Gas humidity controlled composite honeycomb material and method for manufacturing the same

Abstract

To provide a composite honeycomb body material for controlling gas humidity and a method for manufacturing the same in which the deterioration of dynamic performance and hygroscopic capacity due to the extension of use time is reduced.SOLUTION: A moisture control composite honeycomb material, comprising a honeycomb substrate and a functional coating layer on a surface of the honeycomb substrate, wherein the honeycomb substrate is made of a glass fiber felt or a ceramic fiber felt, the functional coating layer comprises a hygroscopic material and an inorganic component, a mass ratio of the hygroscopic material to the inorganic component is 1: (0. 4-1), and the hygroscopic material is any two selected from the group consisting of a molecular sieve, a silica gel, a metal organic framework material and a polymeric hygroscopic material; The inorganic component is any one selected from silica sol, alumina sol and pseudo-boehmite, and the functional coating layer is intermittently distributed on the surface of the honeycomb substrate to form functional coating regions and blank regions on the surface of the honeycomb substrate.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention belongs to the field of advanced environmental protection materials technology. More specifically, it relates to a gas humidity control composite honeycomb material and a method for manufacturing the same. [Background technology]

[0002] Honeycomb moisture-absorbing materials are novel materials with special structures and functions, and their inspiration usually comes from the honeycomb structure found in nature, which is known for its characteristics such as being lightweight and having a large specific surface area.

[0003] Honeycomb moisture-absorbing materials typically have a highly porous structure, providing a large surface area that contributes to improved moisture absorption capacity. They achieve their moisture absorption function primarily by trapping and retaining moisture through their porous structure. Generally, honeycomb moisture-absorbing materials can be manufactured and obtained by various methods, including chemical vapor deposition, sol-gel methods, and template methods. In the manufacturing process, material selection can include natural or synthetic polymers, metal-organic structural materials, aerogels, and the like.

[0004] However, there is currently a risk of durability issues arising with honeycomb moisture-absorbing materials. Specifically, as the usage time is extended, the material itself experiences frequent changes in humidity, which degrades its mechanical performance and moisture absorption capacity. Therefore, how to maintain its moisture absorption capacity and stabilize its structure remains a technical problem that those skilled in the art must solve. [Overview of the project]

[0005] The technical problem that this invention aims to solve is that, for honeycomb moisture-absorbing materials, as the usage time is extended, the frequent changes in the humidity of the material itself cause a decrease in its mechanical performance and moisture absorption capacity, affecting the product's lifespan. Therefore, this invention provides a gas humidity-controlled composite honeycomb material and a method for manufacturing the same.

[0006] The present invention aims to provide a gas humidity control composite honeycomb material.

[0007] Another object of the present invention is to provide a method for manufacturing a gas humidity controlled composite honeycomb material.

[0008] The above objectives of the present invention are achieved by the following technical solutions. A gas humidity controlled composite honeycomb material comprising a honeycomb substrate and a functional coating layer on the surface of the honeycomb substrate, The aforementioned honeycomb substrate uses glass fiber felt or ceramic fiber felt. The functional coating layer comprises a hygroscopic material and an inorganic component. The mass ratio of the hygroscopic material to the inorganic component is 1:(0.4-1). The aforementioned moisture-absorbing material is any two selected from molecular sieves, silica gel, metal-organic structural materials, or polymeric moisture-absorbing materials. The aforementioned inorganic component is one selected from silica sol, alumina sol, and pseudoboehmite. Furthermore, the functional coating layer is intermittently distributed on the surface of the honeycomb substrate such that it forms functional coating areas and blank areas on the surface of the honeycomb substrate. This intermittent distribution means that the functional coating areas and blank areas are distributed with a gap between them, and the ratio of the area of ​​the functional coating areas to the area of ​​the blank areas is (2.0-2.2):1.

