CN113385050A - Method for manufacturing product formed by phase transfer method and product - Google Patents
Method for manufacturing product formed by phase transfer method and product Download PDFInfo
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- CN113385050A CN113385050A CN202110555573.0A CN202110555573A CN113385050A CN 113385050 A CN113385050 A CN 113385050A CN 202110555573 A CN202110555573 A CN 202110555573A CN 113385050 A CN113385050 A CN 113385050A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
Abstract
The invention discloses a manufacturing method of a product formed by a phase transfer method and the product, and the technical scheme key points of the method comprise the following steps: s01, immersing a template into a solution, wherein the template comprises spaced apart openings, the solution comprises a first solvent and a polymer soluble in the first solvent; s02, introducing a second solvent into the solution to cause phase inversion of the solution and form an article over the template; the article includes an article body formed on top thereof, and spaced apart channels extending from the article surface to the article body, the channels being dendritic. The product of the invention can accelerate mass and heat transfer, reduce material transmission resistance, increase the specific surface area in the product and provide a good place for chemical reaction.
Description
Technical Field
The present invention relates to a method for producing a product molded by a phase transfer method, and a product.
Background
The prior Chinese patent with the publication number of CN105188893B discloses a product with a channel and a manufacturing method thereof, wherein the method comprises the following steps: contacting a template having spaced apart openings with a solution comprising a first solvent and a polymer soluble in the first solvent; introducing a second solvent into the solution through the openings of the template to cause phase inversion of the solution and form an article having spaced apart channels extending from the surface of the article to a substantially planar body of the article.
The main body of the product is a spongy pore layer (refer to fig. 1), but in the method, a second solvent is introduced into the solution through the opening of the template, so that the formed spongy pore layer has a larger thickness (usually 30-300 μm), and the mass and heat transfer can be influenced in practical application, and additional material conveying resistance is caused.
Disclosure of Invention
Aiming at the defects in the prior art, one of the purposes of the invention is to provide a method for manufacturing a product formed by using a phase transfer method, wherein the thickness of a spongy pore layer of the manufactured product is smaller, the mass and heat transfer can be accelerated, the material transfer resistance is reduced, and meanwhile, the dendritic channel also increases the specific surface area in the product, thereby providing a good place for chemical reaction.
In order to achieve the purpose, the invention provides the following technical scheme:
a method of manufacturing an article formed by phase transfer molding, comprising the steps of:
s01, immersing a template into a solution, wherein the template comprises spaced apart openings, the solution comprises a first solvent and a polymer soluble in the first solvent;
s02, introducing a second solvent into the solution to cause phase inversion of the solution and form an article over the template; the article includes an article body formed on top thereof, and spaced apart channels extending from the article surface to the article body, the channels being dendritic.
Through adopting above-mentioned scheme, compare in prior art, place the template in the deeper position of solution, the second solvent need not pass the template and directly get into solution, there is spaced apart passageway in the goods that form above the template after the phase transition, but single passageway can be gradually the branching shape of branch and branch, after a plurality of forks, the thickness of the spongy pore layer (being the goods main part) that the goods top formed can greatly reduced, the whole plane that is of goods main part, thickness is usually at 1-10 mu m, thereby can accelerate mass transfer heat transfer greatly, reduce material transmission resistance, and the branching passageway links to each other, the inside specific surface area of goods has been increased, good place is provided for chemical reaction.
Further, in step S01, the depth of the template immersed in the solution is defined as H, and H > 0.03 mm.
Further, in step S01, H is more than 0.03mm and less than or equal to 3 mm.
Further, the method also comprises the following steps:
s03, removing the template after phase inversion.
After phase inversion the template is removed, leaving the channels exposed or open. While the article may be sold in this state without any further processing, the method may further include the additional step of drying, fixing, heating or sintering the article. For example, if the solution is a ceramic material, the ceramic article obtained after phase inversion is in a green state, and it is common for the method of making a ceramic article to further comprise the step of sintering the ceramic article to form a sintered ceramic article.
Further, the solution also includes particulate material suspended in the solution.
