SiO2 / alpha-Al2O3 composite hydrogen-resistant coating for hydrogen delivery pipeline and preparation method of SiO2 / alpha-Al2O3 composite hydrogen-resistant coating

Abstract

The invention discloses a SiO2 / alpha-Al2O3 composite hydrogen-resistant coating for a hydrogen conveying pipeline and a preparation method of the SiO2 / alpha-Al2O3 composite hydrogen-resistant coating, and belongs to the technical field of hydrogen resistance of hydrogen conveying pipelines. The composite hydrogen-resistant coating disclosed by the invention is of a sandwich composite structure of a base material, namely SiO2-alpha-Al2O3; a radio frequency magnetron sputtering method is adopted, the composite coating with the related thickness is flexibly prepared by controlling parameters, the preparation method is simple and easy to implement, the preparation cost is low, and according to related experimental results, it is proved that the obtained SiO2 / alpha-Al2O3 composite hydrogen resistance coating for the hydrogen conveying pipeline is compact in structure, bonding between a base material and SiO2 and between SiO2 and alpha-Al2O3 interfaces is tight, and the film-substrate bonding force is 8.5 N; the hydrogen permeation activation energy is 146.2-177.9 kJ. / mol, the hydrogen permeation pressure index is 0.73-0.91, the problems of hydrogen permeation and hydrogen embrittlement of the hydrogen conveying pipeline can be greatly solved, and the service safety of the hydrogen conveying pipeline is guaranteed.

Description

Technical Field

[0001] The present invention belongs to the technical field of hydrogen-blocking technology for hydrogen pipelines, and particularly relates to a SiO2 / α-Al2O3 composite hydrogen-blocking coating for hydrogen pipelines and a preparation method thereof. Background Art

[0002] Hydrogen energy storage and transportation technology is a key link in the utilization of hydrogen energy. At present, the main hydrogen transportation methods include gaseous transportation by long tube trailers, pipeline transportation, solid-state transportation, and liquid hydrogen transportation. Among them, pipeline transportation is the safest, most efficient, and most economical method. Hydrogen has a strong penetration ability and can quickly penetrate almost all metal materials, causing hydrogen embrittlement, resulting in unpredictable brittle fracture of materials under conditions far lower than the design strain, bringing incalculable accident hazards to human life safety, property safety, ecological environment, etc. Therefore, in view of the current situation that the existing pipeline steel materials have a high hydrogen penetration rate and are prone to hydrogen embrittlement, covering a hydrogen-blocking ceramic coating on its surface has extremely important practical significance for solving the problems of hydrogen penetration and hydrogen embrittlement.

[0003] At present, the development of hydrogen embrittlement-resistant and hydrogen-blocking coatings is still in its infancy. The method for solving hydrogen embrittlement in hydrogen pipelines is to use low-grade pipeline steel to replace high-grade pipeline steel for small-diameter and low-pressure transportation, which cannot meet the future needs of large-scale hydrogen transportation and use. Therefore, it is crucial to seek a method for hydrogen resistance and hydrogen blocking for high-grade pipeline steel. Summary of the Invention

[0004] In order to overcome the above-mentioned disadvantages of the prior art, the purpose of the present invention is to provide a SiO2 / α-Al2O3 composite hydrogen-blocking coating for hydrogen pipelines and a preparation method thereof, so as to solve the technical problems such as high hydrogen penetration rate and high hydrogen embrittlement sensitivity of traditional high-grade pipeline steel.

[0005] In order to achieve the above purpose, the present invention adopts the following technical solutions:

[0006] The present invention discloses a SiO2 / α-Al2O3 composite hydrogen-blocking coating for hydrogen pipelines, and the SiO2 / α-Al2O3 composite hydrogen-blocking coating for hydrogen pipelines is attached to the surface of the hydrogen pipeline; the SiO2 / α-Al2O3 composite hydrogen-blocking coating has a sandwich composite structure of matrix material - SiO2 - α-Al2O3.

[0007] Further, the bonding force between the SiO2 / α-Al2O3 composite hydrogen-blocking coating for hydrogen pipelines and the surface of the hydrogen pipeline is 8.5 N.

