Gas humidity control composite honeycomb material and method of making 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] The present invention belongs to the advanced environmental protection material technical field, and more particularly to a gas humidity control composite honeycomb body material and its manufacturing method. [Background technology]

[0002] Honeycomb moisture-absorbing materials are novel materials with special structures and functions, and their inspiration is usually derived from honeycomb structures in nature, which are well-known for their characteristics such as light weight and large specific surface area.

[0003] Honeycomb moisture-absorbing materials typically have a highly porous structure, providing a large amount of surface area to enhance moisture absorption capacity, and achieve their moisture absorption function by capturing and retaining moisture through the porous structure. Generally, honeycomb moisture-absorbing materials can be manufactured and obtained by various methods, including chemical vapor deposition, sol-gel, and template methods. In the manufacturing process, materials can include natural or synthetic polymers, metal-organic framework materials, aerogels, etc.

[0004] However, there is currently a risk of problems with the durability of honeycomb moisture-absorbing materials. Specifically, as the usage period extends, the material itself experiences frequent humidity changes, which reduces its mechanical performance and moisture absorption capacity. Therefore, how to maintain its moisture absorption capacity and stabilize its structure is one of the technical problems that those skilled in the art must solve. Summary of the Invention

[0005] The technical problem that the present invention aims to solve is the problem that, as the use time of honeycomb moisture-absorbing materials increases, the material itself experiences frequent humidity changes, which reduces its mechanical performance and moisture absorption capacity, affecting the product's service life. To this end, a gas humidity control composite honeycomb material and a manufacturing method thereof are provided.

[0006] SUMMARY OF THE INVENTION An object of the present invention is to provide a gas humidity control composite honeycomb body material.

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

[0008] The above object of the present invention is achieved by the following technical solutions. A gas humidity control composite honeycomb body material, comprising: a honeycomb substrate; and a functional coating layer on a surface of the honeycomb substrate; The honeycomb substrate is made of glass fiber felt or ceramic fiber felt, the functional coating layer includes a moisture-absorbing material and an inorganic component; the mass ratio of the moisture-absorbing material to the inorganic component is 1:(0.4-1); the moisture-absorbing material is any two selected from a molecular sieve, a silica gel, a metal-organic framework material, and a polymer moisture-absorbing material; the inorganic component is any one selected from silica sol, alumina sol, and pseudoboehmite, Furthermore, the functional coating layer is distributed intermittently on the surface of the honeycomb substrate so as to form 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.

[0009] Regarding honeycomb structure materials, the stability of the overall structure can be ensured based on the honeycomb structure. However, the inventor found that when using it as the base material for a moisture-absorbing material and coating the moisture-absorbing material on the surface of the honeycomb structure substrate, if the coating is completely coated all over, during the humidity change process, the volume of the moisture-absorbing material on the surface of the honeycomb material may change as the moisture absorption and drying processes alternate, which causes changes in internal stress. As a result, stress is likely to concentrate at the corners of the honeycomb material, and as the use period increases, the mechanical performance at these points will be impaired due to the repeated changes in stress. In addition, it is relatively difficult for honeycomb materials with stable structures to release stress, and stress release is particularly difficult at the corners. In the long term, the bonding strength between the surface coating layer and the substrate will weaken, and the functional coating layer will gradually come off. The above technical solution is applied to the honeycomb substrate intermittently, specifically by adopting 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, and the area ratio of the functional coating areas to the blank areas is adjusted. By arranging them in this way, stress is also generated between the functional coating areas and the blank areas during the use of the product, which is mainly because stress is less likely to be generated in the blank areas and they act as buffer zones for stress release in the functional coating areas, thereby achieving effective release of internal stress. Furthermore, the existence of blank areas in the honeycomb structure is advantageous for gas diffusion, and by combining with the functional coating areas, the wet gas after diffusion can be uniformly adsorbed throughout the entire honeycomb structure, thereby avoiding local stress concentration caused by local over-adsorption.

