Impermeable deposits inside substrate
By forming an obstructive deposit inside the substrate, the problem of moisture penetration caused by defects on the substrate is solved, and the effect of extending the life of the substrate and improving performance is achieved.
Patent Information
- Application Number
- CN202380049452.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2022-06-29
- Filing Date
- 2023-06-19
- Publication Date
- 2025-02-11
AI Technical Summary
In the prior art, the barrier coating on the substrate may contain defects, such as pinholes, which lead to moisture penetration of the surrounding environment and affect the life of the substrate.
By introducing the substrate into the reaction space, the substrate is simultaneously exposed to water and the first chemical substance, and the water and the first chemical substance are diffused into the defects of the substrate by diffusion treatment, forming an obstruction sediment to block the defects.
Effectively plug defects inside the substrate, reduce moisture penetration, extend the life of the substrate, and improve the performance of the substrate.
Smart Images
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Abstract
Description
Technical Field
[0001] The present invention relates to a method for forming an impeding deposit inside a substrate comprising a defect. Furthermore, the present invention relates to a substrate comprising an impeding deposit inside the substrate. The present invention also relates to the use of the method. Background Art
[0002] Protection of different kinds of substrates from the surrounding environment is usually performed by depositing a barrier coating on the substrate. Such coating techniques may include atomic layer deposition (ALD), chemical vapor deposition (CVD) and physical vapor deposition (PVD). However, such barrier coatings may include defects such as pinholes, through which moisture from the surrounding environment can penetrate and reach the substrate through the barrier coating, thereby affecting, for example, the lifetime of the substrate. One approach to solving the above problems is to prepare multiple layers of barrier materials one layer on top of the other, however, there is still a need to find a way to protect substrates for different applications. Summary of the invention
[0003] The present invention discloses a method for forming an obstructing deposit inside a substrate including defects. The method comprises introducing the substrate into a reaction space, wherein:
[0004] The substrate contains water and / or is exposed to water, and at the same time the substrate is exposed to a first chemical, wherein the first chemical is configured to react with the water; and,
[0005] The substrate is subjected to a diffusion process to allow the water and the first chemical substance to diffuse into the defects of the substrate to react with each other inside the substrate to form a barrier deposit inside the substrate to plug the defects in the substrate.
[0006] The present invention also discloses a substrate, which comprises a blocking deposit existing inside the substrate and blocking defects existing in the substrate, wherein the blocking deposit can be obtained by the method disclosed in this specification.
[0007] The present invention also discloses a substrate, which comprises a blocking deposit existing inside the substrate and blocking defects existing in the substrate, wherein the blocking deposit comprises metal oxide, metal carbonate or metal hydroxide or consists of metal oxide, metal carbonate or metal hydroxide.
[0008] The invention also discloses a use of the method as defined in the present specification for reducing the conductivity of a substrate.
[0009] The present invention also discloses the use of a method as defined in this specification for minimizing the diffusion of molecules from the surroundings of a substrate into and / or through said substrate. BRIEF DESCRIPTION OF THE DRAWINGS
[0010] The accompanying drawings are included to provide a further understanding of the method and substrate and constitute a part of this specification, illustrate embodiments, and together with the description help explain the above principles. In the drawings:
[0011] Figure 1 A method of forming an obstructing deposit inside a substrate according to one embodiment is shown;
[0012] Figure 2 A method of forming an obstructing deposit inside a substrate according to another embodiment is shown; and
[0013] Figure 3 A method of forming a barrier deposit within a substrate according to another embodiment is shown. DETAILED DESCRIPTION
[0014] The present invention discloses a method for forming an obstructing deposit inside a substrate including defects. The method comprises introducing a substrate into a reaction space, wherein the substrate contains water and / or is exposed to water, and simultaneously exposing the substrate to a first chemical substance, wherein the first chemical substance is configured to react with the water; and,
[0015] The substrate is subjected to a diffusion process to allow the water and the first chemical substance to diffuse into the defects of the substrate to react with each other inside the substrate to form a barrier deposit inside the substrate to plug the defects in the substrate.