[0009] While honeycomb structure materials can ensure overall structural stability based on their structure, the inventors have found that when using a honeycomb structure as a substrate and applying the hygroscopic material to the surface of the honeycomb structure, if the coating is applied completely to the entire surface, the volume of the hygroscopic material on the surface of the honeycomb material may change during humidity changes due to the alternating processes of moisture absorption and drying. This can cause changes in internal stress, leading to stress concentration at the corners of the honeycomb material. As the usage period lengthens, repeated stress changes impair the mechanical performance at these points. Furthermore, stress release is relatively difficult for the structurally stable honeycomb material, and stress release is especially difficult at the corners. Over the long term, the bonding force between the surface coating layer and the substrate weakens, and the functional coating layer gradually detaches. The above proposed technology involves intermittently coating a honeycomb substrate, specifically employing a method in which functional coating areas and blank areas are distributed at intervals to form a functional coating layer on the surface of the honeycomb substrate. By adjusting the area ratio between the functional coating areas and blank areas and installing them in this manner, stress can be generated at intervals between the functional coating areas and blank areas during the product's use. This primarily reduces stress generation in the blank areas, allowing for effective release of internal stress by acting as a buffer zone for stress release in the functional coating areas. Furthermore, the presence of blank areas in the honeycomb structure is advantageous for gas diffusion. By combining with the functional coating areas, the diffused wet gas can be uniformly adsorbed throughout the entire honeycomb structure, avoiding localized stress concentration due to localized excessive adsorption.

[0010] Preferably, in the functional coating region, the functional coating layer is distributed in an island-like manner on the surface of the honeycomb substrate.

[0011] The inventors found that in actual use, the process of gas absorption in the functional coating area is substantially an adsorption process between the functional groups of the active material in the functional coating layer and its vacancy structure. When the functional coating is applied continuously, the cohesive force of the coating layer in the functional coating area is large, making it difficult to form effective vacancies, and the functional groups also form strong hydrogen bonds with each other, making them difficult to expose, so that the majority of the functional material does not exert a substantial hygroscopic effect. Conversely, when the functional coating is distributed in an island-like manner, the functional coating layer can effectively wet and spread on the surface of the substrate. On the other hand, during the drying process, the evaporation of solvents such as water makes it easy to form abundant vacancies, and at the same time, the active components can also be sufficiently wet and spread on the surface, exposing the active functional groups, and allowing equivalent or higher hygroscopic capacity to be obtained with a small amount of coating.

[0012] Preferably, the surface density of the glass fiber felt or ceramic fiber felt is 30-50 g / m². 2 That is the case.

[0013] Preferably, the surface density of the functional coating layer on the surface of the honeycomb substrate is 8-10 g / m². 2 That is the case.

[0014] Preferably, the polymeric moisture-absorbing material is one selected from polyvinyl alcohol or polyethylene glycol.

[0015] Preferably, in the functional coating region, a coupling agent is present between the functional coating layer and the honeycomb substrate. The coupling agent is selected from among silane coupling agent KH-550, silane coupling agent KH-560, or silane coupling agent KH-570.

[0016] A method for manufacturing a gas humidity-controlled composite honeycomb material, the specific manufacturing steps being: A flat fiber substrate is subjected to press molding after applying a hygroscopic material slurry to the functional coating area so that the functional coating area and the blank area are separated, thereby obtaining a wavy fiber substrate coated with the hygroscopic material. Another flat fiber substrate is coated with a moisture-absorbing material slurry in a functional coating area such that the functional coating area and the blank area are separated, and then bonded to the corrugated fiber substrate coated with the moisture-absorbing material, dried, and heat-treated to obtain a composite honeycomb body material.

[0017] Preferably, the applied moisture-absorbing material slurry Mask the blank area of a flat fiber substrate so that the functional coating area and the blank area are separated, expose the functional coating area, and then form a functional coating layer in the functional coating area by spray coating, including forming a functional coating layer distributed in an island shape in the functional coating area.

[0018] Preferably, the applied moisture-absorbing material slurry Mask the blank area of a flat fiber substrate so that the functional coating area and the blank area are separated, expose the functional coating area, and then spray-apply a coupling agent solution to the current functional coating area by spray coating, and after drying, spray-coat the functional coating area to form a functional coating layer, including forming a functional coating layer distributed in an island shape in the functional coating area.

