Graphene composite nano ceramic slurry capable of preventing hydrogen embrittlement as well as preparation method and application of graphene composite nano ceramic slurry

Abstract

The invention belongs to the technical field of hydrogen embrittlement prevention coatings, and particularly discloses hydrogen embrittlement prevention graphene composite nano ceramic slurry as well as a preparation method and application thereof. The coating comprises the following components: 5 to 15 parts of graphene, 8 to 12 parts of aluminum oxide, 2 to 5 parts of zirconium oxide, 2 to 5 parts of boron nitride, 0.01 to 1 part of yttrium oxide, 0.01 to 1 part of cerium oxide, 0.1 to 1 part of chromate, 0.1 to 1 part of molybdate, 10 to 25 parts of epoxy resin, 5 to 20 parts of polyurethane, 1 to 10 parts of a magnetoelectric ion complexing agent, 0.1 to 1.5 parts of a wetting agent, 0.1 to 0.5 part of a water-based coalescing agent, 0.2 to 0.4 part of a water-based nano dispersant, 0.2 to 4 parts of a composite coupling agent, 0.2 to 0.5 part of a water-based stabilizer and 150 to 300 parts of water. The hydrogen embrittlement prevention coating prepared from the slurry has an excellent hydrogen embrittlement prevention effect and suitable surface resistance, and is suitable for hydrogen storage or hydrogen transportation workpieces.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrogen embrittlement prevention coatings, and particularly to a graphene composite nano-ceramic slurry for preventing hydrogen embrittlement, its preparation method and application. Background Art

[0002] With the rapid development of hydrogen energy technology, hydrogen storage equipment and hydrogen transportation pipelines, as key links in the hydrogen energy industry chain, their material properties are directly related to the safety and efficiency of the hydrogen energy system. However, traditional metal materials are prone to hydrogen embrittlement in a high-pressure hydrogen environment, that is, hydrogen atoms penetrate into the material interior and accumulate under the action of stress, resulting in a decrease in material toughness, generation of microcracks, and even fracture. The hydrogen embrittlement problem seriously affects the service life and safety of hydrogen storage equipment and hydrogen transportation pipelines, and has become one of the bottlenecks restricting the large-scale application of hydrogen energy technology.

[0003] To solve the hydrogen embrittlement problem, researchers have begun to explore new anti-hydrogen embrittlement materials. Ceramic materials are considered potential alternative materials due to their high hardness, corrosion resistance, and chemical stability. However, traditional ceramic materials are brittle and have poor impact resistance, making it difficult to meet the requirements of hydrogen storage equipment and hydrogen transportation pipelines for material toughness and strength. In recent years, nano-ceramic materials have received extensive attention due to their unique mechanical properties and adjustable microstructure. By introducing nano-particles, it is expected to improve the toughness and crack resistance of ceramic materials, but their long-term stability in a high-pressure hydrogen environment still needs to be further improved.

[0004] Graphene, as a two-dimensional carbon nano-material, has excellent physical and chemical properties. However, the problem of its combination with ceramics, how they interact with each other, and its dispersion uniformity in the slurry are still technical difficulties. In addition, for the special application scenarios of hydrogen storage equipment and hydrogen transportation pipelines, how to achieve the efficient preparation and large-scale application of graphene composite nano-ceramic slurry still needs further research.

[0005] Therefore, how to provide a graphene composite nano-ceramic slurry for preventing hydrogen embrittlement, its preparation method and application, optimize the interfacial bonding between graphene and the ceramic matrix, improve the dispersibility and stability of the slurry, and obtain a coating material with excellent anti-hydrogen embrittlement performance, high strength, and corrosion resistance, so as to improve the safety and service life of hydrogen storage equipment and hydrogen transportation pipelines is an urgent problem to be solved in this field. Summary of the Invention

[0006] In view of this, the present invention provides a graphene composite nano-ceramic slurry for preventing hydrogen embrittlement, its preparation method and application, so as to avoid hydrogen embrittlement of hydrogen storage materials and improve the safety and service life of hydrogen storage equipment.

[0007] To achieve the above object, the present invention adopts the following technical solutions:

[0008] A graphene composite nano-ceramic slurry for preventing hydrogen embrittlement, which is prepared from raw materials including the following mass parts:

[0009] 5-15 parts of graphene, 8-12 parts of alumina, 2-5 parts of zirconia, 2-5 parts of boron nitride, 0.01-1 part of yttrium oxide, 0.01-1 part of cerium oxide, 0.1-1 part of chromate, 0.1-1 part of molybdate, 10-25 parts of epoxy resin, 5-20 parts of polyurethane, 1-10 parts of magnetoelectric ion composite agent, 0.1-1.5 parts of wetting agent, 0.1-0.5 part of waterborne film-forming auxiliary agent, 0.2-0.4 part of waterborne nano-dispersant, 0.2-4 parts of composite coupling agent, 0.2-0.5 part of waterborne stabilizer, 150-300 parts of water.