[0016] The present invention also discloses a substrate, which comprises a blocking deposit existing inside the substrate and blocking defects existing in the substrate, wherein the blocking deposit can be obtained by the method disclosed in this specification.
[0017] The present invention also discloses a substrate, which comprises a blocking deposit existing inside the substrate and blocking defects existing in the substrate, wherein the blocking deposit comprises metal oxide, metal carbonate or metal hydroxide or consists of metal oxide, metal carbonate or metal hydroxide.
[0018] The invention also discloses a use of the method as defined in the present specification for reducing the conductivity of a substrate.
[0019] The present invention also discloses the use of a method as defined in this specification for minimizing the diffusion of molecules from the surroundings of a substrate into and / or through said substrate.
[0020] Unless otherwise stated, the expression "defect" in this specification should be understood to refer to cracks, fissures and / or pinholes present in the substrate. For example, due to its production process, the substrate may include defects of different sizes and shapes inside the substrate. In one embodiment, at least some of the defects are surrounded by the material of the substrate. Such defects are not open to the (top) surface of the substrate, but are located inside the substrate. In one embodiment, at least some of the defects in the substrate lead to the surface of the substrate. In one embodiment, the obstructing deposit at least partially fills the defects of the substrate so that the obstructing deposit can conform to the shape of the defect surface. In one embodiment, the obstructing deposit fills and / or blocks substantially all substrate defects.
[0021] Different substrates, such as films or coatings, are used in many applications, for example in industry. A typical disadvantage is that such substrates, such as films with coatings thereon, may include pinholes or other defects which limit their performance to a level below the intrinsic performance of the intact substrate. The inventors surprisingly found a way to plug such defects present in a substrate in order to improve the performance of the substrate. The inventors surprisingly found that when a blocking deposit is formed in a defect inside the substrate, the blocking deposit is also mechanically protected by the substrate itself. This can advantageously reduce its wear and tear, thereby extending the life of the substrate.
[0022] The substrate to be treated can be formed in different ways and from different materials. In one embodiment, the substrate is formed from a polymer, paper, ceramic, porous metal, porous glass and / or wood. In one embodiment, the substrate comprises or consists of a polymer, paper, ceramic, porous metal, porous glass and / or wood.
[0023] In one embodiment, the substrate consists of a barrier coating formed on a web formed of a polymer, paper, or wood. That is, the substrate may include or consist of a separate barrier coating formed on a film.
[0024] In one embodiment, the substrate is porous.
[0025] Typically, a barrier coating deposited on a substrate may contain defects, such as pinholes, through which moisture from the surrounding environment can penetrate and pass through the barrier coating to the substrate. For example, the substrate may be a plastic film used, for example, in the food processing industry. Such a plastic film easily absorbs moisture from the environment through its defects, thereby adversely affecting the product to be protected by the plastic film. The method disclosed in this specification has the additional benefit of plugging these defects. By the method disclosed in this specification, such defects can be deposited with more coating material, thereby forming a barrier deposit. The substrate may contain water. The water that the substrate may contain, for example, comes from its production process or because the substrate is made of a material that absorbs water from the surroundings or the environment. Water may be present in the substrate as moisture.
[0026] The first chemical used in the method is a chemical that can react with water to form an impeding deposit inside the defect of the substrate. In one embodiment, the first chemical is selected from the group consisting of metal halides, metal organics, or organometallics. Other chemicals used as precursors in atomic layer deposition (ALD) or chemical vapor deposition (CVD) to form solid materials through gas phase reactions can also be used as the first chemical. TiCl4, SiCl4 and SnCl4 can be used as examples of metal halides. Ti(OEt)4, Ti(O i Pr)4 and Cu(hfac)2 can be used as examples of metal organics. AlMe3, Ti(N(Me2))4 and MgCp2 can be used as examples of organometallics. However, other chemicals can also be selected within the knowledge of those skilled in the art, depending on the material of the barrier deposit to be formed.
[0027] The hindering deposit may comprise or consist of a metal oxide, a metal carbonate or a metal hydroxide. Merely as examples of such hindering deposits, mention may be made of TiO2, MgCO3 and Al(OH)3, respectively.
