CN106750500A - A kind of preparation method of structuring compliant conductive porous material and products thereof - Google Patents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/042—Elimination of an organic solid phase
- C08J2201/0422—Elimination of an organic solid phase containing oxygen atoms, e.g. saccharose
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/044—Elimination of an inorganic solid phase
- C08J2201/0444—Salts
- C08J2201/0446—Elimination of NaCl only
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
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Abstract
本发明公开了一种结构化柔性导电多孔材料的制备方法，包括如下步骤：根据实际需求，设计结构化模具；在所述模具中先后依次加入填充粒子和聚二甲基硅氧烷预聚体，制备具有结构化外形的柔性多孔材料；在所述结构化柔性多孔材料中快速且均匀充分的填充导电材料，得到结构化柔性导电多孔材料。本发明还公开了一种应用所述方法制备的结构化柔性导电多孔材料。本发明的制备方法，综合结构化模具成型、填充粒子分级筛选、填充粒子表面微量融合固化处理和负压促渗等技术，使制备出的柔性导电多孔材料具备结构化外形，柔性多孔材料的孔隙大小可控且具有较高孔隙互联互通率，填充粒子浸出充分，同时，总体制备速度相比现有方法能提高2到3倍。
The invention discloses a method for preparing a structured flexible conductive porous material, which comprises the following steps: designing a structured mold according to actual needs; adding filling particles and polydimethylsiloxane prepolymer to the mold successively preparing a flexible porous material with a structured shape; filling the structured flexible porous material quickly and uniformly with a conductive material to obtain a structured flexible conductive porous material. The invention also discloses a structured flexible conductive porous material prepared by applying the method. The preparation method of the present invention integrates technologies such as structured mold forming, filling particle classification and screening, micro-fusion curing treatment on the surface of filling particles, and negative pressure permeation promotion, so that the prepared flexible conductive porous material has a structured shape and the pores of the flexible porous material The size is controllable and has a high pore interconnection rate, and the filling particles are fully leached. At the same time, the overall preparation speed can be increased by 2 to 3 times compared with the existing method.
Description
技术领域technical field
本发明属于导电多孔材料领域，更具体地，涉及一种结构化柔性导电多孔材料的制备方法及应用该方法制备的柔性导电多孔材料。The invention belongs to the field of conductive porous materials, and more specifically relates to a method for preparing a structured flexible conductive porous material and a flexible conductive porous material prepared by applying the method.
背景技术Background technique
结构化柔性多孔材料及结构化柔性导电多孔材料在科研和实际生活中都具有非常广泛的用途。例如，医学研究中细胞培养、生物组织工程等需要依附于某种生物相容性好、孔径大小可控、具有高互联互通率的柔性多孔材料；用于治理海洋污染的油吸附材料则需要某种具有高油吸附能力(即高互联互通率)、超疏水性和超亲油性、环保、可回收重复利用的柔性多孔材料；以柔性多孔材料为载体制作出的柔性导电多孔材料则可以作为压阻材料应用于触觉传感设备，也可以利用其多孔特性和超疏水性制作成为漂浮电极等。Structured flexible porous materials and structured flexible conductive porous materials have a very wide range of applications in scientific research and practical life. For example, cell culture and biological tissue engineering in medical research need to be attached to a flexible porous material with good biocompatibility, controllable pore size, and high interconnection rate; A flexible porous material with high oil adsorption capacity (that is, high interconnection rate), superhydrophobicity and superlipophilicity, environmental protection, and recyclable reuse; flexible conductive porous materials made of flexible porous materials as carriers can be used as pressure Resistive materials are used in tactile sensing devices, and can also be made into floating electrodes by taking advantage of their porous properties and superhydrophobicity.
综上，如何用灵活、高效且低成本的方法，制备出具有结构化外形、高孔隙互联互通率、孔径大小可控的柔性多孔材料及柔性导电多孔材料成为人们的研究重点。In summary, how to prepare flexible porous materials and flexible conductive porous materials with structured shape, high pore interconnection rate and controllable pore size by flexible, efficient and low-cost methods has become the focus of research.