Further, the solution is ceramic slurry, and the particulate material is a particulate ceramic material.
By adopting the above scheme, in the formation of the ceramic article, the first solvent, the polymer and the particulate ceramic material are contained in the solution, the particulate ceramic material may be insoluble in the solution, and the combination of the first solvent, the polymer and the particulate ceramic material is also referred to as ceramic slurry.
Further, the solution also comprises polyvinylpyrrolidone, polyethylene glycol, protonic acid or surfactant.
By adopting the above scheme, in the method of the present invention, the phase inversion process can be carried out in the presence of additional components that assist in the formation of the article. One example of such an additional component is a dispersant, the function of which is to prevent agglomeration of the components of the solution or slurry comprising the first solvent, the polymer and optionally the particulate material. Agglomeration can lead to non-uniform solutions and non-uniform products, which is undesirable. Examples of suitable dispersing agents include polyvinylpyrrolidone (PVP), polyethylene glycol, protonic acid (prionic acid) or surfactants such as Span-80.
It is another object of the present invention to provide an article made by the above method comprising an article body and spaced apart channels extending from the article surface to the article body, the channels being dendritic.
Further, the article is a ceramic membrane.
The article produced by the above process may take the form of a channeled membrane, such as a ceramic membrane, although other forms may be used.
In conclusion, the invention has the following beneficial effects:
compared with the prior art, the invention achieves unexpected technical effect and remarkable progress by changing the placing depth of the template; the product formed by the invention is essentially different from the product in the prior art in channel structure, a single channel in the invention can gradually take the shape of a dendritic branch, and after a plurality of times of branching, a spongy pore layer (namely a product main body) is formed, the thickness of the spongy pore layer is greatly reduced, so that the mass and heat transfer are greatly accelerated, the material transmission resistance is reduced, and the smaller channels also increase the specific surface area in the product, thereby providing a good place for chemical reaction.
Drawings
FIG. 1 is a scanning electron micrograph image of a cross-section of an article of the background art;
FIG. 2 is a schematic view of a method for producing an article molded by the phase transfer method in example 1;
FIG. 3 is a scanning electron micrograph image one of a cross section of the article of example 1;
FIG. 4 is scanning electron micrograph image two of a cross section of the article of example 1;
FIG. 5 is a graph showing the comparison of oxygen flux at different temperatures between the product of example 1 and the product of the prior art, wherein line A corresponds to the product of this example and line B corresponds to the product of the prior art;
in the figure: 1. a mold; 2. a template; 3. a solution; 4. a second solvent; 5. an article of manufacture.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Example 1:
a method of manufacturing an article formed by phase transfer molding, comprising the steps of:
s01, immersing a template into a solution, wherein the template comprises spaced openings, and the solution comprises a first solvent and a polymer soluble in the first solvent;
s02, introducing a second solvent into the solution to cause phase inversion of the solution and form an article over the template; the article includes an article body formed on top thereof, and spaced apart channels extending from the article surface to the article body, the channels being dendritic;
s03, removing the template after phase inversion.
Referring to fig. 2, specifically, both the template 2 and the solution 3 are placed in the mold 1, and the template 2 in this embodiment is entirely immersed in the solution 3 and is placed at a position deeper in the solution 3 than the method in the background art; then introducing a second solvent 4 into the solution 3 to cause phase inversion of the solution 3 and form a desired article 5 above the template 2, followed by separation of the article 5 from the template 2, while a product formed below the template 2 is not desired; in this embodiment, the depth of the template 2 immersed in the solution 3 is defined as H, and then H is greater than 0.03mm and less than or equal to 3mm, but in other alternative embodiments, the depth H may also be adjusted as needed, and the desired product 5 may be formed above the template 2, which is not limited herein.