[0010] Preferably, the particle sizes of the alumina, zirconia, boron nitride, yttrium oxide and cerium oxide are independently 1-300 nm.

[0011] Preferably, the chromate includes sodium chromate and / or potassium chromate, and the molybdate includes one or more of sodium molybdate, potassium molybdate and zinc molybdate.

[0012] Preferably, the epoxy resin includes one or more of bisphenol A epoxy resin, phenolic epoxy resin and alicyclic epoxy resin;

[0013] The polyurethane includes one or more of aliphatic polyurethane, aromatic polyurethane and waterborne polyurethane.

[0014] Preferably, the magnetoelectric ion composite agent includes one or more of [bmim]FeCl4, [bpy]FeCl4, [bmp]FeCl4 and [pbmim](FeCl4)2.

[0015] Preferably, the wetting agent includes one or more of carbon fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether;

[0016] The waterborne film-forming auxiliary agent includes one or more of Texanol, Coasol, Nexcoat795, LusolvanFBH, DAL-PADC, EEH, OE400, FX511 and alcohol ester 12;

[0017] The waterborne nano-dispersant includes sodium polyacrylate and / or ammonium polyacrylate;

[0018] The composite coupling agent includes one or more of aluminum zirconium coupling agent, silane coupling agent and titanate coupling agent;

[0019] The waterborne stabilizer includes SILRESMP50E and / or HD-020.

[0020] Another object of the present invention is to provide a method for preparing a graphene composite nano-ceramic slurry for preventing hydrogen embrittlement, comprising the following steps:

[0021] 1) Mix graphene, alumina, zirconia, boron nitride, yttrium oxide, cerium oxide, chromate, molybdate, epoxy resin, polyurethane, aqueous nano-dispersant, magnetoelectric ion composite agent, composite coupling agent and water, and carry out aging to obtain an aged liquid;

[0022] 2) Grind and disperse the aged liquid, and add a wetting agent, an aqueous film-forming aid, and an aqueous stabilizer for mixing to obtain a graphene composite nano-ceramic slurry for preventing hydrogen embrittlement.

[0023] Preferably, in step 1), the aging temperature is 20-80°C; the aging time is 2-48 h;

[0024] In step 2), the particle size after grinding and dispersion is 0.05-1 μm; the mixing time is 2-48 h.

[0025] Still another object of the present invention is to provide an application of a graphene composite nano-ceramic slurry for preventing hydrogen embrittlement as an anti-hydrogen embrittlement coating, and the application comprises the following steps:

[0026] S1: Magnetically pre-treat the workpiece to be processed to obtain a pre-treated workpiece;

[0027] S2: Under the condition of matching magnetic field control, carry out liquid-phase nano-deposition of the pre-treated workpiece in the graphene composite nano-ceramic slurry for preventing hydrogen embrittlement to obtain a first-treated workpiece;

[0028] S3: Under the condition of matching magnetic field control, carry out impurity removal treatment of the first-treated workpiece in the circulating liquid to obtain a second-treated workpiece controlled by the magnetic field;

[0029] S4: Under the condition of matching magnetic field control, carry out rearrangement densification treatment of the second-treated workpiece to obtain a third-treated workpiece;

[0030] S5: Under the conditions of normal pressure heating and matching magnetic field control, introduce a protective atmosphere, and carry out gas-phase nano-deposition of the third-treated workpiece by using the graphene composite nano-ceramic slurry for preventing hydrogen embrittlement to obtain a workpiece with an anti-hydrogen embrittlement coating.

[0031] Preferably, the workpiece to be processed includes a hydrogen storage tank or a hydrogen transportation pipeline;

[0032] In step S1, the magnetizing voltage of the magnetic pre-treatment is 300-1000 V, and the magnetizing time is 4-10 s;

[0033] In step S2, the magnetic force of the matching magnetic field is 50-1000 N, and the time is 1-5 h;

[0034] The magnetic force of the matching magnetic field described in step S3 is 50 - 1000 N, and the time is 0.1 - 1 h; the circulating liquid is water;

[0035] The magnetic force of the matching magnetic field described in step S4 is 50 - 1000 N, and the time is 0.1 - 1 h; the heating temperature is 45 - 280 °C;

[0036] The magnetic force of the matching magnetic field described in step S5 is 0.8 - 7200 N, and the time is 0.1 - 1 h; the heating temperature is 45 - 280 °C.