在现有的文献和专利中提出的柔性多孔材料、柔性导电多孔材料的制备方法中，存在诸多不足和缺陷，如不具备结构化外形，多孔结构的孔隙大小不易控制，孔隙之间互联互通率差，粒子浸出不充分，制备速度慢等。In the preparation methods of flexible porous materials and flexible conductive porous materials proposed in the existing literature and patents, there are many deficiencies and defects, such as no structured shape, the pore size of the porous structure is not easy to control, and the interconnection rate between pores Poor, insufficient particle leaching, slow preparation speed, etc.
文献“Flexible,compressible,hydrophobic,floatable,and conductivecarbon nanotube-polymer sponge”(Han J W,Kim B,Li J,et al.Applied physicsletters,2013,102(5):051903.)公开了一种柔性多孔材料的制备方法：采用方糖作为多孔材料反结构，将混合好的聚二甲基硅氧烷预聚体连续滴加在方糖上，利用毛细作用使聚二甲基硅氧烷预聚体填满方糖中的空隙。待聚二甲基硅氧烷完成固化后，修剪多余的聚二甲基硅氧烷直至方糖表面暴露出来，将其放置在超声水浴的热水中两个小时以除去方糖。方糖溶解完全后，即可获得柔性多孔材料。其次，作者通过在多孔材料中填充单壁碳纳米管的方法获得柔性导电多孔材料：将单壁碳纳米管分散在二甲基甲酰胺(DMF)缓冲液中，然后用获得的溶液滴加在挤压状态的柔性多孔材料上，当压力释放时，多孔材料吸收溶液，此时，分散在缓冲液中的单壁碳纳米管进入材料内部的孔隙当中，得到柔性导电多孔材料。The document "Flexible, compressible, hydrophobic, floatable, and conductivecarbon nanotube-polymer sponge" (Han J W, Kim B, Li J, et al. Applied physics letters, 2013, 102(5): 051903.) discloses a flexible porous material The preparation method: using cube sugar as the reverse structure of the porous material, continuously drop the mixed polydimethylsiloxane prepolymer on the cube sugar, and use the capillary action to make the polydimethylsiloxane prepolymer fill Fill voids in sugar cubes. After the polydimethylsiloxane has finished curing, trim off excess polydimethylsiloxane until the surface of the sugar cube is exposed, and place it in hot water in an ultrasonic water bath for two hours to remove the sugar cube. After the sugar cube is completely dissolved, a flexible porous material can be obtained. Secondly, the authors obtained flexible conductive porous materials by filling single-walled carbon nanotubes in porous materials: dispersing single-walled carbon nanotubes in dimethylformamide (DMF) buffer, and then using the obtained solution to drop in On the flexible porous material in the extruded state, when the pressure is released, the porous material absorbs the solution. At this time, the single-walled carbon nanotubes dispersed in the buffer solution enter the pores inside the material to obtain a flexible conductive porous material.
在这一整套方法中，首先作者采用方糖作为多孔材料的反结构，制备出的多孔材料外形同方糖一样呈现出块状结构，不能根据不同需求灵活的制备各种结构化的外形。In this whole set of methods, the author first uses sugar cubes as the reverse structure of the porous material. The shape of the prepared porous material is the same as the sugar cube, showing a block structure, and it is not possible to flexibly prepare various structured shapes according to different needs.