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

[0011] The inventors have discovered that during actual use, the moisture absorption process of gas in the functional coating region is essentially an adsorption process with the functional groups of the active material in the functional coating layer or its pore structure, and that when the functional coating region is continuously coated, the coating layer in the functional coating region has a high cohesive force, making it difficult to form effective pores, and the functional groups also form strong hydrogen bonds with each other and are difficult to expose, so that most of the functional material does not essentially exhibit a moisture absorption effect. Conversely, when distributed in an island-like manner, the functional coating layer can effectively wet and spread on the surface of the substrate, while during the drying process, evaporation of solvents such as water makes it easy to form abundant pores, and at the same time, the active ingredient also easily wets and spreads sufficiently on the surface, exposing the active functional groups, and thereby achieving the same or higher moisture absorption capacity with a smaller coating amount.

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

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

[0014] Preferably, the polymeric moisture-absorbing material is any one selected from polyvinyl alcohol and 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 silane coupling agent KH-550, silane coupling agent KH-560, and silane coupling agent KH-570.

[0016] A method for manufacturing a gas humidity control composite honeycomb material, the specific manufacturing steps of which are: a flat fiber substrate is coated with a moisture-absorbing material slurry in a functional application area so that the functional application area and a blank area are spaced apart, and then the substrate is press-molded to obtain a ripple-shaped fiber substrate coated with the moisture-absorbing material; The method includes applying a moisture-absorbing material slurry to the functional application area of ​​another flat fiber substrate so that the functional application area and the blank area are spaced apart, and then bonding the rippled fiber substrate to which the moisture-absorbing material has been applied, drying, and heat-treating the substrate to obtain a composite honeycomb body material.

[0017] Preferably, the applied moisture absorbing material slurry is The method includes masking a flat fiber substrate with a blank area so that the functional coating area and the blank area are separated, exposing the functional coating area, and then forming a functional coating layer on the functional coating area by a spray coating method, thereby forming a functional coating layer distributed in an island pattern on the functional coating area.

[0018] Preferably, the applied moisture absorbing material slurry is The method includes masking a flat fiber substrate with a blank area so that the functional coating area and the blank area are separated, exposing the functional coating area, spraying a coupling agent solution onto the current functional coating area using a spray coating method, drying the functional coating area, and then spraying the functional coating area to form a functional coating layer, thereby forming a functional coating layer distributed in an island shape on the functional coating area. DETAILED DESCRIPTION OF THE INVENTION

[0019] The present invention will be further described below with reference to specific examples, but the examples are not intended to limit the present invention. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

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

[0021] [Example 1] A flat fiber substrate is masked with a blank area so that the functional application area and the blank area are spaced apart, exposing the functional application area, and the ratio of the area of ​​the functional application area to the area of ​​the blank area is 2.0:1. Specifically, adhesive tape is used to attach to the blank area, masking the blank area. Next, a coupling agent solution is sprayed onto the current functional application area by a spray coating method. The coupling agent solution is a mixture of a coupling agent and an ethanol solution with a mass fraction of 60% at a mass ratio of 1:10. When spraying the coupling agent solution, the amount of coupling agent used in the spray application area is 25 mL / m. 2 After controlling the temperature and drying, a moisture-absorbing material slurry is spray-coated on the functional coating area to form a functional coating layer distributed in an island shape on the functional coating area, and the functional coating layer is press-molded at a temperature of 160°C to obtain a ripple-shaped fiber substrate coated with the moisture-absorbing material. Another flat fiber substrate is masked with a blank area so that the functional application area and the blank area are spaced apart, exposing the functional application area. The area ratio of the functional application area to the blank area is 2.0:1. Specifically, adhesive tape is used to attach to the blank area, masking the blank area. Next, a coupling agent solution is sprayed onto the current functional application area by spray coating. The coupling agent solution is a mixture of a coupling agent and a 60% ethanol solution at a mass ratio of 1:10. When spraying the coupling agent solution, the amount of coupling agent used in the spray coating area is 25 mL / m. 2 After controlling the temperature and drying, a moisture absorbing material slurry is sprayed onto the functional coating area to form a functional coating layer distributed in an island shape in the functional coating area, and then the functional coating area is bonded to a rippled fiber substrate coated with the moisture absorbing material, dried, and then heat-treated at a temperature of 280°C for 2 hours to obtain a composite honeycomb body material. The flat fiber 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 / m 2 and The surface density of the functional coating layer on the surface of the honeycomb substrate is 8 g / m2 and The coupling agent is selected from the silane coupling agent KH-550, wherein the moisture-absorbing material slurry contains a moisture-absorbing material and the inorganic component in a mass ratio of 1:0.4, and further contains water in an amount six times the mass of the moisture-absorbing material; The moisture absorbing material is selected from 4A molecular sieves; The inorganic component is selected from silica sol having 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 body material is 15 mm.