[0028] In one embodiment, the substrate comprises water or is exposed to water. In one embodiment, the substrate comprises water and is exposed to water. In one embodiment, the matrix comprises water. In one embodiment, the substrate is exposed to water.
[0029] In one embodiment, the substrate contains water while the substrate is exposed to the first chemical. In one embodiment, the substrate is exposed to water while the substrate is exposed to the first chemical. In one embodiment, the substrate contains water and is exposed to water while the substrate is exposed to the first chemical.
[0030] In the method, the substrate is simultaneously subjected to or exposed to water and a first chemical substance, so that the water and the first chemical substance diffuse into defects of the substrate and thereby form a barrier deposit therein, for example, by a reaction occurring between the water and the first chemical substance. When the water and the first chemical substance are allowed to exist simultaneously in the reaction space, the reaction between them effectively occurs.
[0031] The diffusion treatment may be performed simultaneously with exposing the substrate to the first chemical and optionally water. Alternatively, the substrate may be first exposed to the first chemical and optionally water, followed by the diffusion treatment.
[0032] The term "diffusion process" is to be understood as allowing water and the first chemical species to diffuse into defects of the substrate so that they can react with each other inside the substrate.
[0033] In one embodiment, the diffusion treatment is carried out at a temperature of 0-1000°C, or 20-600°C, or 40-400°C, or 60-300°C, or 80-200°C, or 100-150°C. The temperature used in the diffusion treatment may depend on the material of the substrate to be treated and the first chemical substance. In one embodiment, the substrate comprises or consists of plastic, and the diffusion treatment is carried out at a temperature of 0-300°C, or 20-200°C, or 40-100°C. In one embodiment, the substrate comprises or consists of ceramic or porous metal, and the diffusion treatment is carried out at a temperature of 0-1000°C, or 100-600°C, or 200-400°C. The temperature used may have the effect of promoting a reaction between water and the first chemical substance. The reaction may be accelerated, for example, by the temperature used.
[0034] In one embodiment, the diffusion process is performed by providing a pressure difference between different sides of the substrate.
[0035] In one embodiment, the substrate includes a first outer surface and a second outer surface opposite to the first outer surface, and the diffusion treatment is performed by setting a different pressure on the first outer surface side of the substrate than on the second outer surface side of the substrate in the reaction space.
[0036] In one embodiment, the substrate includes a first outer surface and a second outer surface opposite to the first outer surface, and the diffusion treatment is performed by setting a different pressure on the first outer surface side of the substrate than on the second outer surface side of the substrate in the reaction space, wherein the pressure difference causes the water and the first chemical substance to diffuse into the defects of the substrate.
[0037] The pressure on the side of the first outer surface of the substrate may be higher than the pressure on the side of the second outer surface of the substrate, and vice versa. The pressure difference has the additional effect of causing the first chemical and optionally water to diffuse into defects in the substrate to react with each other.
[0038] In one embodiment, the pressure difference is 1-1000000 Pa, or 10-10000 Pa, or 100-1000 Pa. In one embodiment, the pressure on the side of one of the first surface and the second surface of the substrate is 1-1000000 Pa, or 100-200000 Pa, or 1000-110000 Pa, and the pressure on the side of the other of the first surface and the second surface is 1-110000 Pa, or 100-101325 Pa, or 1000-101325 Pa. In one embodiment, the pressure on the side of one of the first surface and the second surface of the substrate is 1-1000000 Pa, or 100-200000 Pa, or 1000-110000 Pa, and the pressure on the side of the other of the first surface and the second surface is 1-110000 Pa, or 100-101325 Pa, or 1000-101325 Pa, wherein the pressure is selected so that the pressure difference is 1-1000000 Pa, or 10-10000 Pa, or 100-1000 Pa. The occurrence of the reaction can be accelerated by adjusting the pressure or pressure difference used.