其次，采用方糖作为多孔材料反结构制备出的多孔材料，其孔隙大小取决于糖的粒度，具有孔隙大小不可控的缺点。有其他文献采用经过分级筛选的氯化钠颗粒作为填充粒子，将聚二甲基硅氧烷与氯化钠颗粒进行充分混合后，对聚二甲基硅氧烷进行固化处理，接着再浸出氯化钠颗粒，最终制备出柔性多孔材料，这一方法虽然可以通过对填充粒子的大小进行分级筛选来控制多孔材料的孔隙大小，但是由于填充粒子之间相互分离，在进行粒子浸出时，部分填充粒子被完全包裹在聚二甲基硅氧烷中，导致填充粒子浸出速度慢且浸出不完全、多孔材料内部孔隙互联互通率差等问题。Secondly, the porous material prepared by using cube sugar as the reverse structure of the porous material has the disadvantage that the pore size depends on the particle size of the sugar, and the pore size is uncontrollable. There are other literatures that use graded and screened sodium chloride particles as filler particles. After fully mixing polydimethylsiloxane and sodium chloride particles, polydimethylsiloxane is cured, and then chlorine is leached out. Sodium chloride particles are used to prepare flexible porous materials. Although this method can control the pore size of the porous material by grading and screening the size of the filled particles, due to the separation of the filled particles, when the particles are leached, the partial filling Particles are completely encapsulated in polydimethylsiloxane, which leads to problems such as slow and incomplete leaching of filled particles, and poor interconnection rate of pores inside porous materials.
再者，作者利用毛细作用使聚二甲基硅氧烷预聚体填满方糖中的空隙，这一过程较为缓慢，且不易判断聚二甲基硅氧烷预聚体何时填满空隙。而且，待聚二甲基硅氧烷固化完成后还要修剪多余的聚二甲基硅氧烷，浪费部分材料。Furthermore, the author uses capillary action to make the polydimethylsiloxane prepolymer fill the voids in the sugar cube. This process is relatively slow, and it is not easy to judge when the polydimethylsiloxane prepolymer fills the voids. . Moreover, after the curing of the polydimethylsiloxane is completed, the excess polydimethylsiloxane will be trimmed, which wastes part of the material.
最后，作者提出通过挤压柔性多孔材料使其吸收含有导电材料的溶液的方法来制备柔性导电多孔材料，这不能保证多孔材料内部全部吸收到了溶液，即不确定导电材料是否均匀充分的进入多孔材料的孔隙内部，具有一定的工艺不确定性，同时不利于实现后续的工艺自动化。Finally, the author proposes to prepare a flexible conductive porous material by extruding the flexible porous material to absorb a solution containing a conductive material. This cannot ensure that the inside of the porous material is completely absorbed into the solution, that is, it is not sure whether the conductive material enters the porous material evenly and fully. Inside the pores, there is a certain process uncertainty, and it is not conducive to the realization of subsequent process automation.
发明内容Contents of the invention
针对现有技术的以上缺陷或改进需求，本发明提供了一种结构化柔性导电多孔材料的制备方法及应用该方法制备的柔性导电多孔材料，其目的在于通过填充粒子分级筛选、填充粒子表面微量融合固化处理和负压促渗相结合的处理方法，使得制备过程中填充粒子浸出速度快且浸出充分，制备出的柔性多孔材料孔隙大小可控且具有较高孔隙互联互通率。In view of the above defects or improvement needs of the prior art, the present invention provides a method for preparing a structured flexible conductive porous material and the flexible conductive porous material prepared by applying the method. The combination of curing treatment and negative pressure permeation-promoting treatment method makes the leaching speed of filling particles fast and sufficient during the preparation process, and the pore size of the prepared flexible porous material is controllable and has a high pore interconnection rate.