[0008] Further, the hydrogen penetration activation energy of the SiO2 / α-Al2O3 composite hydrogen-blocking coating for hydrogen pipelines is 146.2 - 177.9 kJ / mol, and the hydrogen penetration pressure index is 0.73 - 0.91.

[0009] The present invention also discloses a method for preparing the SiO2 / α-Al2O3 composite hydrogen barrier coating for the hydrogen transmission pipeline, which includes the following steps:

[0010] Pretreat the surface of the hydrogen transmission pipeline, and then deposit the SiO2 / α-Al2O3 composite hydrogen barrier coating on the surface of the hydrogen transmission pipeline by radio frequency magnetron sputtering;

[0011] Among them, the target materials used in the radio frequency magnetron sputtering method are Si target and Al target, the starting gas is argon with a purity of 99.99%, and the reaction gas is oxygen with a purity of 99.99%.

[0012] Further, the pretreatment is to polish, ultrasonically clean and dry the surface of the hydrogen transmission pipeline in sequence.

[0013] Further, the ultrasonic cleaning is to ultrasonically clean with acetone and alcohol for 15 - 30 min.

[0014] Further, first deposit the SiO2 coating on the surface of the hydrogen transmission pipeline by radio frequency magnetron sputtering. The vacuum degree of the radio frequency magnetron sputtering method is ≥4×10 -3 Pa, the sputtering power is 70 - 120 W, the sputtering gas pressure is 0.25 - 1.5 Pa, the O2 / Ar gas mixing ratio is 1:10 - 1:5. When depositing the SiO2 coating, the heating temperature of the hydrogen transmission pipeline is 400 - 500 °C.

[0015] Further, in the SiO2 / α-Al2O3 composite hydrogen barrier coating, the deposition rate of the SiO2 coating is 150 nm / h - 253 nm / h, and the thickness is 50 - 122 nm.

[0016] Further, secondly, deposit the α-Al2O3 coating on the surface of the SiO2 coating by radio frequency magnetron sputtering. The vacuum degree of the radio frequency magnetron sputtering method is ≥4×10 -3 Pa, the sputtering power is 50 - 160 W, the sputtering gas pressure is 1 - 2 Pa, and the O2 / Ar gas mixing ratio is within the range of 1:10 - 1:5; when depositing the α-Al2O3 coating, the heating temperature of the hydrogen transmission pipeline is 500 - 600 °C.

[0017] Further, in the SiO2 / α-Al2O3 composite hydrogen barrier coating, the deposition rate of the α-Al2O3 coating is 89 nm / h - 140 nm / h, and the thickness is 120 - 172 nm.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] The present invention discloses a SiO2 / α-Al2O3 composite hydrogen-blocking coating for hydrogen transmission pipelines, which has a sandwich composite structure of substrate material - SiO2 - α-Al2O3, can effectively protect hydrogen transmission pipelines, and effectively solve the problems of high hydrogen permeation rate and high hydrogen embrittlement sensitivity of steel; at the same time, the prepared composite hydrogen-blocking coating has uniform particles, a dense structure, excellent hydrogen-blocking performance, and a tight interface bonding, and has broad application prospects.

[0020] The present invention also discloses a preparation method of the above composite hydrogen-blocking coating. By using the radio frequency magnetron sputtering method and controlling parameters, a composite coating with a relevant thickness can be flexibly prepared. The preparation method is simple and easy to implement, and the preparation cost is low. According to relevant experimental results, the SiO2 / α-Al2O3 composite hydrogen-blocking coating for hydrogen transmission pipelines obtained has a dense structure, a tight bonding between the substrate material and SiO2, and between SiO2 and α-Al2O3 interfaces, and the film-substrate bonding force is 8.5 N; the hydrogen permeation activation energy is 146.2 - 177.9 kJ / mol, and the hydrogen permeation pressure index is 0.73 - 0.91, which can greatly reduce the hydrogen permeation and hydrogen embrittlement problems of hydrogen transmission pipelines and ensure the service safety of hydrogen transmission pipelines. Specific embodiments

[0021] To enable those skilled in the art to understand the features and effects of the present invention, the following provides a general description and definition of the terms and phrases mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meanings understood by those skilled in the art regarding the present invention. In case of conflicts, the definitions in this specification shall prevail.