[0037] From the above technical solutions, it can be seen that compared with the prior art, the present invention has the following beneficial effects:

[0038] 1. In the graphene composite nano-ceramic slurry disclosed by the present invention, graphene has high strength, high conductivity and chemical stability, can effectively block the penetration of hydrogen atoms, and reduce the risk of hydrogen embrittlement; alumina and zirconia can enhance the barrier property and corrosion resistance of the coating, boron nitride can enhance the mechanical property and barrier property; chromate and molybdate can slow down hydrogen penetration and corrosion; yttrium oxide and cerium oxide can improve the corrosion resistance and mechanical property of the coating, and yttrium oxide can also stabilize zirconia, improving the anti-hydrogen embrittlement property and stability of the coating. In addition, graphene can also be coated with the above ceramic components to form a chemically stable and dense coating, effectively preventing the penetration of hydrogen atoms;

[0039] Epoxy resin and polyurethane have the characteristics of strong adhesion, good corrosion resistance, high stability and low hydrogen permeability. When used together, they also have good flexibility, can adapt to the deformation of the substrate, prevent the coating from cracking, improve the anti-hydrogen embrittlement effect, and are suitable for the coatings of hydrogen storage tanks and pipelines; epoxy resin and polyurethane also have a compounding effect with graphene and ceramic materials, and can cooperate to obtain a coating with excellent properties such as wear resistance and mechanical strength. Based on the resin wrapping effect, the slow-release anti-corrosion components can also be realized, prolonging the anti-corrosion effect.

[0040] 2. Based on the nano-deposited coating process technology, the present invention can achieve ionic-level densification of the coating, avoid hydrogen penetration, and improve the anti-hydrogen embrittlement effect.

[0041] 3. The workpiece treated by the present invention has excellent anti-hydrogen embrittlement performance and the advantage of long service life; in addition, the surface resistance of the anti-hydrogen embrittlement coating prepared by the present invention is between 10 5 ~10 8 . When applied to hydrogen storage pipelines, it can avoid static electricity accumulation and prevent fire or explosion. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only the embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained according to the provided drawings.

[0043] Figure 1 It is a control diagram of the neutral salt spray test of the graphene composite nano-ceramic slurry prepared in Embodiments 1-3 of the present invention;

[0044] Figure 2 It is the anti-hydrogen embrittlement test result of the graphene composite nano-ceramic slurry in Embodiment 1 of the present invention, where Current density - current density, Time - time. Specific embodiments

[0045] The present invention provides an anti-hydrogen embrittlement graphene composite nano-ceramic slurry, which is prepared from raw materials including the following parts by mass:

[0046] 5 to 15 parts of graphene, 8 to 12 parts of alumina, 2 to 5 parts of zirconia, 2 to 5 parts of boron nitride, 0.01 to 1 part of yttrium oxide, 0.01 to 1 part of cerium oxide, 0.1 to 1 part of chromate, 0.1 to 1 part of molybdate, 10 to 25 parts of epoxy resin, 5 to 20 parts of polyurethane, 1 to 10 parts of magnetoelectric ion composite agent, 0.1 to 1.5 parts of wetting agent, 0.1 to 0.5 parts of waterborne film-forming aid, 0.2 to 0.4 parts of waterborne nano-dispersant, 0.2 to 4 parts of composite coupling agent, 0.2 to 0.5 parts of waterborne stabilizer, 150 to 300 parts of water; under the above mass ratio, the addition amount of graphene can specifically be 6 parts, 8 parts, 10 parts, 12 parts, 14 parts; the addition amount of alumina can specifically be 9 parts, 10 parts, 11 parts; the addition amount of zirconia can specifically be 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts; the addition amount of boron nitride can specifically be 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts; the addition amount of yttrium oxide can specifically be 0.02 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.2 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.8 parts; the addition amount of cerium oxide can specifically be 0.02 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.2 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.8 parts; the addition amount of chromate can specifically be 0.2 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.8 parts; the addition amount of molybdate can specifically be 0.2 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.8 parts; the addition amount of epoxy resin can specifically be 12 parts, 15 parts, 18 parts, 20 parts, 22 parts; the addition amount of polyurethane can specifically be 8 parts, 10 parts, 12 parts, 14 parts, 15 parts, 16 parts, 18 parts; the addition amount of magnetoelectric ion composite agent can specifically be 2 parts, 4 parts, 5 parts, 6 parts, 8 parts; the addition amount of wetting agent can specifically be 0.2 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.8 parts, 1 part, 1.2 parts, 1.4 parts; the addition amount of waterborne film-forming aid can specifically be 0.2 parts, 0.3 parts, 0.4 parts; the addition amount of waterborne nano-dispersant can specifically be 0.25 parts, 0.3 parts, 0.35 parts; the addition amount of composite coupling agent can specifically be 0.5 parts, 1 part, 2 parts, 3 parts; the addition amount of waterborne stabilizer can specifically be 0.25 parts, 0.3 parts, 0.35 parts, 0.4 parts, 0.45 parts; the addition amount of water can specifically be 160 parts, 180 parts, 200 parts, 220 parts, 250 parts, 280 parts.