为了实现上述目的，本发明提供一种结构化柔性导电多孔材料的制备方法，该方法包括如下步骤：In order to achieve the above object, the present invention provides a method for preparing a structured flexible conductive porous material, the method comprising the following steps:
(1)设计模具；(1) Design the mold;
(2)向所述模具中加入填充粒子，并将模具置入封闭潮湿的环境中处理，使得填充粒子相互接触的表面部分通过微量溶解实现融合，之后放入烘箱中进行干燥处理；(2) adding filler particles to the mold, and placing the mold in a closed and humid environment for processing, so that the surface parts of the filler particles in contact with each other are fused through a small amount of dissolution, and then put into an oven for drying;
(3)将聚二甲基硅氧烷的预聚体注入经步骤(2)处理后的所述填充粒子上，再将所述模具放入真空抽气机中进行负压促渗处理，待气泡完全消失后取出模具，之后将所述模具送入烘箱中进行聚二甲基硅氧烷的固化处理，再将所述模具放入去离子水中以浸出填充粒子，浸出完成后进行干燥处理从而得到结构化柔性多孔材料；(3) Inject the prepolymer of polydimethylsiloxane onto the filled particles treated in step (2), and then put the mold into a vacuum pump for negative-pressure permeation-promoting treatment. After the air bubbles completely disappeared, the mold was taken out, and then the mold was sent into an oven for curing of polydimethylsiloxane, and then the mold was put into deionized water to extract the filling particles, and after the leaching was completed, drying treatment was carried out so that Obtain structured flexible porous materials;
(4)将上述制备的结构化柔性多孔材料完全浸入到含有导电材料的溶液中，并放入真空抽气机中进行负压促渗处理，待气泡消失干净后，取出所述结构化柔性多孔材料进行干燥处理，即可得到结构化柔性导电多孔材料。(4) Completely immerse the structured flexible porous material prepared above into the solution containing the conductive material, and put it into a vacuum pump for negative pressure permeation promotion treatment. After the bubbles disappear, take out the structured flexible porous material The material is dried to obtain a structured flexible conductive porous material.
进一步地，所述填充粒子为糖或氯化钠的颗粒状粒子。Further, the filler particles are granular particles of sugar or sodium chloride.
进一步地，所述填充粒子的大小通过分级筛选进行控制。Further, the size of the filler particles is controlled by graded screening.
优选地，所述填充粒子大小为150um以下、150um～300um、300um～450um或450um以上。Preferably, the size of the filler particles is less than 150um, 150um-300um, 300um-450um or more than 450um.
进一步地，所述聚二甲基硅氧烷的预聚体为聚二甲基硅氧烷的前基体和固化剂的混合物。Further, the prepolymer of polydimethylsiloxane is a mixture of a pre-matrix of polydimethylsiloxane and a curing agent.
进一步地，所述导电材料为石墨、碳纳米管、碳纳米线或银纳米线材料。Further, the conductive material is graphite, carbon nanotube, carbon nanowire or silver nanowire material.
按照本发明的另一个方面，提供一种应用所述的一种结构化柔性导电多孔材料的制备方法制备的结构化柔性导电多孔材料。According to another aspect of the present invention, a structured flexible conductive porous material prepared by applying the method for preparing a structured flexible conductive porous material is provided.
总体而言，通过本发明所构思的以上技术方案与现有技术相比，能够取得下列有益效果：Generally speaking, compared with the prior art, the above technical solutions conceived by the present invention can achieve the following beneficial effects:
(1)本发明的制备方法，在制备结构化柔性导电多孔材料的过程中，通过填充粒子分级筛选、填充粒子表面微量融合固化处理和负压促渗相结合的处理方法，使得制备过程中填充粒子浸出速度快且浸出充分，制备出的柔性多孔材料孔隙大小可控且具有较高孔隙互联互通率。(1) The preparation method of the present invention, in the process of preparing the structured flexible conductive porous material, through the treatment method of combining the filling particle classification and screening, the micro fusion curing treatment on the surface of the filling particle and the negative pressure permeation promotion, the filling The leaching speed of the particles is fast and sufficient, and the pore size of the prepared flexible porous material is controllable and has a high pore interconnection rate.