[0039] In one embodiment, the diffusion treatment lasts for 0.01-1000 minutes, or 0.1-100 minutes, or 1-10 minutes. The time period for how long the diffusion treatment is allowed to last can depend on the number and / or size of defects present in the substrate, and for example, depends on how many obstruction deposits are to be formed. In one embodiment, the thickness of the obstruction deposit formed is 1-10000nm, or 5-500nm, or 20-100nm. The thickness of the obstruction deposit formed can be measured using a scanning electron microscope from a cross section of the substrate with the obstruction deposit. The diffusion treatment can also be repeated one or more times.
[0040] In one embodiment, the substrate includes a first outer surface and a second outer surface opposite to the first outer surface.
[0041] In one embodiment, the substrate includes a first outer surface and a second outer surface opposite to the first outer surface, and wherein one of the first surface and the second surface of the substrate is exposed to one of water and the first chemical, and the other of the first surface and the second surface is exposed to the other of water and the first chemical.
[0042] In one embodiment, the substrate contains water and is exposed to the first chemical only. In one embodiment, the substrate contains water and is exposed to the first chemical only from the first outer surface and / or the second outer surface side. The substrate may contain water, such as moisture, due to its production process and / or due to absorption of moisture from the surrounding environment, such as during storage.
[0043] In one embodiment, the method includes forming a barrier deposit within a substrate to minimize diffusion of molecules from the surrounding environment of the substrate into and / or through the substrate.
[0044] In one embodiment, the method includes forming a barrier deposit within the substrate to reduce the conductivity of the substrate.
[0045] The methods disclosed herein have the additional utility of plugging defects present within the substrate, thereby, for example, extending the life of the substrate and improving the performance of the substrate.
[0046] Plugging defects present within the substrate has the additional effect of forming a barrier deposit that is mechanically protected by the substrate.
[0047] Example
[0048] Reference will now be made in detail to the described embodiments, examples of which are illustrated in the accompanying drawings.
[0049] The following description discloses some embodiments in such detail that a person skilled in the art can utilize methods based on the present invention.Since many steps will be obvious to a person skilled in the art based on this description, all steps of the embodiments are not discussed in detail.
[0050] For simplicity, in the following exemplary embodiments, repeated components will keep the same component numbers.
[0051] Figure 1 It shows how to form a barrier deposit in a substrate according to one embodiment described in this specification. In this embodiment, the substrate 1 is formed by a barrier coating on a web formed of a polymer. The substrate includes a first outer surface 1a and a second outer surface 1b. The substrate 1 is inserted into a reaction space 2, wherein the substrate 1 is exposed to a first chemical substance from the first outer surface 1a side and is simultaneously exposed to water from the second outer surface 1b side. The substrate is subjected to a diffusion treatment so that the first chemical substance and water diffuse into the substrate, resulting in the formation of a barrier deposit in a defect existing in the substrate.
[0052] Figure 2How to form an obstructing deposit in a substrate according to another embodiment described in this specification is shown. In this embodiment, the substrate is a dry polymer film. The substrate includes a first outer surface 1a and a second outer surface 1b. The substrate 1 is inserted into a reaction space 2, wherein the substrate is exposed to a first chemical substance from the first outer surface 1a side and is exposed to water from the second outer surface 1b side. The substrate is subjected to a diffusion treatment so that the first chemical substance and water diffuse into the substrate, resulting in the formation of an obstructing deposit 3 in a defect existing in the substrate.
[0053] Figure 3 It is shown how to form an obstructing deposit inside a substrate according to another embodiment described in this specification. In this embodiment, the substrate is a polymer film that contains moisture due to absorption of moisture from the surrounding environment. The substrate includes a first outer surface 1a and a second outer surface 1b. The substrate 1 is inserted into a reaction space 2, wherein the substrate 1 is exposed to a first chemical substance from the side of the first outer surface 1a. A diffusion process is performed by setting a higher pressure on the first outer surface side and a lower pressure on the second outer surface side. Due to the pressure difference between the first outer surface and the second outer surface, the first chemical substance diffuses into the substrate. When the first chemical substance diffuses into the substrate, it contacts the moisture contained in the substrate and thus reacts with the moisture, thereby forming an obstructing deposit 3.