[0022] The theories or mechanisms described and disclosed herein, whether correct or incorrect, shall not limit the scope of the present invention in any way, that is, the content of the present invention can be implemented without being limited by any specific theory or mechanism.

[0023] In this article, all features defined in the form of numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are only for the sake of brevity and convenience. Accordingly, the description of numerical ranges or percentage ranges should be regarded as having covered and specifically disclosed all possible sub-ranges and individual numerical values within the range (including integers and fractions).

[0024] In this article, unless otherwise specified, terms such as "comprise", "include", "contain", "have", or similar terms cover the meanings of "consist of" and "consist essentially of". For example, "A comprises a" covers the meanings of "A comprises a and others" and "A only comprises a".

[0025] The present invention discloses a preparation method of a SiO2 / α-Al2O3 composite hydrogen-blocking coating for hydrogen transmission pipelines, and a SiO2 / α-Al2O3 composite coating is deposited by radio frequency magnetron sputtering; wherein the target materials are Si (99.99%) target and Al (99.99%) target, the starting gas is Ar gas with a purity of 99.99%, and the reaction gas is O2 gas with a purity of 99.99%.

[0026] Preferably, the radio frequency power supply adopts a SY-type radio frequency power source with a power of 150 - 200W, the vacuum degree ≥ 4×10 -3 Pa, the sputtering power is 50 - 160W, the sputtering gas pressure is 0.25 - 2Pa, the O2 / Ar gas mixing ratio is in the range of 1:10 - 1:5, and the heating temperature of the pipe substrate is 400 - 600°C.

[0027] Preferably, first, a SiO2 coating needs to be prepared on the substrate material by radio frequency magnetron sputtering. The target material is a Si (99.99%) target, the starting gas is Ar gas with a purity of 99.99%, and the reaction gas is O2 gas with a purity of 99.99%. The vacuum degree ≥ 4×10 -3 Pa, the sputtering power is 70 - 120W, the sputtering gas pressure is 0.25 - 1.5Pa, the O2 / Ar gas mixing ratio is in the range of 1:10 - 1:5, and the heating temperature of the pipe substrate is 400 - 500°C; the deposition rate of the SiO2 coating is 150nm / h - 253nm / h, and the prepared SiO2 thickness is 50 - 122nm.

[0028] Preferably, an α-Al2O3 coating needs to be prepared on the SiO2 coating by radio frequency magnetron sputtering. The target material is an Al (99.99%) target, the starting gas is Ar gas with a purity of 99.99%, and the reaction gas is O2 gas with a purity of 99.99%; the vacuum degree ≥ 4×10 -3 Pa, the sputtering power is 50 - 160W, the sputtering gas pressure is 1 - 2Pa, the O2 / Ar gas mixing ratio is in the range of 1:10 - 1:5, and the heating temperature of the pipe substrate is 500 - 600°C. The deposition rate of the α-Al2O3 coating is 89nm / h - 140nm / h, and the prepared α-Al2O3 thickness is 120 - 172nm.

[0029] Preferably, the composite hydrogen-blocking coating has a dense structure, and the bonding between the substrate material and SiO2, and between SiO2 and α-Al2O3 interfaces is tight. The film-substrate bonding force is 8.5N; the hydrogen permeation activation energy is 146.2 - 177.9kJ / mol, and the hydrogen permeation pressure index is 0.73 - 0.91.

[0030] In this text, for the sake of concise description, not all possible combinations of all technical features in each implementation or embodiment are described. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each implementation or embodiment can be combined arbitrarily, and all possible combinations should be considered as the scope described in this specification.

[0031] The following further elaborates the present invention in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

[0032] Conventional instruments and equipment in the art are used in the following embodiments. For the experimental methods without specific conditions noted in the following embodiments, they are usually carried out under conventional conditions or according to the conditions recommended by the manufacturer. Various raw materials are used in the following embodiments. Unless otherwise stated, commercially available products are used, and their specifications are conventional specifications in the art. In the specification of the present invention and the following embodiments, unless otherwise specified, "%" represents weight percentage, "parts" represents weight parts, and the ratio represents weight ratio.