(2)本发明提出一种能灵活制备出材料的结构化外形的方法，在结构化柔性导电多孔材料的制备之初，通过结构化模具和填充粒子表面微量融合固化处理这两者相结合，使得人们可以根据不同需求灵活的制备各种结构化的外形。(2) The present invention proposes a method that can flexibly prepare the structured shape of the material. At the beginning of the preparation of the structured flexible conductive porous material, the combination of the structured mold and the micro-fusion and curing treatment on the surface of the filled particles, It allows people to flexibly prepare various structured shapes according to different needs.
(3)本发明的方法，在结构化柔性导电多孔材料的制备当中，为使导电材料快速且均匀充分的进入柔性多孔材料，使用负压促渗的方法，不仅使得导电材料均匀充分的填充进入柔性多孔材料孔隙内部，而且其过程所需时间也大大缩短，进一步提高了制备速度。(3) In the method of the present invention, in the preparation of the structured flexible conductive porous material, in order to make the conductive material enter the flexible porous material quickly and evenly and fully, the method of using negative pressure to promote penetration not only makes the conductive material evenly and fully filled into the Inside the pores of flexible porous materials, and the time required for the process is also greatly shortened, further improving the preparation speed.
附图说明Description of drawings
图1为本发明实施例的一种结构化柔性导电多孔材料的制备方法的流程图；Fig. 1 is a flowchart of a method for preparing a structured flexible conductive porous material according to an embodiment of the present invention;
图2(a)为本发明实施例的一种结构化柔性导电多孔材料的制备方法涉及填充粒子表面微量融合固化处理前的结构示意图；Fig. 2(a) is a schematic diagram of the structure of a method for preparing a structured flexible conductive porous material according to an embodiment of the present invention before micro-fusion and curing treatment on the surface of filled particles;
图2(b)为本发明实施例的一种结构化柔性导电多孔材料的制备方法涉及填充粒子表面微量融合固化处理后的结构示意图；Fig. 2(b) is a schematic diagram of the structure of a method for preparing a structured flexible conductive porous material involving micro-fusion and curing on the surface of filled particles according to an embodiment of the present invention;
图3为本发明实施例的一种结构化柔性导电多孔材料的制备方法制备的结构化柔性导电多孔材料的示意图。Fig. 3 is a schematic diagram of a structured flexible conductive porous material prepared by a method for preparing a structured flexible conductive porous material according to an embodiment of the present invention.
所有附图中，相同的附图标记表示相同的结构元件，其中：1-结构化模具、2-填充粒子、3-密闭潮湿的环境、4-聚二甲基硅氧烷、5-包裹了填充粒子的聚二甲基硅氧烷、6-去离子水、7-多孔结构的聚二甲基硅氧烷、8-含有导电材料的溶液、9-结构化柔性导电多孔材料。In all figures, the same reference numerals indicate the same structural elements, among them: 1-structured mold, 2-filling particles, 3-closed moist environment, 4-polydimethylsiloxane, 5-wrapped Particle-filled polydimethylsiloxane, 6-deionized water, 7-porous structure polydimethylsiloxane, 8-solution containing conductive material, 9-structured flexible conductive porous material.
具体实施方式detailed description
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。In order to make the object, technical solution and advantages of the present invention more clear, the present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below may be combined with each other as long as they do not constitute a conflict with each other.
结构化柔性导电多孔材料制备方法的具体步骤为：根据实际应用需求，设计所需的结构化模具；制备具有结构化外形的柔性多孔材料；在结构化柔性多孔材料中快速且均匀充分的填充导电材料。The specific steps of the preparation method of the structured flexible conductive porous material are as follows: design the required structured mold according to the actual application requirements; prepare the flexible porous material with a structured shape; quickly and uniformly fill the conductive porous material in the structured flexible porous material. Material.
(1)设计制备出符合实际应用需求的结构化模具。模具取材较为广泛，以在后续制备过程中易于脱模为选取原则，其形状可根据不同应用需求灵活设计。(1) Design and prepare a structured mold that meets the actual application requirements. The mold is made of a wide range of materials, and the principle of easy demoulding in the subsequent preparation process is the selection principle. Its shape can be flexibly designed according to different application requirements.