Mode for Carrying Out the Invention

[0019] Hereinafter, the present invention will be further described with reference to specific examples, but the examples do not limit the present invention in any way. Unless otherwise specified, the reagents, methods, and equipment employed in the present invention are ordinary reagents, methods, and equipment in the technical field.

[0020] Unless otherwise specified, all the reagents and materials employed in the following examples are commercially available.

[0021] [Example 1] A flat fiber substrate is masked in the blank area so that the functional coating area and the blank area are separated, exposing the functional coating area, with a ratio of the area of ​​the functional coating area to the area of ​​the blank area being 2.0:1. Specifically, adhesive tape is used to adhere to the blank area to achieve masking of the blank area, and then a coupling agent solution is spray-applied to the functional coating area using a spray application method. Here, the coupling agent solution is made by mixing a coupling agent with a 60% ethanol solution in a mass ratio of 1:10, and when spray-applying the coupling agent solution, the amount of coupling agent used in the spray-applied area is 25 mL / m². 2 After controlling and drying, a hygroscopic material slurry is spray-applied to the functional coating area to form a functional coating layer distributed in an island-like manner in the functional coating area, and press-molding is performed at a temperature of 160°C to obtain a ripple-shaped fibrous substrate coated with the hygroscopic material. Another flat fiber substrate is masked over the blank area so that the functional coating area and the blank area are separated, exposing the functional coating area, with a ratio of the area of ​​the functional coating area to the area of ​​the blank area being 2.0:1. Specifically, adhesive tape is used to adhere to the blank area to achieve masking of the blank area, and then a coupling agent solution is spray-applied to the current functional coating area using a spray application method. Here, the coupling agent solution is made by mixing a coupling agent with a 60% ethanol solution in a mass ratio of 1:10, and when spray-applying the coupling agent solution, the amount of coupling agent used in the spray-applied area is 25 mL / m². 2 After controlling and drying, a hygroscopic material slurry is spray-applied to the functional coating area to form a functional coating layer distributed in an island-like manner in the functional coating area. Furthermore, it is bonded to a wave-shaped fibrous substrate coated with the hygroscopic material, dried, and then heat-treated at a temperature of 280°C for 2 hours to obtain a composite honeycomb material. The above-mentioned flat fibrous substrate is made of glass fiber felt or ceramic fiber felt, and the surface density of the glass fiber felt or ceramic fiber felt is 30 g / m². 2 And, The surface density of the functional coating layer on the surface of the honeycomb substrate is 8 g / m².2 And, The coupling agent mentioned above is selected from the silane coupling agent KH-550. Here, the above-mentioned moisture-absorbing material slurry contains raw materials in a mass ratio of 1:0.4 between the moisture-absorbing material and the inorganic component, and further contains water in an amount equal to six times the mass of the moisture-absorbing material. The above moisture-absorbing material is selected from 4A molecular sieves. The above inorganic components are selected from silica sol with a mass fraction of 40%. Here, the thickness of the flat fiber substrate is 1.5 mm, and the total thickness of the composite honeycomb material is 15 mm.