[0033] Example 1

[0034] A preparation method of a SiO2 / α-Al2O3 composite hydrogen-blocking coating for a hydrogen transmission pipeline includes the following steps:

[0035] For a hydrogen transmission pipeline made of X52 carbon steel pipe, it is ultrasonically cleaned with acetone and alcohol for 15 min, and then dried for later use;

[0036] A SiO2 coating is prepared on the hydrogen transmission pipeline by radio frequency magnetron sputtering. The target is a Si (99.99%) target, the starting gas is Ar gas with a purity of 99.99%, and the reaction gas is O2 gas with a purity of 99.99%; the vacuum degree ≥ 4×10 -3 Pa, the sputtering power is 80 W, the sputtering gas pressure is 1 Pa, the O2 / Ar gas mixing ratio is 1:10, and the heating temperature of the pipe substrate is 400 °C; the deposition rate of the SiO2 coating is 150 nm / h, and the prepared SiO2 thickness is 62 nm;

[0037] Example 2

[0038] A preparation method of a SiO2 / α-Al2O3 composite hydrogen-blocking coating for a hydrogen transmission pipeline includes the following steps:

[0039] The SiO2 coating was prepared on the substrate material by radio frequency magnetron sputtering. The target material was Si(99.99%) target, the starting gas was Ar gas with a purity of 99.99%, and the reaction gas was O2 gas with a purity of 99.99%. The vacuum degree was ≥4*10 -3 Pa, the sputtering power was 100W, the sputtering gas pressure was 1.5Pa, the O2 / Ar gas mixing ratio was 1:10, and the heating temperature of the pipe substrate was 500°C; the deposition rate of the SiO2 coating was 174nm / h, and the thickness of the prepared SiO2 was 97nm;

[0040] Example 3

[0041] A preparation method of SiO2 / α-Al2O3 composite hydrogen-blocking coating for hydrogen transmission pipelines, comprising the following steps:

[0042] The α-Al2O3 coating was prepared on the SiO2 coating by radio frequency magnetron sputtering. The target material was Al(99.99%) target, the starting gas was Ar gas with a purity of 99.99%, and the reaction gas was O2 gas with a purity of 99.99%. The vacuum degree was ≥4*10 -3 Pa, the sputtering power was 120W, the sputtering gas pressure was 2Pa, the O2 / Ar gas mixing ratio was 1:5, and the heating temperature of the pipe substrate was 600°C; the deposition rate of the α-Al2O3 coating was 89nm / h, and the thickness of the prepared α-Al2O3 was 125nm.

[0043] Example 4

[0044] The α-Al2O3 coating was prepared on the SiO2 coating by radio frequency magnetron sputtering. The target material was Al(99.99%) target, the starting gas was Ar gas with a purity of 99.99%, and the reaction gas was O2 gas with a purity of 99.99%. The vacuum degree was ≥4*10 - 3 Pa, the sputtering power was 145W, the sputtering gas pressure was 1.8Pa, the O2 / Ar gas mixing ratio was 1:5, and the heating temperature of the pipe substrate was 550°C; the deposition rate of the α-Al2O3 coating was 92nm / h, and the thickness of the prepared α-Al2O3 was 139nm.

[0045] Example 5

[0046] The preparation process of the SiO2 / α-Al2O3 composite hydrogen-blocking coating in this example:

[0047] The SiO2 coatings obtained in Examples 1-2 were used to prepare α-Al2O3 coatings on their surfaces by the processes of Examples 3-4. After preparation, the sandwich composite structure of the substrate material - SiO2 - α-Al2O3 was subjected to stress relief annealing at 200 °C for 1 h. The prepared composite coating had a dense structure, and the interfaces between the substrate material and SiO2, and between SiO2 and α-Al2O3 were closely bonded. The film-substrate adhesion was 8.5 N; the hydrogen permeation activation energy was 146.2 - 177.9 kJ / mol, and the hydrogen permeation pressure exponent was 0.73 - 0.91.

[0048] In the present invention, the hydrogen transmission pipeline includes X52, X65, X70 and X80 carbon pipeline steels and 304 and 316 stainless steels.

[0049] The above content is only to illustrate the technical idea of the present invention and cannot be used to limit the protection scope of the present invention. Any modifications made on the basis of the technical solution according to the technical idea proposed by the present invention shall fall within the protection scope of the claims of the present invention.