(2)制备具有结构化外形的柔性多孔材料：首先在模具中放入一定量的填充粒子(如图1(a)所示)。常用填充粒子有糖和氯化钠或其他具有相似材料特性的颗粒状粒子。由于填充粒子的大小决定了制备出的柔性多孔材料的孔隙大小，因此可通过对填充粒子大小的分级筛选来对多孔材料的孔隙大小进行控制；(2) Preparation of a flexible porous material with a structured shape: First, a certain amount of filler particles are placed in a mold (as shown in Figure 1(a)). Common filler particles are sugar and sodium chloride or other granular particles with similar material properties. Since the size of the filler particles determines the pore size of the prepared flexible porous material, the pore size of the porous material can be controlled by grading and screening the size of the filler particles;
如图1(b)所示，将模具置入封闭潮湿的环境中处理一段时间，使得填充粒子相互接触的表面部分通过微量溶解实现融合(具体过程如图2所示)，接着放入烘箱中进行干燥处理，固化填充粒子之间的连结，使得全部的填充粒子最终互相连结成为一个整体，构成多孔材料的反结构。As shown in Figure 1(b), the mold is placed in a closed and humid environment for treatment for a period of time, so that the surface parts of the filling particles in contact with each other are fused through a small amount of dissolution (the specific process is shown in Figure 2), and then placed in an oven Perform drying treatment to solidify the connection between the filling particles, so that all the filling particles are finally connected to each other as a whole, forming the reverse structure of the porous material.
然后将聚二甲基硅氧烷的预聚体倒入模具中的填充粒子之上(如图1(c))，放入真空抽气机进行负压促渗处理，帮助聚二甲基硅氧烷预聚体快速充分的进入填充粒子构成的反结构的空隙之中；Then pour the prepolymer of polydimethylsiloxane on the filling particles in the mold (as shown in Figure 1 (c)), put it into a vacuum pump for negative pressure permeation-promoting treatment, and help polydimethylsiloxane The oxane prepolymer quickly and fully enters the void of the anti-structure formed by the filled particles;
待气泡消失干净后取出模具，移除多余的聚二甲基硅氧烷预聚体(如图1(d))，送入烘箱中进行聚二甲基硅氧烷的固化处理。固化完成后，从模具中取出样品(图1(e))，放入去离子水中进行填充粒子的浸出(如图(f))，浸出完成后对样品进行干燥处理即可得到柔性多孔材料，如图1(g)。After the air bubbles disappeared, the mold was taken out, the excess polydimethylsiloxane prepolymer was removed (as shown in Figure 1(d)), and the polydimethylsiloxane was cured in an oven. After the curing is completed, the sample is taken out from the mold (Figure 1(e)), put into deionized water for leaching of the filled particles (as shown in Figure (f)), and after the leaching is completed, the sample is dried to obtain a flexible porous material. Figure 1(g).
(3)在结构化柔性多孔材料中均匀充分的填充导电材料。首先制作含有导电材料的溶液。常用的导电材料有石墨、碳纳米管、碳纳米线、银纳米线等具有微小尺度的材料或其他具有类似材料特性的导电材料。其次将上述步骤制备出的柔性多孔材料完全浸入到溶液当中，如图1(h)，放入真空抽气机进行负压促渗处理。由于多孔材料内的空气被抽出，含有导电材料的溶液快速且充分均匀的进入多孔材料的孔隙内部。待气泡消失干净后，取出样品进行干燥处理，即可得到最终的结构化柔性导电多孔材料，如图3所示。(3) Fill the conductive material evenly and fully in the structured flexible porous material. First make a solution containing the conductive material. Commonly used conductive materials include graphite, carbon nanotubes, carbon nanowires, silver nanowires and other materials with small scales or other conductive materials with similar material properties. Secondly, the flexible porous material prepared in the above steps is completely immersed in the solution, as shown in Figure 1(h), and put into a vacuum pump for negative pressure permeation promotion treatment. Since the air in the porous material is drawn out, the solution containing the conductive material enters the pores of the porous material quickly and uniformly. After the air bubbles disappeared, the sample was taken out for drying treatment to obtain the final structured flexible conductive porous material, as shown in Figure 3.