Referring to fig. 1, 3 and 4, in contrast to the method of the background art, in the present embodiment, by changing the depth of the template, a different channel structure is formed in the article; specifically, in the background art, the second solvent passes through the template and enters the solution, so that a regular, uniform and single vertical microchannel is formed in the product; in this embodiment, the template is placed at a deeper position in the solution, the second solvent directly enters the solution without passing through the template, spaced channels also exist in the product formed above the template after phase inversion, but a single channel gradually takes the shape of a dendritic bifurcation, after a plurality of bifurcations, the thickness of a spongy pore layer (i.e., a product main body) formed at the top of the product is greatly reduced, the product main body is integrally planar and is usually 1-10 μm thick, so that mass and heat transfer can be greatly accelerated, the material transmission resistance is reduced, and the bifurcated channels are connected with each other, so that the specific surface area inside the product is increased, and a good place is provided for chemical reaction.
The first solvent may be any solvent that together with the second solvent causes phase inversion to occur. The first solvent is miscible with the second solvent and may be referred to as an anti-solvent-miscible solvent. The first solvent is also a solvent suitable for dissolving the polymer. Examples of suitable first solvents include 1-methyl-2-pyrrolidone (NMP), acetone, dimethyl sulfoxide (DMSO), Dimethylformamide (DMF) and Tetrahydrofuran (THF), dimethylacetamide (DMAc), Formylpiperidine (FP), dioxane, acetic acid (HAc), Morpholine (MP).
The second solvent may be any solvent that is miscible with the first solvent but does not dissolve the polymer to allow phase inversion to occur. Examples of suitable second solvents include water, ethanol, ethylene glycol, isopropanol, or mixtures thereof. Preferably, the second solvent is or comprises water.
The polymer may be referred to as a polymer binder and these terms may be used interchangeably. There are many options for polymers that can be used as the polymer or polymer binder, as long as they are soluble in the first solvent and insoluble in the second solvent. Examples of some suitable polymers include Polyethersulfone (PESF), Ethylene Vinyl Alcohol (EVAL), Cellulose Acetate (CA), polysulfone (Psf), Polyacrylonitrile (PAN), cellulose, polyvinylidene fluoride (PVDF), Polyimide (PI), Polyamide (PA), acrylonitrile-butadiene-styrene (ABS), Polycarbonate (PC), polylactic acid (PLA), High Density Polyethylene (HDPE), PC/ABS, and polyphenylsulfone (PPSU), or mixtures thereof. The amount of polymer used in the process can contribute to the final structure of the ceramic article.
The term "article" as used in this specification refers to an object containing spaced apart channels. The article may have any shape or configuration suitable for its application. The article may be provided in a shape or configuration suitable for application to a battery (e.g., sodium sulfur), to a thermal-to-electrical converter (e.g., an alkali metal thermal-to-electrical converter, also known as a Sodium Heat Engine (SHE)), to a fuel cell (e.g., a molten carbonate fuel cell), a Solid Oxide Fuel Cell (SOFC), and a Solid Oxide Electrolysis Cell (SOEC), or to a microreactor. The article may also be provided in a shape or configuration suitable for application in gas separation, such as in the production of oxygen and hydrogen from a gas stream, in oxygen or hydrogen separation or in applications such as natural gas conversion and the production of hydrogen/syngas from fossil fuels and renewable energy sources, partial reduction of carbon dioxide to carbon monoxide or partial catalytic oxidation of methane to syngas. By way of example, the article may be formed to have an article body that is substantially planar (or entirely planar).
Referring to fig. 5, in the application of the oxygen permeable membrane, the oxygen permeability of the product in this embodiment is much higher than that of the product in the background art at different temperatures, because the dendritic channel structure in the product in this embodiment accelerates the mass transfer rate of oxygen and provides a larger specific surface area for the chemical reaction of oxygen on the surface of the product.
Also included in this embodiment are particulate materials suspended in a solution, specifically a ceramic slurry, the particulate materials being particulate ceramic materials, to form a ceramic article, i.e., a ceramic membrane; in this embodiment, the solution further comprises polyvinylpyrrolidone, polyethylene glycol, protonic acid, or surfactant.