[0022] [Example 2] A flat fiber substrate is masked in the blank area so that the functional coating area and the blank area are separated, exposing the functional coating area, with a ratio of the area of ​​the functional coating area to the area of ​​the blank area being 2.1:1. Specifically, adhesive tape is used to adhere to the blank area to achieve masking of the blank area, and then a coupling agent solution is spray-applied to the functional coating area using a spray application method. Here, the coupling agent solution is made by mixing a coupling agent and a 60% ethanol solution in a mass ratio of 1:10, and when spray-applying the coupling agent solution, the amount of coupling agent used in the spray-applied area is 25 mL / m². 2 After controlling and drying, a hygroscopic material slurry is spray-applied to the functional coating area to form a functional coating layer distributed in an island-like manner in the functional coating area, and press-molding is performed at a temperature of 180°C to obtain a ripple-shaped fibrous substrate coated with the hygroscopic material. Mask another flat fiber substrate in the blank area so that the functional coating area and the blank area are separated, expose the functional coating area, and the ratio of the area of the functional coating area to the area of the blank area is 2.1:1. Specifically, use an adhesive tape to adhere to the blank area to achieve masking of the blank area. Next, in the form of spray coating, spray the coupling agent solution onto the current functional coating area. Here, the coupling agent solution is formed by mixing a coupling agent and an ethanol solution with a mass fraction of 60% in a mass ratio of 1:10. When spraying the coupling agent solution, control the usage amount of the coupling agent in the spray coating area to 25 mL / m 2 After drying, spray the hygroscopic material slurry onto the functional coating area to form a functional coating layer distributed in an island shape on the functional coating area. Bond it to the corrugated fiber substrate coated with the hygroscopic material, and after drying, perform heat treatment at a temperature of 290 °C for 2 h to obtain a composite honeycomb body material. Use a glass fiber felt or a ceramic fiber felt for the flat fiber substrate, and the surface density of the glass fiber felt or the ceramic fiber felt is 40 g / m 2 Yes. The surface density of the functional coating layer on the surface of the honeycomb substrate is 9 g / m 2 Yes. The coupling agent is selected from the silane coupling agent KH-560. Here, the hygroscopic material slurry contains raw materials with a mass ratio of the hygroscopic material to the inorganic component of 1:0.8, and further contains water six times the mass of the hygroscopic material. The hygroscopic material is selected from silica gel. The inorganic component is selected from alumina sol with a mass fraction of 35%. Here, the thickness of the flat fiber substrate is 1.5 mm, and the total thickness of the composite honeycomb body material is 15 mm.

[0023] [Example 3] A flat fiber substrate is masked in the blank area so that the functional coating area and the blank area are separated, exposing the functional coating area, with a ratio of the area of ​​the functional coating area to the area of ​​the blank area being 2.2:1. Specifically, adhesive tape is used to adhere to the blank area to achieve masking of the blank area, and then a coupling agent solution is spray-applied to the functional coating area using a spray application method. Here, the coupling agent solution is made by mixing a coupling agent with a 60% ethanol solution in a mass ratio of 1:10, and when spray-applying the coupling agent solution, the amount of coupling agent used in the spray-applied area is 25 mL / m². 2 After controlling and drying, a hygroscopic material slurry is spray-applied to the functional coating area to form a functional coating layer distributed in an island-like manner in the functional coating area, and press-molding is performed at a temperature of 220°C to obtain a ripple-shaped fibrous substrate coated with the hygroscopic material. Another flat fiber substrate is masked over the blank area so that the functional coating area and the blank area are separated, exposing the functional coating area, with a ratio of the area of ​​the functional coating area to the area of ​​the blank area being 2.2:1. Specifically, adhesive tape is used to adhere to the blank area to achieve masking of the blank area, and then a coupling agent solution is spray-applied to the current functional coating area using a spray application method. Here, the coupling agent solution is made by mixing a coupling agent with a 60% ethanol solution in a mass ratio of 1:10, and when spray-applying the coupling agent solution, the amount of coupling agent used in the spray-applied area is 25 mL / m². 2 After controlling and drying, a hygroscopic material slurry is spray-applied to the functional coating area to form a functional coating layer distributed in an island-like manner in the functional coating area. Furthermore, it is bonded to a wave-shaped fibrous substrate coated with the hygroscopic material, dried, and then heat-treated at a temperature of 300°C for 2 hours to obtain a composite honeycomb material. The above-mentioned flat fibrous substrate is made of glass fiber felt or ceramic fiber felt, and the surface density of the glass fiber felt or ceramic fiber felt is 50 g / m². 2 And, The surface density of the functional coating layer on the surface of the honeycomb substrate is 10 g / m².2 And, The coupling agent mentioned above was selected from the silane coupling agent KH-570. Here, the above-mentioned moisture-absorbing material slurry contains raw materials in a mass ratio of 1:1 between the moisture-absorbing material and the inorganic component, and further contains water in an amount equal to six times the mass of the moisture-absorbing material. The above moisture-absorbing material is selected from metal-organic structural materials (aluminum fumarate). The above inorganic components are selected from pseudoboehmite. Here, the thickness of the flat fiber substrate is 1.5 mm, and the total thickness of the composite honeycomb material is 15 mm.