图1为本发明实施例的一种结构化柔性导电多孔材料的制备方法的流程图。如图1所示，本实施例采用一个底部为球形凹面的有机玻璃(PMMA)容器作为结构化模具1，选取氯化钠颗粒作为填充粒子2。为了控制多孔材料的孔隙大小，可以对盐粒进行分级筛选。Fig. 1 is a flowchart of a method for preparing a structured flexible conductive porous material according to an embodiment of the present invention. As shown in FIG. 1 , in this embodiment, a organic glass (PMMA) container with a spherical concave bottom is used as a structured mold 1 , and sodium chloride particles are selected as filling particles 2 . In order to control the pore size of porous materials, the salt particles can be graded and screened.
在本发明的优选实施例中，将盐粒分为150微米以下、150微米到300微米、300微米到450微米、450微米以上四个级别，可以制作出不同孔隙大小的多孔材料。In a preferred embodiment of the present invention, the salt particles are divided into four grades: below 150 microns, from 150 microns to 300 microns, from 300 microns to 450 microns, and above 450 microns, so that porous materials with different pore sizes can be produced.
首先在结构化模具中倒入一定量的经过分级筛选的氯化钠颗粒2，使盐粒尽量水平的分布在模具中，然后将水浴锅设置为45摄氏度，将装好氯化钠颗粒的模具放置在水浴锅潮湿封闭的空气3中两个小时，待氯化钠颗粒之间有表面微量融合后取出放入烘箱65摄氏度烘干固化两个小时，此时经过表面微量融合固化处理后的氯化钠颗粒相互连结成为一个整体。将聚二甲基硅氧烷的前基体和固化剂以10:1的比例进行充分混合得到聚二甲基硅氧烷预聚体4，然后将预聚体放入真空抽气机除去气泡，再倒入模具，覆盖在连结为整体的氯化钠之上。First pour a certain amount of graded and screened sodium chloride particles 2 into the structured mold, so that the salt particles are distributed in the mold as horizontally as possible, then set the water bath to 45 degrees Celsius, and put the mold filled with sodium chloride particles Place it in the moist and closed air of the water bath for two hours. After there is a small amount of surface fusion between the sodium chloride particles, take it out and put it in an oven for drying and curing at 65 degrees Celsius for two hours. Sodium chloride particles are interconnected to form a whole. Fully mix the pre-matrix of polydimethylsiloxane and curing agent at a ratio of 10:1 to obtain polydimethylsiloxane prepolymer 4, then put the prepolymer into a vacuum pump to remove air bubbles, It is then poured into a mold, covering the sodium chloride that is connected as a whole.
在本发明的优选实施例中，所述聚二甲基硅氧烷的预聚体为聚二甲基硅氧烷的前基体和固化剂以10:1的比例进行充分混合后的混合物，所制得的柔性多孔材料(即聚二甲基硅氧烷)的杨氏模量根据前基体和固化剂的比例确定，比例越大，其材料的杨氏模量越小，反之，越大。In a preferred embodiment of the present invention, the polydimethylsiloxane prepolymer is a mixture of the polydimethylsiloxane pre-matrix and the curing agent in a ratio of 10:1 after thorough mixing, so The Young's modulus of the prepared flexible porous material (ie, polydimethylsiloxane) is determined according to the ratio of the pre-matrix and the curing agent. The larger the ratio, the smaller the Young's modulus of the material, and vice versa.