[0022] [Example 2] A flat fiber substrate is masked with a blank area so that the functional application area and the blank area are spaced apart, exposing the functional application area, and the area ratio of the functional application area to the blank area is 2.1:1. Specifically, adhesive tape is used to attach to the blank area, masking the blank area. Next, a coupling agent solution is sprayed onto the current functional application area by a spray coating method. The coupling agent solution is a mixture of a coupling agent and an ethanol solution with a mass fraction of 60% at a mass ratio of 1:10. When spraying the coupling agent solution, the amount of coupling agent used in the spray application area is 25 mL / m. 2 After controlling the temperature and drying, a moisture-absorbing material slurry is spray-coated on the functional coating area to form a functional coating layer distributed in an island shape on the functional coating area, and the functional coating layer is press-molded at a temperature of 180°C to obtain a ripple-shaped fiber substrate coated with the moisture-absorbing material. Another flat fiber substrate is masked with a blank area so that the functional coating area and the blank area are spaced apart, exposing the functional coating area. The area ratio of the functional coating area to the blank area is 2.1:1. Specifically, adhesive tape is used to attach to the blank area, masking the blank area. Next, a coupling agent solution is sprayed onto the current functional coating area by spray coating. The coupling agent solution is a mixture of a coupling agent and a 60% ethanol solution at a mass ratio of 1:10. When spraying the coupling agent solution, the amount of coupling agent used in the spray coating area is 25 mL / m. 2 After controlling the temperature and drying, a moisture absorbing material slurry is sprayed onto the functional coating area to form a functional coating layer distributed in an island shape in the functional coating area, and the functional coating area is bonded to the rippled fiber substrate coated with the moisture absorbing material, dried, and then heat-treated at a temperature of 290°C for 2 hours to obtain a composite honeycomb body material. The flat fiber 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 40 g / m 2 and The surface density of the functional coating layer on the surface of the honeycomb substrate is 9 g / m 2 and The coupling agent is selected from the silane coupling agent KH-560, wherein the moisture-absorbing material slurry contains a moisture-absorbing material and the inorganic component in a mass ratio of 1:0.8, and further contains water in an amount six times the mass of the moisture-absorbing material; The moisture-absorbing material is selected from silica gel; The inorganic component is selected from alumina sol having 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 with a blank area so that the functional application area and the blank area are spaced apart, exposing the functional application area, and the ratio of the area of ​​the functional application area to the area of ​​the blank area is 2.2:1. Specifically, adhesive tape is used to attach to the blank area, masking the blank area. Next, a coupling agent solution is sprayed onto the current functional application area by a spray coating method. The coupling agent solution is a mixture of a coupling agent and an ethanol solution with a mass fraction of 60% at a mass ratio of 1:10. When spraying the coupling agent solution, the amount of coupling agent used in the spray application area is 25 mL / m. 2 After controlling the temperature and drying, a moisture-absorbing material slurry is spray-coated on the functional coating area to form a functional coating layer distributed in an island shape on the functional coating area, and the functional coating layer is press-molded at a temperature of 220°C to obtain a ripple-shaped fiber substrate coated with the moisture-absorbing material. Another flat fiber substrate is masked with a blank area so that the functional coating area and the blank area are spaced apart, exposing the functional coating area. The area ratio of the functional coating area to the blank area is 2.2:1. Specifically, adhesive tape is used to attach to the blank area, masking the blank area. Next, a coupling agent solution is sprayed onto the current functional coating area by a spray coating method. The coupling agent solution is a mixture of a coupling agent and a 60% ethanol solution at a mass ratio of 1:10. When spraying the coupling agent solution, the amount of coupling agent used in the spray coating area is 25 mL / m. 2 After controlling the temperature and drying, a moisture-absorbing material slurry is spray-coated on the functional coating area to form a functional coating layer distributed in an island shape on the functional coating area, and then the functional coating area is bonded to a ripple-shaped fiber substrate coated with the moisture-absorbing material, dried, and then heat-treated at a temperature of 300°C for 2 hours to obtain a composite honeycomb body material. The flat fiber 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 / m 2 and The surface density of the functional coating layer on the surface of the honeycomb substrate is 10 g / m2 and The coupling agent is selected from the silane coupling agent KH-570, wherein the moisture-absorbing material slurry contains a moisture-absorbing material and the inorganic component in a mass ratio of 1:1, and further contains water in an amount six times the mass of the moisture-absorbing material; The moisture-absorbing material is selected from metal-organic framework materials (aluminum fumarate), The inorganic component is selected from pseudoboehmite, 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.