The term "particulate ceramic material" as used in this specification refers to ceramic materials of the well-known type. During manufacture, the ceramic material is prepared in the form of particles for preparation into the desired ceramic article shape to be produced. The ceramic material used to form the ceramic article is provided by a commercially available ceramic powder of the desired composition. The powder can then be processed to obtain the necessary physical powder properties to allow good dispersion, which is an important parameter to achieve uniformity of the resulting article. Further processing steps or treatments of commercial powders (e.g., milling to obtain a suitable particle size, drying, and addition of other additives) may be performed to achieve the necessary physical powder properties. In some embodiments, the ceramic materials may be those having selective gas or ion transport capabilities.
The ceramic material may comprise a metal oxide or a mixed metal oxide. Examples of suitable metal oxides include perovskites, fluorites, beta alumina ceramics, and mixtures thereof. Mixed ceramic materials may also be used, such as mixtures of two or more materials, wherein the particulate materials used in the mixture and their relative amounts will be selected to take advantage of the respective best properties.
Example 2:
an article made by the method of example 1, in particular, the article comprising an article body, and spaced apart channels extending from the article surface to the article body, the channels being dendritic: in this example the article is a ceramic membrane.
Claims (9)
1. A method for manufacturing an article molded by a phase transfer method, comprising the steps of:
s01, immersing a template into a solution, wherein the template comprises spaced apart openings, the solution comprises a first solvent and a polymer soluble in the first solvent;
s02, introducing a second solvent into the solution to cause phase inversion of the solution and form an article over the template; the article includes an article body formed on top thereof, and spaced apart channels extending from the article surface to the article body, the channels being dendritic.
2. The method of manufacturing an article molded by phase transfer method according to claim 1, characterized in that: in step S01, the depth of immersion of the template into the solution is defined as H, and H > 0.03 mm.
3. The method of manufacturing an article molded by phase transfer molding according to claim 2, characterized in that: in step S01, H is more than 0.03mm and less than or equal to 3 mm.
4. The method of manufacturing an article molded by phase transfer method according to claim 1, characterized in that: further comprising the steps of:
s03, removing the template after phase inversion.
5. The method of manufacturing an article molded by phase transfer method according to claim 1, characterized in that: the solution also includes particulate material suspended in the solution.
6. The method of manufacturing an article molded by phase transfer molding according to claim 5, wherein: the solution is ceramic slurry, and the granular material is granular ceramic material.
7. The method of manufacturing an article molded by phase transfer method according to claim 1, characterized in that: the solution also comprises polyvinylpyrrolidone, polyethylene glycol, protonic acid or surfactant.
8. An article made by the method of any of claims 1-7, wherein: the article includes an article body, and spaced-apart channels extending from a surface of the article to the article body, the channels being dendritic.
9. The article of claim 8, wherein: the article is a ceramic membrane.
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| CN202110555573.0A CN113385050A (en) | 2021-05-21 | 2021-05-21 | Method for manufacturing product formed by phase transfer method and product |
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| CN202110555573.0A CN113385050A (en) | 2021-05-21 | 2021-05-21 | Method for manufacturing product formed by phase transfer method and product |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0474424A2 (en) * | 1990-09-01 | 1992-03-11 | The British Petroleum Company P.L.C. | Membranes |
| CN105188893A (en) * | 2013-04-26 | 2015-12-23 | 科廷科技大学 | Channeled articles and methods for their manufacture |
| CN110813108A (en) * | 2019-11-05 | 2020-02-21 | 济南大学 | Separation membrane with bifurcated pore structure and preparation method thereof |
| CN112436171A (en) * | 2020-11-24 | 2021-03-02 | 济南大学 | Solid electrolyte support body and preparation method and application thereof |
-
2021
- 2021-05-21 CN CN202110555573.0A patent/CN113385050A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0474424A2 (en) * | 1990-09-01 | 1992-03-11 | The British Petroleum Company P.L.C. | Membranes |
| CN105188893A (en) * | 2013-04-26 | 2015-12-23 | 科廷科技大学 | Channeled articles and methods for their manufacture |
| CN110813108A (en) * | 2019-11-05 | 2020-02-21 | 济南大学 | Separation membrane with bifurcated pore structure and preparation method thereof |
| CN112436171A (en) * | 2020-11-24 | 2021-03-02 | 济南大学 | Solid electrolyte support body and preparation method and application thereof |
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Application publication date: 20210914 |
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