接着将模具放入真空抽气机中进行负压促渗处理，聚二甲基硅氧烷的预聚体进入氯化钠颗粒之间的空隙。待气泡消失干净即聚二甲基硅氧烷的预聚体对空隙填充完毕之后，取出模具，用针管移除上面多余的聚二甲基硅氧烷预聚体，然后送入烘箱中65摄氏度烘干两个小时，使聚二甲基硅氧烷预聚体固化。固化完成后，将包裹氯化钠的聚二甲基硅氧烷5从模具中取出，放入去离子水6中浸泡以除去氯化钠。中途可以多次换水，加快粒子的浸出。经过约24小时的浸泡，粒子基本可以浸出完全，浸泡时间可根据实际情况进行调整。将浸出完全的聚二甲基硅氧烷多孔材料进行烘干，除去水分，此时结构化柔性多孔材料7制备完成。Next, the mold is put into a vacuum pump for negative-pressure permeation-promoting treatment, and the prepolymer of polydimethylsiloxane enters the gap between the sodium chloride particles. After the bubbles disappear, that is, the polydimethylsiloxane prepolymer fills the gap, take out the mold, remove the excess polydimethylsiloxane prepolymer with a needle, and then send it to an oven at 65 degrees Celsius Dry for two hours to cure the polydimethylsiloxane prepolymer. After the curing is completed, the sodium chloride-wrapped polydimethylsiloxane 5 is taken out of the mold and soaked in deionized water 6 to remove the sodium chloride. The water can be changed several times in the middle to speed up the leaching of particles. After about 24 hours of immersion, the particles can basically be leached completely, and the immersion time can be adjusted according to the actual situation. The fully leached polydimethylsiloxane porous material is dried to remove moisture, and the structured flexible porous material 7 is now prepared.
本实施例选取生活中随处可见的黑色墨汁作为含有导电材料的溶液。将之前制备好的多孔材料完全浸泡在墨汁中，然后放入真空抽气机中进行负压促渗处理。由于气压作用，墨汁进入多孔材料的内部孔隙。待气泡消失干净，此时，墨汁基本充分均匀的填满多孔材料的孔隙。取出样品并进行烘干，墨汁中的导电材料就会粘附在多孔材料的内部孔壁之上。此时即得到结构化柔性导电多孔材料9。In this embodiment, black ink, which can be seen everywhere in daily life, is selected as the solution containing conductive materials. The previously prepared porous material is completely soaked in the ink, and then placed in a vacuum pump for negative pressure permeation promotion treatment. Due to the air pressure, the ink enters the inner pores of the porous material. After the air bubbles disappear, the ink basically completely and evenly fills the pores of the porous material. When the sample is taken out and dried, the conductive material in the ink adheres to the inner pore walls of the porous material. At this point, the structured flexible conductive porous material 9 is obtained.
本领域的技术人员容易理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。Those skilled in the art can easily understand that the above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention, All should be included within the protection scope of the present invention.
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| CN111363192A (en) * | 2020-03-02 | 2020-07-03 | 石家庄铁道大学 | A kind of porous flexible membrane material and its preparation method and application |
| CN111363192B (en) * | 2020-03-02 | 2022-06-14 | 石家庄铁道大学 | Porous flexible membrane material and preparation method and application thereof |
| CN111964813B (en) * | 2020-08-18 | 2021-10-26 | 西安电子科技大学 | Wireless-driven high-sensitivity flexible pressure sensor and preparation method thereof |
| CN111964813A (en) * | 2020-08-18 | 2020-11-20 | 西安电子科技大学 | A wirelessly driven high-sensitivity flexible pressure sensor and preparation method thereof |
| CN113292856A (en) * | 2021-05-19 | 2021-08-24 | 清华大学 | Mechanoluminescence device and method for producing same |
| CN113372609A (en) * | 2021-06-24 | 2021-09-10 | 中南大学 | Porous flexible GNP/PDMS composite material, preparation method thereof and application thereof in strain sensor |
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