[0024] [Example 4] This example differs from Example 1 in that it uses an ethanol solution with an equal mass fraction of 60% instead of a coupling agent solution; all other conditions remain the same.

[0025] [Comparative Example 1] This comparative example differs from Example 1 in that it uses a roll coating method instead of spray coating. Specifically, this is described below. A flat fiber substrate is masked in the blank area so that the functional coating area and the blank area are separated, exposing the functional coating area, with a ratio of the area of ​​the functional coating area to the area of ​​the blank area being 2.0:1. Specifically, adhesive tape is used to adhere to the blank area to achieve masking of the blank area, and then a coupling agent solution is roll-applied to the current functional coating area using a roll coating method. Here, the coupling agent solution is made by mixing a coupling agent with a 60% ethanol solution in a mass ratio of 1:10, and when the coupling agent solution is roll-applied, the amount of coupling agent used in the roll-applied area is 25 mL / m². 2 After controlling and drying, a hygroscopic material slurry is roll-applied to the functional coating area to form a functional coating layer continuously distributed in the functional coating area, and press-molded at a temperature of 160°C to obtain a ripple-shaped fibrous substrate coated with the hygroscopic material. Another flat fiber substrate is masked over the blank area so that the functional coating area and the blank area are separated, exposing the functional coating area, with a ratio of the area of ​​the functional coating area to the area of ​​the blank area being 2.0:1. Specifically, adhesive tape is used to adhere to the blank area to achieve masking of the blank area. Next, a coupling agent solution is roll-applied to the current functional coating area using a roll coating method. Here, the coupling agent solution is made by mixing a coupling agent with an ethanol solution with a mass fraction of 60% in a mass ratio of 1:10, and when roll-applying the coupling agent solution, the amount of coupling agent used in the roll-applied area is 25 mL / m². 2 After controlling the temperature and drying, a hygroscopic material slurry is roll-applied to the functional coating area to form a functional coating layer that is continuously distributed in the functional coating area. This layer is then bonded to a ripple-shaped fibrous substrate coated with the hygroscopic material, dried, and then heat-treated at a temperature of 280°C for 2 hours to obtain a composite honeycomb material.

[0026] All other conditions remain unchanged.

[0027] [Comparative Example 2] This comparative example differs from Example 1 in that no blank area is provided, while all other conditions remain the same.

[0028] [Comparative Example 3] This comparative example differs from Example 1 in that the ratio of the area of ​​the functional coating region to the area of ​​the blank region is 1.8:1, while all other conditions remain the same.

[0029] Performance measurements were performed on the products obtained in Examples 1-4 and Comparative Examples 1-3. The specific measurement methods and results are as follows.

[0030] Measurement of planar tensile strength: Products from each example or comparative example were sampled, with a sampling size of 60 mm x 60 mm. The planar tensile strength of the products before and after moisture absorption was measured. This measurement was performed using an INSTRON 8801 testing machine in accordance with ASTM C297 "Test Method for Tensile Strength of Sandwich Structures." During the test, a tensile load was applied at a loading rate of 0.5 mm / min until the maximum load was reached and the load decreased by 30% from the maximum load. Detailed measurement results are shown in Table 1. Here, the specific processing steps for the sample after moisture absorption were as follows: the 14d treatment was continued under conditions of a temperature of 75°C and a relative humidity of 85%, after which the sample was removed and dried under conditions of a temperature of 100°C until a constant weight was reached. The dried sample was then subjected to this moisture absorption-drying process 10 times to complete the moisture absorption treatment. [Table 1] As can be seen from the measurement results in Table 1, the product obtained in this invention not only has beneficial initial mechanical performance, but also maintains its mechanical performance at a high level even after long-term moisture absorption and drying cycles.