[0024] [Example 4] This example differs from Example 1 in that an ethanol solution with a mass fraction of 60% is used instead of the coupling agent solution, but the other conditions remain the same.

[0025] [Comparative Example 1] This comparative example differs from Example 1 in that roll coating is used instead of spray coating. Specific details are as follows. A flat fiber substrate is masked with a blank area so that the functional application area and the blank area are spaced apart, exposing the functional application area. The area ratio of the functional application area to the blank area is 2.0:1. Specifically, adhesive tape is used to attach to the blank area, thereby masking the blank area. Then, a coupling agent solution is roll-coated onto the current functional application area by roll coating. The coupling agent solution is a mixture of a coupling agent and an ethanol solution with a mass fraction of 60% at a mass ratio of 1:10. When the coupling agent solution is roll-coated, the amount of coupling agent used in the roll-coated area is 25 mL / m. 2 After controlling the temperature and drying, a moisture-absorbing material slurry is roll-coated on the functional coating area to form a functional coating layer that is continuously distributed on the functional coating area, and the functional coating layer is press-molded at a temperature of 160°C to obtain a ripple-shaped fiber substrate coated with the moisture-absorbing material. Another flat fiber substrate is masked with a blank area so that the functional coating area and the blank area are separated, exposing the functional coating area, and the ratio of the area of ​​the functional coating area to the area of ​​the blank area is 2.0:1. Specifically, adhesive tape is used to attach to the blank area to mask the blank area. Next, a coupling agent solution is roll-coated onto the current functional coating area using a roll-coating method. The coupling agent solution is a mixture of a coupling agent and an ethanol solution with a mass fraction of 60% at a mass ratio of 1:10. When the coupling agent solution is roll-coated, the amount of coupling agent used in the roll-coated area is 25 mL / m. 2 After controlling the temperature and drying, a moisture-absorbing material slurry is roll-coated onto the functional coating area to form a functional coating layer that is continuously distributed in the functional coating area, which is then bonded to a rippled fiber substrate to which the moisture-absorbing material has been applied, dried, and then heat-treated at a temperature of 280°C for 2 hours to obtain a composite honeycomb body material.

[0026] Other conditions remain the same.

[0027] Comparative Example 2 This comparative example differs from Example 1 in that no blank area is provided, but the 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 application region to the area of ​​the blank region is 1.8:1, with the other conditions remaining the same.

[0029] The performance of the products obtained in Examples 1-4 and Comparative Examples 1-3 was measured, and the specific measurement methods and results are as follows.