[0047] In the present invention, the particle sizes of the alumina, zirconia, boron nitride, yttrium oxide and cerium oxide are independently 1 to 300 nm, and can specifically be 5 nm, 10 nm, 20 nm, 50 nm, 80 nm, 100 nm, 150 nm, 200 nm, 250 nm.

[0048] In the present invention, the chromate includes sodium chromate and / or potassium chromate, and the molybdate includes one or more of sodium molybdate, potassium molybdate, and zinc molybdate.

[0049] In the present invention, the epoxy resin includes one or more of bisphenol A epoxy resin, phenolic epoxy resin, and alicyclic epoxy resin.

[0050] In the present invention, the polyurethane includes one or more of aliphatic polyurethane, aromatic polyurethane, and aqueous polyurethane.

[0051] In the present invention, the magnetoelectric ion composite agent includes one or more of [bmim]FeCl4, [bpy]FeCl4, [bmp]FeCl4, and [pbmim](FeCl4)2.

[0052] In the present invention, the wetting agent includes one or more of carbon fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, and fatty alcohol polyoxyethylene ether.

[0053] In the present invention, the aqueous film-forming aid includes one or more of Texanol, Coasol, Nexcoat795, Lusolvan FBH, DAL-PADC, EEH, OE400, FX511, and alcohol ester 12.

[0054] In the present invention, the aqueous nano-dispersant includes sodium polyacrylate and / or ammonium polyacrylate.

[0055] In the present invention, the composite coupling agent includes one or more of aluminum zirconium coupling agent, silane coupling agent, and titanate coupling agent.

[0056] In the present invention, the aqueous stabilizer includes SILRES MP50E and / or HD-020.

[0057] The present invention also provides a method for preparing a hydrogen embrittlement-proof graphene composite nano-ceramic slurry, comprising the following steps:

[0058] 1) Mix graphene, alumina, zirconia, boron nitride, yttrium oxide, cerium oxide, chromate, molybdate, epoxy resin, polyurethane, aqueous nano-dispersant, magnetoelectric ion composite agent, composite coupling agent, and water, and carry out aging to obtain an aged liquid;

[0059] 2) Grind and disperse the aged liquid, and add a wetting agent, an aqueous film-forming aid, and an aqueous stabilizer to obtain a hydrogen embrittlement-proof graphene composite nano-ceramic slurry.

[0060] In the present invention, the curing temperature in step 1) is 20 to 80 °C, specifically it can be 25 °C, 30 °C, 35 °C, 40 °C, 50 °C, 60 °C; the curing time is 2 to 48 h, specifically it can be 4 h, 5 h, 10 h, 12 h, 24 h, 30 h, 40 h.

[0061] In the present invention, the particle size after grinding and dispersion in step 2) is 0.05 to 1 μm, specifically it can be 0.08 μm, 0.1 μm, 0.2 μm, 0.5 μm, 0.8 μm; the mixing time is 2 to 48 h, specifically it can be 4 h, 5 h, 10 h, 12 h, 24 h, 30 h, 40 h.

[0062] The present invention also provides an application of a hydrogen embrittlement - resistant graphene composite nanoceramic slurry as a hydrogen embrittlement - resistant coating, and the application includes the following steps:

[0063] S1: Magnetically pre - treat the workpiece to be processed to obtain a pre - treated workpiece;

[0064] S2: Under the condition of matching magnetic field control, perform liquid - phase nano - deposition of the pre - treated workpiece in the hydrogen embrittlement - resistant graphene composite nanoceramic slurry to obtain a first - treated workpiece;

[0065] S3: Under the condition of matching magnetic field control, perform impurity removal treatment of the first - treated workpiece in the circulating liquid to obtain a second - treated workpiece controlled by the magnetic field;

[0066] S4: Under the condition of matching magnetic field control, perform rearrangement and densification treatment of the second - treated workpiece to obtain a third - treated workpiece;

[0067] S5: Under the conditions of normal - pressure heating and matching magnetic field control, introduce a protective atmosphere, and perform gas - phase nano - deposition of the third - treated workpiece using the hydrogen embrittlement - resistant graphene composite nanoceramic slurry to obtain a workpiece with a hydrogen embrittlement - resistant coating.