[0054] exist Figure 1-3 In the embodiment of the present invention, the barrier deposit is present in the form of a layer. However, the barrier deposit may be formed only in defects of the substrate, thereby not forming a continuous layer, but forming individual deposits in the defects.
[0055] Example 1 - Formation of a barrier deposit inside a substrate
[0056] In this embodiment, an obstructing deposit is formed inside the substrate. A molded polymer housing (polypropylene, 50×10 mm) is used as a substrate, and an electronic device is arranged inside the housing. The polymer housing contains some moisture (H2O) absorbed from the surrounding atmosphere. The polymer housing is placed in a reaction space, in which the substrate is exposed to a nitrogen environment with a saturated concentration of Al(Me)3 from one side of the first outer surface at a temperature of 70°C for 60 minutes. During exposure to Al(Me)3, Al(Me)3 diffuses into the polymer housing and encounters H2O present in the polymer housing at the surface of the polymer housing and reacts. This results in the formation of an Al2O3 layer on the surface of the polymer component. Part of the Al(Me)3 diffuses into the "wall" of the polymer housing and reacts with the moisture inside the polymer housing, resulting in the formation of an Al2O3 obstructing deposit inside the polymer housing.
[0057] As the diffusion process continues, the barrier deposit that forms becomes increasingly dense. Diffusion of the Al(Me)3 through the polymer shell then occurs primarily through the remaining defects in the barrier deposit. This results in more reactions taking place around the defects, causing them to be blocked by the Al2O3.
[0058] Thus, the polymer shell has an Al2O3 barrier deposit extending from an outer surface of the shell to an opposing surface of the polymer shell.
[0059] Example 2 - Formation of a barrier deposit inside a substrate
[0060] In this embodiment, an obstructing deposit is formed inside the substrate. A pre-dried 1200 mm wide polymer film (polyethylene, thickness 50 μm) is used as the substrate. The polymer film is continuously moved through the reaction space, wherein one side of the first outer surface of the polymer film is exposed to a nitrogen environment saturated with TiCl4 at 70°C, and one side of the second outer surface is simultaneously exposed to an air environment including water vapor (90% RH at 70°C). The reaction space is one meter (1m) long, and the polymer film moves from one end to the other end through the reaction space at a linear speed of 1m / min. Within 1 minute that a portion of the film moves through the reaction space, TiCl4 and H2O diffuse into the film from the opposite direction or opposite side of the polymer film, meet and react with each other in the polymer film. This results in the formation of TiO2 obstructing deposits inside the polymer film.
[0061] As the diffusion process continues, the barrier deposit that forms becomes increasingly dense. Diffusion of TiCl4 and H2O through the polymer film then occurs primarily through the remaining defects in the barrier deposit. This results in more reactions taking place around the defects, causing them to be blocked by TiO2.
[0062] Thus, a polymer film having TiO2 barrier deposits inside the polymer film is formed.
[0063] Example 3 - Formation of a barrier deposit inside a substrate
[0064] In this embodiment, an obstructing deposit is formed inside the substrate. A 100×100 mm polymer film (PET, 100 μm thick) that absorbs moisture from the surrounding atmosphere is used as a substrate. The polymer film is placed in a reaction space, wherein one side of the first outer surface of the polymer film is connected to a vacuum pump, and the absolute pressure of this side of the polymer film is maintained at a pressure of 3000+ / -100 Pa. The second outer surface side of the polymer film is connected to another vacuum pump and maintained at a pressure of 1000+ / -100 Pa. The reaction space with the polymer film is maintained at a temperature of 100° C. A steady flow of 100 sccm of Al(Me)3 vapor is applied on one side of the first outer surface of the polymer film for 10 minutes. During exposure to Al(Me)3, Al(Me)3 diffuses into the polymer film and reacts with moisture in the polymer film. This results in the formation of Al2O3 obstructing deposits inside the polymer film.
[0065] As the diffusion process continues, the barrier deposit that forms becomes increasingly dense. Diffusion of Al(Me)3 through the polymer film then occurs primarily through the remaining defects in the barrier deposit. This results in more reactions taking place around the defects, causing them to be blocked by Al2O3.