Claims

1. A SiO2 / α-Al2O3 composite hydrogen-blocking coating for hydrogen transmission pipelines, characterized in that, The SiO2 / α-Al2O3 composite hydrogen-blocking coating for hydrogen transmission pipelines adheres to the surface of the hydrogen transmission pipelines; the SiO2 / α-Al2O3 composite hydrogen-blocking coating has a sandwich composite structure of substrate material - SiO2 - α-Al2O3.

2. The SiO2 / α-Al2O3 composite hydrogen-blocking coating for a hydrogen transmission pipeline according to claim 1, wherein, The bonding strength between the SiO2 / α-Al2O3 composite hydrogen-blocking coating for hydrogen transmission pipelines and the surface of the hydrogen transmission pipelines is 8.5 N.

3. The SiO2 / α-Al2O3 composite hydrogen-blocking coating for hydrogen transmission pipelines according to claim 1, characterized in that, For the SiO2 / α-Al2O3 composite hydrogen-blocking coating for hydrogen transmission pipelines, the hydrogen permeation activation energy is 146.2 - 177.9 kJ / mol, and the hydrogen permeation pressure exponent is 0.73 - 0.

91.

4. A method for preparing a SiO2 / α-Al2O3 composite hydrogen-blocking coating for a hydrogen transmission pipeline according to any one of claims 1 to 3, characterized in that, It includes the following steps: Pre-treat the surface of the hydrogen transmission pipelines, and then deposit the SiO2 / α-Al2O3 composite hydrogen-blocking coating on the surface of the hydrogen transmission pipelines by radio frequency magnetron sputtering method; Among them, the target materials used in the radio frequency magnetron sputtering method are Si target and Al target, the starting gas is argon with a purity of 99.99%, and the reaction gas is oxygen with a purity of 99.99%.

5. The preparation method of a SiO2 / α-Al2O3 composite hydrogen-blocking coating for a hydrogen transmission pipeline according to claim 4, characterized in that, The pre-treatment is to polish, ultrasonically clean and dry the surface of the hydrogen transmission pipelines in sequence.

6. The preparation method of a SiO2 / α-Al2O3 composite hydrogen-blocking coating for a hydrogen transmission pipeline according to claim 5, characterized in that, The ultrasonic cleaning is to ultrasonically clean with acetone and alcohol for 15 - 30 min.

7. The preparation method of a SiO2 / α-Al2O3 composite hydrogen-blocking coating for a hydrogen transmission pipeline according to claim 4, characterized in that, First, deposit a SiO2 coating on the surface of the hydrogen transmission pipeline by radio frequency magnetron sputtering. The vacuum degree of the radio frequency magnetron sputtering method is ≥4×10 -3 Pa, the sputtering power is 70-120 W, the sputtering gas pressure is 0.25-1.5 Pa, the O2 / Ar gas mixing ratio is 1:10-1:

5. When depositing the SiO2 coating, the heating temperature of the hydrogen transmission pipeline is 400-500 °C.

8. The preparation method of a SiO2 / α-Al2O3 composite hydrogen-blocking coating for a hydrogen transmission pipeline according to claim 7, characterized in that, In the SiO2 / α-Al2O3 composite hydrogen-blocking coating, the deposition rate of the SiO2 coating is 150 nm / h - 253 nm / h, and the thickness is 50 - 122 nm.

9. The preparation method of a SiO2 / α-Al2O3 composite hydrogen-blocking coating for a hydrogen transmission pipeline according to claim 4, characterized in that, Secondly, an α-Al2O3 coating is deposited on the surface of the SiO2 coating by radio frequency magnetron sputtering. The vacuum degree of the radio frequency magnetron sputtering method is ≥4×10 -3 Pa, the sputtering power is 50-160 W, the sputtering gas pressure is 1-2 Pa, and the O2 / Ar gas mixing ratio is in the range of 1:10-1:5; when depositing the α-Al2O3 coating, the temperature of the hydrogen transmission pipeline is heated to 500-600 °C.

10. The preparation method of a SiO2 / α-Al2O3 composite hydrogen-blocking coating for a hydrogen transmission pipeline according to claim 9, characterized in that, In the SiO2 / α-Al2O3 composite hydrogen-blocking coating, the deposition rate of the α-Al2O3 coating is 89 nm / h - 140 nm / h, and the thickness is 120 - 172 nm.