[0068] In the present invention, the workpiece to be processed includes a hydrogen storage tank or a hydrogen transportation pipeline;

[0069] In the present invention, the magnetizing voltage of the magnetic pre - treatment in step S1 is 300 to 1000 V, specifically it can be 400 V, 500 V, 600 V, 800 V; the magnetizing time is 4 to 10 s, specifically it can be 5 s, 6 s, 7 s, 8 s, 9 s.

[0070] In the present invention, the magnetic force of the matching magnetic field in step S2 is 50 to 1000 N, specifically it can be 80 N, 100 N, 200 N, 400 N, 500 N, 600 N, 800 N; the time is 0.1 to 1 h, specifically it can be 0.2 h, 0.4 h, 0.5 h, 0.6 h, 0.8 h.

[0071] In the present invention, the magnetic force of the matching magnetic field in step S3 is 50 to 1000 N, specifically, it can be 80 N, 100 N, 200 N, 400 N, 500 N, 600 N, 800 N; the time is 0.1 to 1 h, specifically, it can be 0.2 h, 0.4 h, 0.5 h, 0.6 h, 0.8 h; the circulating liquid is water.

[0072] In the present invention, the magnetic force of the matching magnetic field in step S4 is 50 to 1000 N, specifically, it can be 80 N, 100 N, 200 N, 400 N, 500 N, 600 N, 800 N; the time is 0.1 to 1 h, specifically, it can be 0.2 h, 0.4 h, 0.5 h, 0.6 h, 0.8 h; the heating temperature is 45 to 280 °C, specifically, it can be 50 °C, 80 °C, 100 °C, 120 °C, 150 °C, 180 °C, 200 °C, 220 °C, 250 °C.

[0073] In the present invention, the magnetic force of the matching magnetic field in step S5 is 0.8 to 7200 N, specifically, it can be 1 N, 5 N, 10 N, 50 N, 100 N, 200 N, 500 N, 800 N, 1000 N, 2000 N, 5000 N, 7000 N; the time is 0.1 to 1 h, specifically, it can be 0.2 h, 0.4 h, 0.5 h, 0.6 h, 0.8 h; the heating temperature is 45 to 280 °C, specifically, it can be 50 °C, 80 °C, 100 °C, 120 °C, 150 °C, 180 °C, 200 °C, 220 °C, 250 °C.

[0074] Next, the technical solutions in the embodiments of the present invention will be described clearly and completely. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts shall fall within the protection scope of the present invention.

[0075] Example 1

[0076] Preparation of graphene composite nano-ceramic slurry for hydrogen embrittlement prevention:

[0077] Take alumina, zirconia, boron nitride, yttrium oxide and cerium oxide with particle sizes all of 50 to 100 nm for standby.

[0078] 12 parts of graphene, 10 parts of aluminum oxide, 4 parts of zirconium oxide, 3 parts of boron nitride, 0.3 parts of yttrium oxide, 0.1 parts of cerium oxide, 0.5 parts of sodium chromate, 0.5 parts of sodium molybdate, 20 parts of bisphenol A epoxy resin, 8 parts of aliphatic polyurethane, 5 parts of magnetic ion composite agent [bmim] FeCl4, 0.3 parts of sodium polyacrylate, 2 parts of aluminum zirconium coupling agent and 250 parts of water were fully mixed at a stirring speed of 500rpm, and then placed at 50°C for 13h to obtain a aging liquid. Then the above aging liquid was ground and dispersed (particle size was 0.1-0.5μm), and then 1 part of carbon fatty alcohol polyoxyethylene ether, 0.4 parts of water-based film-forming aid Texanol, and 0.3 parts of water-based stabilizer SILRESMP50E were added and mixed for 12h to obtain a graphene composite nano-ceramic slurry that is resistant to hydrogen embrittlement.

[0079] Preparation of anti-hydrogen embrittlement coating:

[0080] Under normal temperature and pressure conditions, the hydrogen storage tank is subjected to magnetization pretreatment using a magnetizer at a magnetizing voltage of 500 V and a magnetizing time of 6 s to obtain a pretreated hydrogen storage tank;

[0081] The pre-treated hydrogen storage tank is immersed in the nano-deposition liquid, the magnetic field of the nano-deposition liquid is adjusted to match the magnetic field of the pre-treated hydrogen storage tank, and the magnetic field force of the matching magnetic field is controlled to be 100N to achieve liquid phase deposition of the nano-deposition liquid, and the hydrogen storage tank treated with nano-deposition is obtained after 1 hour;

[0082] The hydrogen storage tank treated with nano-deposition was placed in a normal temperature and pressure aqueous solution (circulated) controlled by a matching magnetic field of 100N to remove impurities for 30 minutes, thereby forming a hydrogen storage tank controlled by a magnetic field;

[0083] Under the condition of a matching magnetic field of 100N, the hydrogen storage tank controlled by the magnetic field is heated to 250°C for rearrangement and densification for 1 hour to obtain a rearranged and densified hydrogen storage tank;

[0084] The rearranged and densified hydrogen storage tank was placed in a matching magnetic field of 100N and 200°C, and argon gas was introduced to perform gas phase nano-deposition for 1 hour to obtain a hydrogen storage tank with an anti-hydrogen embrittlement coating.