[0066] Therefore, a polymer film having Al2O3 barrier deposits inside the polymer film is formed.
[0067] It is obvious to a person skilled in the art that, as technology advances, the basic idea can be implemented in various ways. Therefore, the embodiments are not limited to the examples described above; instead, they may vary within the scope of the claims.
[0068] The embodiments described above can be used in any combination with each other. A plurality of embodiments can be combined together to form further embodiments. The method, substrate or use disclosed in the present invention may include at least one embodiment described above. It should be understood that the above benefits and advantages may relate to one embodiment or may relate to several embodiments. The embodiments are not limited to embodiments that solve any or all of the problems described, or those embodiments that have any or all of the benefits and advantages described. It should also be understood that reference to "a" item refers to one or more of those items. The term "comprising" in this specification is used to indicate that the features or actions that follow are included, without excluding the presence of one or more additional features or actions.
Claims
1. A method for forming an obstructing deposit inside a substrate including a defect, wherein: The method comprises introducing the substrate into a reaction space, wherein: The substrate contains water and / or is exposed to water, and at the same time the substrate is exposed to a first chemical, wherein the first chemical is configured to react with the water; and, The substrate is subjected to a diffusion process to allow the water and the first chemical substance to diffuse into defects of the substrate to react with each other inside the substrate, thereby forming a barrier deposit inside the substrate to plug the defects in the substrate.
2. The method according to claim 1, wherein: The first chemical substance is selected from the group consisting of metal halides, metal organics or organometallics.
3. The method according to claim 1, wherein: The diffusion treatment is performed at a temperature of 0-1000°C, or 20-600°C, or 40-400°C, or 60-300°C, or 80-200°C, or 100-150°C.
4. A method according to any one of the preceding claims, wherein: The substrate includes a first outer surface and a second outer surface opposite to the first outer surface, and the diffusion treatment is performed by setting a different pressure on the first outer surface side of the substrate than on the second outer surface side of the substrate in the reaction space, wherein the pressure difference causes the water and the first chemical substance to diffuse into the defects of the substrate.
5. A method according to any one of the preceding claims, wherein: The diffusion treatment lasts for 0.01-1000 minutes, or 0.1-100 minutes, or 1-10 minutes.
6. A method according to any one of the preceding claims, wherein: The substrate is formed of polymer, paper, ceramic, porous metal, porous glass and / or wood.
7. A method according to any one of the preceding claims, wherein: The substrate consists of a barrier coating formed on a web and the secondary material is formed of a polymer, paper and / or wood.
8. A method according to any one of the preceding claims, wherein: The substrate is porous.
9. A method according to any one of the preceding claims, wherein: The thickness of the formed barrier deposit is 1-10000 nm, or 5-500 nm, or 20-100 nm.
10. A method according to any one of the preceding claims, wherein: The substrate includes a first outer surface and a second outer surface opposite the first outer surface, and wherein one of the first surface and the second surface of the substrate is exposed to one of water and the first chemical, and the other of the first surface and the second surface is exposed to the other of water and the first chemical.
11. A method according to any one of the preceding claims, wherein: The method includes forming the barrier deposit within the interior of the substrate to minimize diffusion of molecules from the surrounding environment of the substrate into and / or through the substrate.
12. A method according to any one of the preceding claims, wherein: The method includes forming the barrier deposit inside the substrate to reduce the conductivity of the substrate.
13. A substrate comprising a blocking deposit existing inside the substrate and blocking defects existing in the substrate, wherein: The barrier deposit is obtained by the method according to any one of claims 1-12.
14. A substrate comprising a blocking deposit existing inside the substrate and blocking defects existing in the substrate, wherein: The barrier deposit comprises or consists of a metal oxide, a metal carbonate or a metal hydroxide.
15. Use of the method defined in any one of claims 1 to 12 for reducing the electrical conductivity of a substrate.
16. Use of a method as defined in any one of claims 1 to 12 for minimizing the diffusion of molecules from the surroundings of a substrate into and / or through said substrate.