page 17 1248376 VI. Patent application range Micron to sub-micron (500 μm - 0 · 5 u m). 5) The method of preparing a hollow aluminum cerium zirconium material having a shape as described in the first aspect of the patent application, wherein the first solvent comprises at least water, such as methanol, ethanol, ethylene glycol, glycerin. Classes, etc. 6. A technique for preparing a hollow aluminum cerium-zirconium material having a shape as described in claim 1 of the patent application, wherein the first solvent is water. 7 (Material weight: The material concentration of the material in the first solvent is at least greater than 0.1. The first solvent weighs). 8 · Preparation of a shape of hollow aluminum cerium zirconium material by interfacial precipitation as described in claim 1 of the patent application, wherein the material comprises: chloroaluminum compound (ACH) 5 sodium silicate solution, ZrCl20.8H20 , SnCl4.5H20, A1C13.6H20, etc. 9. A technique for preparing a hollow aluminum bismuth material using interface precipitation as described in claim 1 of the patent application, wherein the dispersion technique comprises: a spray method, an ultrasonic wave, an electrovaporization method, and an injection molding method. 1 0 · Prepare a shape using interface precipitation as described in item 1 of the patent application Page 18 1248376 6. The patented hollow aluminum cerium zirconium material technology, wherein the second solvent includes at least: ethanol, acetone, and the like. The method for removing the first solvent and the second solvent includes: filtration, vacuum drying, natural evaporation, drying, calcination, and the like. 1 1 A technique for preparing a hollow aluminum cerium-zirconium material having a shape as described in the first aspect of the patent application, wherein the first solvent and the second solvent are completely miscible and partially miscible. 1 2 - A technique for preparing a hollow aluminum bismuth material using interfacial precipitation as described in claim 1 of the patent application, wherein the density of the first solvent is greater than the density of the second solvent. Page 19