[0085] Example 2

[0086] Preparation of graphene composite nano-ceramic slurry with anti-hydrogen embrittlement:

[0087] Alumina, zirconium oxide, boron nitride, yttrium oxide and cerium oxide with particle sizes of 50 to 100 nm are prepared for use.

[0088] Fifteen parts of graphene, eight parts of aluminum oxide, five parts of zirconium oxide, five parts of boron nitride, 0.1 part of yttrium oxide, 0.1 part of cerium oxide, 0.8 part of sodium chromate, 0.3 part of sodium molybdate, 25 parts of phenolic epoxy resin, five parts of waterborne polyurethane, eight parts of magnetoelectric ion composite agent [bmp]FeCl4, 0.2 part of sodium polyacrylate, three parts of aluminum zirconium coupling agent and 220 parts of water were fully mixed at a stirring speed of 500 rpm, and then cured at 40 °C for 36 h to obtain a cured liquid. Then, the above-mentioned cured liquid was ground and dispersed (particle size of 0.1 - 0.5 μm), and then 0.5 part of alkylphenol polyoxyethylene ether, 0.2 part of waterborne film-forming auxiliary agent Nexcoat795, and 0.2 part of waterborne stabilizer SILRES MP50E were added and mixed for 12 h to obtain a graphene composite nano-ceramic slurry for preventing hydrogen embrittlement.

[0089] Preparation of hydrogen embrittlement prevention coating:

[0090] Under normal temperature and pressure conditions, the hydrogen storage tank was magnetically pre-treated using a magnetizer at a magnetizing voltage of 800 v and a magnetizing time of 4 s to obtain a pre-treated hydrogen storage tank;

[0091] The pre-treated hydrogen storage tank was immersed in the nano-deposition liquid, and the magnetic field of the nano-deposition liquid was adjusted to match the magnetic field of the pre-treated hydrogen storage tank. The magnetic force of the matching magnetic field was controlled at 200 N to achieve liquid-phase deposition of the nano-deposition liquid. After 1 h, a hydrogen storage tank treated by nano-deposition was obtained;

[0092] The hydrogen storage tank treated by nano-deposition was decontaminated in an aqueous solution (recycled) under normal temperature and pressure controlled by a matching magnetic field of 200 N for 30 min to form a hydrogen storage tank with a controlled magnetic field;

[0093] Under the condition that the matching magnetic field was controlled at 200 N, the hydrogen storage tank with a controlled magnetic field was heated to 200 °C for 1 h for rearrangement and densification to obtain a hydrogen storage tank with rearrangement and densification;

[0094] The hydrogen storage tank with rearrangement and densification was introduced with argon at a matching magnetic field of 200 N and 150 °C for 1 h for gas-phase nano-deposition to obtain a hydrogen storage tank with a hydrogen embrittlement prevention coating.

[0095] Example 3

[0096] Preparation of graphene composite nano-ceramic slurry for preventing hydrogen embrittlement:

[0097] Aluminum oxide, zirconium oxide, boron nitride, yttrium oxide and cerium oxide with particle sizes of 80 - 120 nm were taken for standby.

[0098] 8 parts of graphene, 8 parts of alumina, 2 parts of zirconia, 3 parts of boron nitride, 0.05 part of yttrium oxide, 0.3 part of cerium oxide, 0.3 part of sodium chromate, 0.1 part of zinc molybdate, 15 parts of bisphenol A epoxy resin, 10 parts of aliphatic polyurethane, 4 parts of magnetoelectric ion composite agent [bmim]FeCl4, 0.2 part of sodium polyacrylate, 1 part of aluminum zirconium coupling agent and 180 parts of water were fully mixed at a stirring speed of 500 rpm, and then cured at 45°C for 32 h to obtain a cured liquid. Then, the above cured liquid was ground and dispersed (particle size: 0.1 - 0.5 μm), and then 0.8 part of fatty alcohol polyoxyethylene ether, 0.2 part of waterborne film-forming auxiliary agent Coasol, and 0.3 part of waterborne stabilizer HD-020 were added and mixed for 12 h to obtain a graphene composite nano-ceramic slurry for preventing hydrogen embrittlement.