[0030] Flat tensile strength test: The products of each Example or Comparative Example were sampled, with a sampling size of 60 mm x 60 mm, and the flat tensile strength of the products was measured before and after moisture absorption. The measurement was carried out 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. The detailed measurement results are shown in Table 1. Here, the specific treatment process for the moisture-absorbed sample was as follows: after treatment for 14 days under conditions of a temperature of 75°C and a relative humidity of 85%, the sample was removed and further dried at a temperature of 100°C until it reached a constant weight. 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 products obtained according to the present invention not only have beneficial initial mechanical properties, but also maintain their mechanical properties at a high level even after long periods of moisture absorption and drying cycles.

[0031] The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention are all equivalent substitution methods and fall within the protection scope of the present invention.

Claims

1. A gas humidity control composite honeycomb body material, comprising: a honeycomb substrate and a functional coating layer on a surface of the honeycomb substrate; wherein the honeycomb substrate is made of glass fiber felt or ceramic fiber felt, the functional coating layer includes a moisture-absorbing material and an inorganic component; the mass ratio of the moisture-absorbing material to the inorganic component is 1:(0.4-1); the moisture-absorbing material is any two selected from a molecular sieve, a silica gel, a metal-organic framework material, and a polymer moisture-absorbing material; the inorganic component is any one selected from silica sol, alumina sol, and pseudoboehmite; Furthermore, the functional coating layer is distributed intermittently on the surface of the honeycomb substrate so as to form 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 at intervals, and the ratio of the area of ​​the functional coating areas to the area of ​​the blank areas is (2.0-2.2):

1.

2. 2. The gas humidity control composite honeycomb body material according to claim 1, wherein in the functional coating region, the functional coating layer is distributed in an island pattern on the surface of the honeycomb substrate.

3. The surface density of the glass fiber felt or ceramic fiber felt is 30-50 g / m ２ 2. The gas humidity control composite honeycomb body material according to claim 1, wherein:

4. The surface density of the functional coating layer on the surface of the honeycomb substrate is 8-10 g / m ２ 2. The gas humidity control composite honeycomb body material according to claim 1, wherein:

5. 2. The gas humidity control composite honeycomb body material according to claim 1, wherein the polymer moisture absorbing material is any one selected from polyvinyl alcohol and polyethylene glycol.

6. In the functional coating region, a coupling agent is present between the functional coating layer and the honeycomb substrate, The gas humidity control composite honeycomb body material according to claim 1, wherein the coupling agent is selected from the group consisting of silane coupling agent KH-550, silane coupling agent KH-560, and silane coupling agent KH-570.

7. A method for manufacturing a gas humidity control composite honeycomb body material according to any one of claims 1 to 6, comprising: The specific manufacturing steps are: a flat fiber substrate is coated with a moisture-absorbing material slurry in a functional application area so that the functional application area and the blank area are spaced apart, and then the substrate is press-molded to obtain a ripple-shaped fiber substrate coated with the moisture-absorbing material; A method for manufacturing a gas humidity control composite honeycomb body material, characterized in that it includes applying a moisture-absorbing material slurry to the functional application area of ​​another flat fiber substrate so that the functional application area and the blank area are spaced apart, then bonding it to the rippled fiber substrate to which the moisture-absorbing material has been applied, drying it, heat-treating it, and then obtaining a composite honeycomb body material.

8. The applied moisture absorbing material slurry is A method for manufacturing a gas humidity control composite honeycomb body material as described in claim 7, characterized in that it includes masking a flat fiber substrate with a blank area so that the functional coating area and the blank area are separated, exposing the functional coating area, and then forming a functional coating layer on the functional coating area by a spray coating method, thereby forming a functional coating layer distributed in an island-like manner on the functional coating area.

9. The applied moisture absorbing material slurry is A method for manufacturing a gas humidity control composite honeycomb body material as described in claim 8, characterized in that it includes masking a flat fiber substrate with a blank area so that the functional coating area and the blank area are separated, exposing the functional coating area, then spraying a coupling agent solution onto the functional coating area using a spray coating method, drying it, and then spraying the functional coating area to form a functional coating layer, thereby forming a functional coating layer distributed in an island shape in the functional coating area.

Images