[0031] While the above embodiments represent preferred embodiments of the present invention, the embodiments of the present invention are not limited to these embodiments. Any other modifications, alterations, substitutions, combinations, or simplifications that do not depart from the spirit and principles of the present invention are all equivalent substitutions and are included within the scope of protection of the present invention.

Claims

1. A gas humidity controlled composite honeycomb material, It comprises a honeycomb substrate and a functional coating layer on the surface of the honeycomb substrate. Here, the honeycomb base is made of glass fiber felt or ceramic fiber felt. The functional coating layer comprises a hygroscopic material and an inorganic component. The mass ratio of the moisture-absorbing material to the inorganic component is 1:(0.4-1). The aforementioned moisture-absorbing material is any two selected from molecular sieves, silica gel, metal-organic structural materials, or polymeric moisture-absorbing materials. The aforementioned inorganic component is one selected from silica sol, alumina sol, and pseudoboehmite. Furthermore, the functional coating layer is intermittently distributed on the surface of the honeycomb substrate such that it forms functional coating areas and blank areas on the surface of the honeycomb substrate, and the intermittent distribution means that the functional coating areas and the blank areas are distributed with a gap between them, and the ratio of the area of ​​the functional coating areas to the area of ​​the blank areas is (2.0 - 2.2):1, characterized in that the gas humidity controlled composite honeycomb material.

2. The gas humidity controlled composite honeycomb material according to claim 1, characterized in that, in the functional coating region, the functional coating layer is distributed in an island-like manner on the surface of the honeycomb substrate.

3. The surface density of the glass fiber felt or ceramic fiber felt is 30-50 g / m². ２ The gas humidity control composite honeycomb material according to claim 1, characterized in that it is the gas humidity control composite honeycomb material.

4. The surface density of the functional coating layer on the surface of the honeycomb substrate is 8-10 g / m². ２ The gas humidity control composite honeycomb material according to claim 1, characterized in that it is the gas humidity control composite honeycomb material.

5. The gas humidity control composite honeycomb material according to claim 1, characterized in that the polymer moisture-absorbing material is selected from polyvinyl alcohol or polyethylene glycol.

6. The gas humidity controlled composite honeycomb material according to claim 1, characterized in that a coupling agent is present between the functional coating layer and the honeycomb substrate in the functional coating region.

7. A method for producing a gas humidity controlled composite honeycomb material according to any one of claims 1 to 6, The specific manufacturing steps are: A flat fiber substrate is subjected to press molding after applying a hygroscopic material slurry to the functional coating area so that the functional coating area and the blank area are separated, thereby obtaining a wavy fiber substrate coated with the hygroscopic material. A method for producing a gas humidity-controlled composite honeycomb material, characterized by comprising: applying a hygroscopic material slurry to the functional coating region of another flat fibrous substrate such that the functional coating region and the blank region are separated; bonding it with the ripple-shaped fibrous substrate to which the hygroscopic material has been applied; drying; and heat treatment to obtain a composite honeycomb material.

8. The aforementioned coated moisture-absorbing material slurry A method for manufacturing a gas humidity controlled composite honeycomb material according to claim 7, characterized in that a flat fibrous substrate is masked in a blank area such that the functional coating area and the blank area are separated, thereby exposing the functional coating area, and then a functional coating layer is formed in the functional coating area by a spray coating method, thereby forming a functional coating layer distributed in an island-like manner in the functional coating area.

9. The aforementioned coated moisture-absorbing material slurry A method for producing a gas humidity controlled composite honeycomb material according to claim 8, characterized by comprising: masking a flat fibrous substrate with a blank area such that the functional coating area and the blank area are separated, exposing the functional coating area; then spray coating a coupling agent solution onto the functional coating area by a spray coating method; drying the solution; and then spray coating the functional coating area to form a functional coating layer, thereby forming a functional coating layer distributed in an island-like manner on the functional coating area.

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