[0099] Preparation of hydrogen embrittlement prevention coating:

[0100] Under normal temperature and pressure conditions, the hydrogen storage tank was magnetically pre-treated using a magnetizer at a magnetizing voltage of 500 v and a magnetizing time of 8 s to obtain a pre-treated hydrogen storage tank;

[0101] The pre-treated hydrogen storage tank was immersed in the nano-deposition liquid, and the magnetic field of the nano-deposition liquid was adjusted to match the magnetic field of the pre-treated hydrogen storage tank. The magnetic force of the matching magnetic field was controlled at 150 N to achieve the liquid-phase deposition of the nano-deposition liquid, and a hydrogen storage tank treated by nano-deposition was obtained after 0.5 h;

[0102] The hydrogen storage tank treated by nano-deposition was purified in an aqueous solution (recycled) under normal temperature and pressure controlled by a matching magnetic field of 150 N for 30 min to form a hydrogen storage tank with a controlled magnetic field;

[0103] Under the condition of being controlled by a matching magnetic field of 150 N, the hydrogen storage tank with a controlled magnetic field was heated to 280°C for rearrangement and densification for 0.5 h to obtain a hydrogen storage tank with rearrangement and densification;

[0104] The hydrogen storage tank with rearrangement and densification was introduced with argon gas under the condition of a matching magnetic field of 150 N and 200°C for gas-phase nano-deposition for 1 h to obtain a hydrogen storage tank with a hydrogen embrittlement prevention coating.

[0105] Comparative Example 1

[0106] The difference between this comparative example and Example 1 is only that graphene is not added.

[0107] Experimental Example 1

[0108] The hydrogen embrittlement prevention coatings obtained using the slurries described in Examples 1 - 3 and Comparative Example 1 were subjected to relevant performance tests, and the test results are shown in Table 1:

[0109] Table 1 Test results of relevant performance of hydrogen embrittlement prevention coating

[0110]

[0111]

[0112] As can be seen from Table 1, the anti-hydrogen embrittlement coating film obtained by the present invention has a flat and smooth surface, strong adhesion, and good flexibility. By comparing the present invention with Example 1, it can be seen that the surface resistance of the anti-hydrogen embrittlement coating prepared by the present invention is lower than that of Comparative Example 1, which can timely conduct static electricity, avoid sparks caused by static electricity accumulation, and reduce the risk of explosion; it can also prevent material aging caused by static electricity and reduce the risk of hydrogen leakage.

[0113] The anti-hydrogen embrittlement graphene composite nano-ceramic slurries obtained in Examples 1 to 3 were respectively denoted as Samples 1 to 3, and a third party was entrusted to conduct a neutral salt spray test (GB / T 10125-2021). The samples before and after the test are as Figure 1 shown. It can be seen through Figure 1 that the coating formed by the composite nano-ceramic slurry disclosed in the present invention has good anti-corrosion performance.

[0114] A third party was entrusted to conduct relevant tests on the anti-hydrogen embrittlement effect. The changes in the current density over time of the samples with the slurry coating of Example 1 (denoted as with coating) and the samples without coating (denoted as without coating) were respectively measured. The test results are as Figure 2 shown. It can be seen through Figure 2 that the present invention has excellent anti-hydrogen embrittlement performance. In the present invention, graphene and ceramic components are mutually coated to form a chemically stable and dense coating, which significantly reduces the penetration of hydrogen atoms and greatly improves the anti-hydrogen embrittlement performance of the coating.

[0115] In this specification, each embodiment is described in a progressive manner. The key point of each embodiment is to illustrate the differences from other embodiments. The same or similar parts among the embodiments can be referred to each other.

[0116] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be obvious to those skilled in the art. The general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but will conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A graphene composite nano-ceramic slurry that is resistant to hydrogen embrittlement, characterized in that: Prepared from the following raw materials in parts by weight: 5 to 15 parts of graphene, 8 to 12 parts of aluminum oxide, 2 to 5 parts of zirconium oxide, 2 to 5 parts of boron nitride, 0.01 to 1 part of yttrium oxide, 0.01 to 1 part of cerium oxide, 0.1 to 1 part of chromate, 0.1 to 1 part of molybdate, 10 to 25 parts of epoxy resin, 5 to 20 parts of polyurethane, 1 to 10 parts of magneto-ionic composite agent, 0.1 to 1.5 parts of wetting agent, 0.1 to 0.5 parts of aqueous film-forming aid, 0.2 to 0.4 parts of aqueous nano-dispersant, 0.2 to 4 parts of composite coupling agent, 0.2 to 0.5 parts of aqueous stabilizer, and 150 to 300 parts of water.

2. The anti-hydrogen embrittlement graphene composite nano-ceramic slurry according to claim 1, characterized in that: The particle sizes of the aluminum oxide, zirconium oxide, boron nitride, yttrium oxide and cerium oxide are independently 1 to 300 nm.

3. The anti-hydrogen embrittlement graphene composite nano-ceramic slurry according to claim 2, characterized in that: The chromate includes sodium chromate and / or potassium chromate, and the molybdate includes one or more of sodium molybdate, potassium molybdate and zinc molybdate.

4. The anti-hydrogen embrittlement graphene composite nano-ceramic slurry according to any one of claims 1 to 3, characterized in that: The epoxy resin includes one or more of bisphenol A epoxy resin, novolac epoxy resin and alicyclic epoxy resin; The polyurethane includes one or more of aliphatic polyurethane, aromatic polyurethane and waterborne polyurethane.

5. The anti-hydrogen embrittlement graphene composite nano-ceramic slurry according to claim 4, characterized in that: The magnetic ion complex agent includes one or more of [bmim]FeCl4, [bpy]FeCl4, [bmp]FeCl4 and [pbmim](FeCl4)2.

6. The anti-hydrogen embrittlement graphene composite nano-ceramic slurry according to claim 5, characterized in that: The wetting agent includes one or more of aliphatic alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether; One or more of the aqueous film-forming aids Texanol, Coasol, Nexcoat795, LusolvanFBH, DAL-PADC, EEH, OE400, FX511 and alcohol ester 12; The aqueous nano-dispersant includes sodium polyacrylate and / or ammonium polyacrylate; The composite coupling agent includes one or more of an aluminum-zirconium coupling agent, a silane coupling agent and a titanate coupling agent; The aqueous stabilizer includes SILRES MP50E and / or HD-020.

7. The method for preparing a hydrogen embrittlement-resistant graphene composite nano-ceramic slurry according to any one of claims 1 to 6, characterized in that: The steps include: 1) mixing graphene, aluminum oxide, zirconium oxide, boron nitride, yttrium oxide, cerium oxide, chromate, molybdate, epoxy resin, polyurethane, aqueous nano-dispersant, magneto-ionic composite agent, composite coupling agent and water, and aging to obtain aging liquid; 2) Grind and disperse the aging liquid, add a wetting agent, an aqueous film-forming aid, and an aqueous stabilizer to mix, and obtain a graphene composite nano-ceramic slurry that is resistant to hydrogen embrittlement.

8. The method for preparing a hydrogen embrittlement-resistant graphene composite nano-ceramic slurry according to claim 7, characterized in that: The aging temperature in step 1) is 20 to 80° C. and the aging time is 2 to 48 hours; The particle size after grinding and dispersion in step 2) is 0.05 to 1 μm; the mixing time is 2 to 48 hours.

9. The use of the anti-hydrogen embrittlement graphene composite nano-ceramic slurry according to any one of claims 1 to 6 as an anti-hydrogen embrittlement coating, characterized in that: The application comprises the following steps: S1: performing magnetization pretreatment on the workpiece to be processed to obtain a pretreated workpiece; S2: Under the condition of matching magnetic field control, liquid phase nano-deposition is performed on the pre-treated workpiece in a graphene composite nano-ceramic slurry that is resistant to hydrogen embrittlement to obtain a first treated workpiece; S3: Under the condition of matching magnetic field control, the first processed workpiece is subjected to impurity removal treatment in the circulating liquid to obtain a second processed workpiece under magnetic field control; S4: Under the condition of matching magnetic field control, the second processed workpiece is rearranged and densified to obtain a third processed workpiece; S5: Under the conditions of normal pressure heating and matching magnetic field control, a protective atmosphere is introduced, and the third processed workpiece is subjected to gas phase nano-deposition using a hydrogen embrittlement-resistant graphene composite nano-ceramic slurry to obtain a workpiece with an anti-hydrogen embrittlement coating.

10. The use of the anti-hydrogen embrittlement graphene composite nano-ceramic slurry as an anti-hydrogen embrittlement coating according to claim 9, characterized in that: The workpiece to be processed includes a hydrogen storage tank or a hydrogen transportation pipeline; The magnetization voltage of the magnetization pretreatment in step S1 is 300-1000V, and the magnetization time is 4-10s; The magnetic field force of the matching magnetic field in step S2 is 50 to 1000 N, and the time is 0.1 to 1 hour; The magnetic field force of the matching magnetic field in step S3 is 50-1000N, and the time is 0.1-1h; the circulating fluid is water; In step S4, the magnetic field force of the matching magnetic field is 50-1000N, and the time is 0.1-1h; the heating temperature is 45-280°C; In step S5, the magnetic field force of the matching magnetic field is 0.8-7200N, and the time is 0.1-1h; the heating temperature is 45-280°C.

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